PROCESS FOR PREPARING A POLYMER COMPOSITION, POLYMER COMPOSITION, USE OF A POLYMER COMPOSITION, WRAP

专利摘要:
process for preparing a polymer composition, polymer composition, use of a polymer composition, wrapping or coating, and, adhesive composition. The present invention relates to a method for preparing a polymer composition, in which an (alpha beta)-ethylenically unsaturated carboxylic acid is subjected to radical polymerization in the presence of at least one polyether component, to the polymer composition. obtained according to said method and for the use thereof.
公开号:BR112015032997B1
申请号:R112015032997-7
申请日:2014-07-02
公开日:2021-08-10
发明作者:Alejandra GARCIA MARCOS；Heike Weber；Helmut Witteler；Yannick Fuchs；Jürgen Detering
申请人:Basf Se；
IPC主号:

专利说明:

FUNDAMENTALS OF THE INVENTION
[001] The present invention relates to a process for preparing a polymer composition, in which an α,β-ethylenically unsaturated carboxylic acid is subjected to a free radical polymerization in the presence of at least one polyether component, to the composition of polymer obtainable by this process in the form of a solid substance, especially a film, a coating on a substrate or a particulate solid and the use of such a polymer composition. TECHNICAL STATUS
[002] A multitude of demands to be satisfied simultaneously are realized in washing, cleaning and dish washing compositions, both in terms of their cleaning performance and in terms of the forms of manufacture and supply. Good performance properties must go hand in hand with convenient user dosing and simplification of the steps necessary to conduct a wash or cleaning procedure. In this context, a multitude of dosage forms have recently been marketed, including not only conventional powders and liquid formulations, but also tableted products ("tabs"), individual film-wrapped portions and dosage systems for multiple dosage of pharmaceutical compositions. washing and cleaning. Current dosage forms can comprise a multitude of separately formulated active ingredients and auxiliaries which are individually released in the cleaning process. There is still a great need here for both active substances and components that are used in films and coatings for dosage forms. Preference is given to components which exhibit a multiple effect, for example as a film-forming component which is soluble under cleaning conditions and, after being dissolved, is involved in the cleaning process.
[003] It is known that polyvinyl alcohol can be used as a water-soluble packaging and coating material for washing, cleaning and dish washing compositions, etc. A disadvantage is that polyvinyl alcohol itself has no detergent action and is not actively involved in the cleaning process.
[004] In household detergents, washing compositions, dish washing compositions, rinsing aids, cosmetics, pharmaceuticals and in formulations for industrial applications, polyethers or surfactants containing ether group are often used together with α-carboxylic acid polymers, β-ethylenically unsaturated and especially polyacrylic acid, in which case polyacrylic acid often takes on the role of a scale inhibitor or dispersant. The problem is that polyethers and ether group-containing surfactants are often zero or only of limited compatibility with polyacrylic acid and thus mixing results in phase separation or precipitates, greatly restricting the possible uses of at least one of the components. Also, polyethers and surfactants are often of a waxy or sticky consistency. In general, while this is not critical to the production of non-adhesive formulations, these components can only be added to powdery formulations to a small degree, because the flowability of the powder is otherwise lost. It is also especially difficult to provide clear films and coatings based on polyester or ether group-containing surfactants along with unsaturated carboxylic acid polymers, as preferred by the consumer, both because of their performance properties and for aesthetic reasons. Therefore, there is a need for compositions based on polymers of unsaturated carboxylic acids and polyethers that can be supplied in the form of a solid substance, especially in the form of a film (for example, as a wrapper for a liquid dishwashing composition. , washing or cleaning) or a coating on a substrate (for example, a dishwashing, washing or cleaning composition tablet) or in the form of a particulate solid (for example, a pelletized material or powder).
[005] F.E. Bailey et al. describe in Polymer Preprints, American Chemical Society, Division of Polymer Chemistry, 1960, vol. 1, issue 2, p. 202-205 and the literature cited therein, the formation of molecular association complexes of ethylene oxide polymers having a very high molecular weight with polymeric acids such as polyacrylic acid in aqueous solutions. The polymerization of acrylic acid in the presence of ethylene oxide polymers is not described.
[006] EP 0971997 B1 describes a liquid detergent formulation comprising a nonionic surfactant and an anionic polymer. The nonionic surfactant can be an ethoxylated C8-C18 alcohol and the anionic polymer can be polyacrylic acid. The polymer has a molecular weight greater than 100,000 g/mol. There is no description of the production of the formulation by the polymerization of at least one polymer containing acid groups in the presence of the nonionic surfactant.
[007] WO 2001/83660 describes the preparation of powders from water-soluble surfactants and polymers by spray drying. The spray drying process is specifically inapplicable to blends comprising polyacrylic acid because they form, together with polyethers and polyether containing surfactants, a rubber-like coagulate that cannot be processed in a spray tower because of its viscosity.
[008] EP 0 499 068 A1 describes reaction products of alkoxylates and vinylic monomers, at least some of which carry functional groups that can react with the OH groups of the alkoxylates in a condensation. The reaction products are prepared by polymerizing the vinyl monomers in the presence of the alkoxylates and then subjecting the polymerization product to a condensation by first polymerizing the vinyl monomers and then subjecting the polymerization product to a condensation with the alkoxylates. In which case acrylic acid is used as vinylic monomer, in which case the reaction product is thus an ester of polyacrylic acid. In the working examples, the alkoxylates used are exclusively EO-PO block copolymers having a high PO content and polytetrahydrofuran. The polymers described serve as emulsion breakers for the rapid dehydration of crude oils. These are prepared by charge polymerization in a first variant, in which case the final product is added as a solidified melt or after being absorbed in a solvent to the crude oil emulsion. In a second variant, the preparation is carried out by solution polymerization in a solvent suitable for use as an emulsion breaker. Suitable solvents are aromatic, aliphatic and cycloaliphatic hydrocarbons, acetone, cyclohexanone, THF and dioxane. There is no description of the use of polymers in solid form, specifically in the form of a film or a solid coating on a substrate or in particulate form.
[009] A similar process is described in DE 4326772 A1 in which toluene or xylene is used as the solvent. The use of aromatic solvents is undesirable for products that are to be used in consumer goods, as complete solvent removal is very time-consuming and energy-intensive. The reaction products are liquids which are described as esterified polyacrylic acids. Ester formation works against the effect of the polymer, for example, as a scale inhibitor and is undesirable in applications where the use of very substantially pure polyacrylic acid is required.
[0010] X. Li et al. in Journal of Solid State Electrochemistry (2011), 15(6), 1271-1277) and J.H. Wu et al. in Advanced Materials, 2007, 19, 4006-4011, describes the preparation processes for polyacrylic acid-polyethylene glycol gels. These publications explain the use of N,N'-methylenebisacrylamide as the crosslinker in the polymerization of acrylic acid, so that the polymers obtained are not soluble in water. Furthermore, the use of a crosslinker results in a very high molecular weight, which makes polymers unstable as scale inhibitors. There is no description of the use of polymers in the form of films, solid coatings or polymeric particles.
[0011] WO 2008/139151 A1 describes a process in which polyethylene glycol is mixed with acrylic acid, isobonryl acrylate and additional components and cured by UV exposure to give a solid gel. On the basis of the composition, it is evident to the person skilled in the art that the gel is not water-soluble. The gel serves as an indicator that a data loader, for example a computer-readable compact disc, has not been used before.
[0012] WO 2010/026178/A2 describes, on page 62 and example 19, a precipitation polymerization in which acrylic acid is polymerized in the presence of glyceryl monostearate and an alkyl-terminated polyethylene glycol matacrylate. The latter is an associative monomer and not a surfactant containing the polyether groups in the context of the present invention. The process additionally requires the use of a large amount of organic solvents based on a relatively small amount of acrylic acid and surfactant.
[0013] Lev Bromberg describes, in Journal of Physical Chemistry B (1998), 102, 11, 1956-1963, a material having thermoreversible gel formation, which is prepared by polymerizing acrylic acid in the presence of a PEO block copolymer -PPO-PEO. The reaction is carried out in the absence of external solvents, in order to reach a high proportion of branching and crosslinking in the obtained products. These are neither water-soluble nor transparent. The possible fields of use mentioned for these polymers, merely in very general terms, are pharmacy and nutrition (p. 1956, left column, "Introduction").
[0014] WO 2005/012378 describes aqueous dispersions of water soluble polymers of water soluble polymers of anionic monomers and the use of these as thickeners for aqueous systems. These are prepared by the polymerization of anionic monomers in the presence of two water-soluble polymers of different grades and these can be polyalkylene glycols among other polymers. Example 4 (page 19 lines 14 to 27) concerns the polymerization of acrylic acid in the presence of two different polypropylene glycols and maltodextrin. Dispersions are used, inter alia, in personal care products and in washing and cleaning compositions. There is no description of use in the form of films, solid coatings or polymeric particles.
[0015] EP 0 639 592 A1 describes graft copolymers obtainable by polymerizing a polymer composition containing (meth)acrylic acid in the presence of a polyether compound having more than 80 mol% ethylene oxide units. Polymerization is carried out essentially without solvent and at temperatures above 100°C. This is considered critical to achieving high graft levels as the solvent content of the reaction mixture is never greater than 5% by weight. The polymers obtained serve as builder for liquid washing compositions or, optionally after post-crosslinking, as water absorbing resins.
WO 2004/099274 describes a process for preparing polymer blends by polymerizing (meth)acrylic acid type monomers in the presence of a compound having a polyalkylene glycol structure. The polymer blends obtained must contain proportions of graft copolymer, polyalkylene glycol component and (meth)acrylic acid component remain homogeneous in the blend even after prolonged storage. Polymerization is necessarily carried out in the presence of water having a high water content in the initial charge at the start of the reaction. The polymer mixtures obtained by the process are suitable for various detergent applications, especially for the prevention of becoming dirty again.
[0017] It is an object of the present invention to provide a novel polymeric composition and a process for the preparation thereof, the polymer composition comprising a homo- or copolymer having a high proportion of incorporated acidic monomers and a polyether component. At the same time, the above-described disadvantages of the prior art are to be avoided. It is also possible to provide the polymeric compositions in the form of a solid substance, specifically in the form of a film, a coating on a substrate or a particulate solid. These should be especially suitable as a water-soluble packaging or coating material, for example, for washing, cleaning, and dishwashing compositions. Furthermore, by themselves, these should use properties as are typical of polymers based on at least one α,β-ethylenically unsaturated carboxylic acid and polyethers, eg interfacial action, deposit inhibiting action, scale inhibiting action, etc. . Especially, it should also be possible to provide the inventive polymer compositions in particulate form (eg powdered or pelletized material) and these should be suitable, for example, as the active component for solid dish washing, cleaning and washing compositions .
[0018] It has now been observed that, surprisingly, this objective is achieved when the polymer composition is prepared by subjecting a monomer composition based on at least one α,β-ethylenically unsaturated carboxylic acid to a free radical polymerization in the presence of the polyether component. SUMMARY OF THE INVENTION
[0019] Firstly, the invention provides a process for preparing a polymer composition, wherein a) a monomer composition M) is provided, comprising A) at least one α,β-ethylenically unsaturated carboxylic acid and B) less than 0.1% by weight, based on the total weight of the monomer composition M), of crosslinking monomers having two or more than two polymerizable α,β-ethylenically unsaturated double bonds per molecule, b) the monomer composition M) provided in step a) is subjected to a free radical polymerization in the presence of at least one polyether PE component) selected from polyetherols having a number average molecular weight of at least 200 g/mol and mono- and di-(alkyl-). C1-C6 ethers) of these, surfactants containing polyether groups and mixtures thereof.
[0020] The invention especially relates to a process for preparing a solid polymer composition, particularly in the form of a film or in the form of a solid coating on a substrate or in particulate form.
[0021] In a specific embodiment, the at least one α,β-ethylenically unsaturated carboxylic acid A) is partially or completely replaced by at least one unsaturated sulfonic acid or at least one unsaturated phosphonic acid (= component C).
[0022] In a specific embodiment, the polyether component PE) comprises or the polyether component PE) consists of at least one polyetherol or a mono- or di-(C 1 -C 2 alkyl ether) thereof comprising predominantly or exclusively units of ethylene oxide as alkylene oxide units. When the polyether component PE) comprises a polyetherol having repeating propylene oxide units or a mono- or di-(C 1 -C 6 -alkyl ether) of a polyetherol having repeating propylene oxide units, the proportion of these units repeating propylene oxide preferably divides no more than 18 units per molecule. The proportion of repeating propylene oxide units especially divides not more than 15 units per molecule, more especially not more than 10 units per molecule.
[0023] In another specific modality, the reaction mixture during polymerization in step b) and the polymer composition obtained in step b) are not subjected to any condensation with the removal of a low molecular weight reaction product and/or in the presence of a condensation catalyst.
[0024] In a first variant of the process according to the invention, a polymer composition is obtained in the form of a transparent film. In a second variant of the process according to the invention, a polymer composition is obtained in the form of a solid coating on a substrate. In a third variant of the process according to the invention, a polymer composition is obtained in the form of a particulate solid substance.
[0025] The invention further provides a process for preparing a polymer composition as defined above and hereinafter in the form of a film, wherein a) a monomer composition M) is provided, comprising A) at least one acid α,β-ethylenically unsaturated carboxylic and B) less than 0.1% by weight, based on the total weight of the monomer composition M), of crosslinking monomers having two or more than two α,β-ethylenically double bonds polymerizable unsaturated compounds per molecule, b) the monomer composition M) provided in step a) is subjected to a free radical polymerization in the presence of at least one polyether PE component) selected from polyetherols having a number average molecular weight of at least 200 g/mol and the mono- and di-(C1-C6-alkyl ethers) of these, surfactants containing polyether groups and mixtures thereof and c) the polymer obtained in step b), optionally after the addition of at least one active ingredient and/ or at least one additive, is subjected to an operation film forming, preferably selected from blow molding, thermoforming, melting and calendering.
[0026] The invention further provides a process for preparing a polymer composition as defined above and hereinafter in the form of a solid coating on a substrate, wherein a) a monomer composition M) is provided, comprising A) at least one α,β-ethylenically unsaturated carboxylic acid and B) less than 0.1% by weight, based on the total weight of the monomer composition M), of crosslinking monomers having two or more than two α double bonds polymerizable ,β-ethylenically unsaturated per molecule, b) the monomer composition M) provided in step a) is subjected to a free radical polymerization in the presence of at least one polyether PE component) selected from polyetherols having a number average molecular weight of at least 200 g/mol and the mono- and di-(C1-C6-alkyl ethers) thereof, surfactants containing polyether groups and mixtures thereof and c) the polymer obtained in step b), optionally after the addition of at least one active ingredient and/or at least one additive. the and/or at least one solvent and optionally while heating, is converted to a free-flowing form, applied to a substrate and allowed to solidify.
[0027] The invention further provides a process for preparing a polymer composition as defined above and hereinafter in particulate form, wherein a) a monomer composition M) is provided, comprising A) at least one α-carboxylic acid ,β-ethylenically unsaturated and B) less than 0.1% by weight, based on the total weight of the monomer composition M), of crosslinking monomers having two or more than two polymerizable α,β-ethylenically unsaturated double bonds per molecule, b) the monomer composition M) provided in step a) is subjected to a free radical polymerization in the presence of at least one polyether component PE) selected from polyetherols having a number average molecular weight of at least 200 g/ mol and the mono- and di-(C1-C6-alkyl ethers) of these, surfactants containing polyether groups and mixtures thereof and c) the polymer obtained in step b), optionally after the addition of at least one additive and/or at least a solvent and optionally while heating, it is co. It is converted to a free-flowing form and a particulate composition is formed therefrom.
[0028] The invention further provides a polymer composition obtainable by a process as defined above and below.
[0029] The invention further provides a polymer composition as defined above and hereinafter in the form of a transparent film, a solid coating on a substrate or a solid particulate substance.
[0030] The invention further provides a polymer composition in the form of a film or a coating on a substrate, comprising at least one active ingredient.
[0031] In a specific execution, the active ingredient is selected from enzymes, formers, bleaches, surfactants, bases, corrosion inhibitors, defoamers, pigments, fragrances, fillers, tabletting aids, disintegrants, thickeners, solubilizers, organic solvents , electrolytes, pH modifiers, perfume carriers, fluorescers, hydrotropes, anti-redeposition agents, optical brighteners, graying inhibitors, shrinkage inhibitors, wrinkle inhibitors, pigment transfer inhibitors, active antimicrobial ingredients, antioxidants, inhibitors corrosion agents, anti-statics, ironing aids, hydrophobic and impregnating agents, swelling and anti-slip agents, UV absorbers and mixtures thereof.
[0032] A specific embodiment of the invention is a polymer composition in the form of a film or a coating on a substrate, comprising at least one enzyme. A further specific embodiment of the invention is a wrapper for a washing composition portion, cleaning portion composition or dishwashing composition portion, in the form of a film or a coating on a substrate, comprising at least one enzyme.
[0033] The invention further provides the use of a polymer composition as defined above and below - in washing and cleaning compositions, - in dishwashing composition and rinsing aids, - in hygiene products, - in compositions cosmetics, - in pharmaceutical compositions, - in crop protection compositions, - in wetting agents, - in varnishes, coating compositions, adhesives, leather treatment compositions or textile care compositions, etc., - in development and/or exploration of underground mineral oil and/or natural gas deposits.
[0034] The invention further provides the use of a polymer composition as defined above and below in liquid or solid washing compositions and in cleaning compositions for solid surfaces.
[0035] The invention further provides the use of a polymer composition as defined above and below to form a shell or in the shell of a solid or liquid washing and cleaning composition.
[0036] The invention further provides the use of a polymer composition as defined above and hereinafter as a coating film or as a component of a coating film for a pharmaceutical composition, animal medicine or edible or drinkable composition, specifically for the production of coated tablets, pellets, microcapsules or crystals.
[0037] The invention further provides an envelope for a washing composition portion, cleaning portion composition or dishwashing composition portion, comprising or consisting of a polymer composition obtainable by a process as defined above and below.
[0038] The invention further provides an adhesive composition comprising or consisting of a polymer composition obtainable by a process as defined above and below. The inventive adhesive composition is suitable for a multitude of uses, for example for coated labels, especially plasticizer-free and/or self-adhesive de-peelable paper labels. DESCRIPTION OF THE INVENTION
[0039] The process according to the invention and the polymeric compositions thus obtained have the following advantages: - The process according to the invention is suitable for the preparation of compositions based on polymers of unsaturated acids (especially unsaturated carboxylic acids ) and polyethers, which can be supplied in the form of a solid substance. The process is variable in terms of the solid polymer composition obtained. Firstly, this is suitable for preparing solid polymeric compositions in the form of a film. In this context, it is possible, for the first time, to provide clear water-soluble films based on polyacrylic acid and polyethers. The process according to the invention is additionally suitable for preparing a coating on a substrate, for example, in or on a tablet of dishwashing, washing or cleaning composition. The process according to the invention is additionally suitable for the preparation of solid polymer particulate and especially pelletized and powdery polymer compositions. Advantageously, these compositions are thickened only to a lesser degree, if at all, and are suitable for the preparation of solid free-flowing formulations. The provision of these specific particulate polymeric compositions is possible through the selection of a suitable glass transition temperature and/or polyether PE component), as explained in detail below. The polymeric compositions obtained by the process according to the invention are notable firstly for good film-forming properties and secondly for their suitability as an active component, for example, of washing, cleaning and dishwashing formulations. In this way, inventive polymer compositions are suitable, for example, as complexing agents, soil release polymers or scale inhibitors. These are advantageously suitable as a polyvinyl alcohol in providing films and coatings for various dosage forms. - on the basis of the aforementioned properties, the inventive polymer compositions can be used in a multitude of dosage forms and in various components of these dosage forms. For example, it is possible for a single portion of a washing, cleaning or dishwashing formulation to comprise the inventive polymer component in a liquid or solid active component and/or in the coating of at least one solid component and/or in the polymer shell. at least one liquid or solid active component. - The process according to the invention allows the substantial or complete elimination of crosslinking monomers in the preparation of polymeric compositions. Therefore, these are advantageously water-soluble. - The polymeric compositions obtained by the process according to the invention are notable both for high compatibility between the polyether component and polyacrylic acid and for high compatibility with additional surfactants. - The dissolution characteristics of the polymeric compositions obtained by the process according to the invention can be controlled within a wide range, for example, by means of the type and quantity of monomers used. Insoluble compositions or those having a slow dissolution rate are advantageously suitable for providing active combinations with a delayed release profile. The polymeric compositions obtained by the process according to the invention are advantageously suitable for the production of films or coatings comprising at least one active ingredient. In this way, it is possible, for example, to provide a casing for a washing composition portion, cleaning portion composition or dishwashing composition portion, from which at least one active ingredient is released in a controlled manner in the course of washing operation, cleaning operation or dish washing operation. - The process according to the invention is additionally suitable for the preparation of polymer compositions for adhesive compositions. The provision of these specific polymer compositions is possible by selecting a suitable glass transition temperature and/or polyether PE component), as explained in detail below.
[0040] In the context of this application, some compounds that can be derived from acrylic acid and methacrylic acid are abbreviated by inserting the syllable "(met)" in the compound derived from acrylic acid.
[0041] In the context of the present invention, C1-C6-alkyl is a linear or branched alkyl radical having from 1 to 5 carbon atoms. Examples of these are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl and positional isomers thereof.
[0042] C7-C30 Alkyl is a linear or branched alkyl radical having from 6 to 30 carbon atoms. Examples of these are heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nondecyl, eicosyl, henicosyl, docosyl, tricosyl tetracosyl and positional isomers thereof.
[0043] The inventive polymer compositions are prepared by the free radical polymerization of the monomer composition M) in the presence of at least one PE polyether component) which, in general, does not have any copolymerizable double bond. This produces specific polymer compositions having advantageous properties. Without being bound by theory, this can be attributable, for example, to an effect of the polyether component PE) as a protective colloid or emulsifier. This can also result, for example, from at least partial grafting onto the polyether component as a grafting base. However, other non-graft mechanisms are also conceivable. The inventive polymer compositions, very generally, comprise the products of free radical polymerization process, which is understood to mean, for example, graft polymers, homo- and copolymers of the monomers present in the monomer mixture M), polymer mixtures of grafting with compounds grafted onto the PE polyether component) and any desired mixtures.
[0044] In a specific preferred embodiment, during and after polymerization in step b), the reaction mixture and the polymer composition obtained in step b) are not subjected to any condensation with the removal of a low molecular weight reaction product and/or in the presence of a condensation catalyst. It is understood to mean that, specifically, no further measures are carried out with the aid of increasing the content of the ester group of the polymeric composition obtained by the process according to the invention. In another preferred embodiment, ester formation is allowed during and/or after the polymerization in step b).
Specifically, the inventive polymer composition is in solid form under standard conditions (23°C, 1013 mbar) (0.1013 kpa). In the context of the invention, the terms "solid substance" and "in solid form" are understood to mean a solvent free solid or solid compositions comprising an inventive polymer composition and at least one solvent. Preferably, the solvent content of the solid compositions is not more than 10% by weight, more preferably not more than 5% by weight, especially not more than 2% by weight, based on the total weight of the polymer composition and solvent. Suitable solvents and solvent mixtures are described below as the S component).
[0046] The inventive polymer composition is not in the form of a gel. Compositions in gel form are the target of parallel orders. In general, inventive polymer compositions including greater than 10% by weight of solvent, based on the total weight of polymer and solvent composition, can form gels.
[0047] In the context of the present invention, the term "film" refers to a flat structure having essentially a two-dimensional shape. The thickness of the inventive films is preferably 0.5 µm to 10 mm, more preferably 1 µm to 5 mm. The length and/or width of the film is generally at least 5 mm and preferably at least 10 mm. The maximum length and/or width of the film, in general, is critical and, depending on the field of use, it can be in the range of millimeters, centimeters or meters.
[0048] If the inventive polymer compositions are in the form of a solid coating on a substrate, the thickness of the coating is preferably within a range from 0.5 µm to 10 mm, more preferably from 1 µm to 5 mm.
[0049] In the context of the present invention, the terms "particulate solid substance" and "particulate polymeric composition" refer to a composition comprising particles having a particle size that preferably ranges from powdery particles to granule size. Preferably, the particle size is within a range from about 50 µm to 10 mm, more preferably from 100 µm to 5 mm.
[0050] The glass transition temperatures (Tg) described in the context of this application can be determined by means of differential scanning calorimetry (DSC). DSC analysis on one or the same sample is appropriately repeated once or twice in order to ensure a defined thermal history of the respective polyamide. Heating and cooling rates were 20 K/minute.
[0051] For use in the form of a film or in the form of a coating on a substrate, preference is given to the use of flexible inventive polymer compositions having a low glass transition temperature TG. Preferably, the inventive polymer compositions for use in the form of a film or in the form of a coating on a substrate have a glass transition temperature TG in the range from 0 to 50°C, preferably from 5 to 20°C.
[0052] For use in the form of a particulate solid substance, preference is given to the use of brittle inventive polymer compositions having a high glass transition temperature TG. Preferably, the inventive polymer compositions for use in the form of a particulate solid substance have a glass transition temperature TG in the range of from 15 to 150 °C, preferably from 30 to 130 °C.
[0053] For use in an adhesive composition, preference is given to the use of inventive polymer compositions having a low glass transition temperature. Preferably, the inventive polymer compositions for use in the adhesive compositions have a glass transition temperature TG in the range of -100 to +10°C, preferably -80 to 0°C.
[0054] The control of the glass transition temperature TG can, in principle, be controlled through the type and proportion of the monomers and the molecular weight. An additional means of controlling the glass transition temperature TG lies in the selection of the PE polyether component. The provision of an inventive polymer composition having the desired glass transition temperature TG is within the ability of the person skilled in the art and can be verified through routine measurements.
[0055] In a preferred embodiment of the first variant, the inventive polymer compositions are in the form of a transparent film. The transparency of a material is determined by its absorption and scattering characteristics, that is, the light and appearance transmitted by looking through the material. Total transmission (transparency) is the ratio of transmitted light tr to incident light. The measure used for transparency is the transmission T: this is the quotient of the luminous flux Φn behind and Φv in front of the material to be tested and is reported as a percentage. This value includes, as well as the absorption, also the scattering and reflection losses. Transmission is generally determined in air and is reported as a function of wavelength.
[0056] In the context of the invention, the transparency (TL) is determined at a wavelength of 500 nm. The benchmark used for maximum transparency (100% TL) is water.
[0057] Preferably, the inventive polymer composition in the form of a transparent film has a TL measured at 500 nm of at least 85%, more preferably at least 90%, based on the transparency of water.
[0058] In a second variant of the process according to the invention, a polymer composition is obtained in the form of a solid substance.
[0059] The characteristic material values suitable for characterizing the polymer composition in the form of a solid substance are in the storage modulus, the loss modulus (G'') and the loss factor tan(δ) corresponding to the quotient G "/G'. M) monomer composition Carboxylic acid monomer A)
[0060] The α,β-ethylenically unsaturated carboxylic acid A) is preferably selected from acrylic acid, methacrylic acid, ethacrylic acid, a-chloroacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid and mixtures thereof. A) monomers also include the salts of the acids already mentioned, especially the sodium, potassium and ammonium salts and also the salts with amines. Monomers A) can be used as is or as mixtures with each other. All stated weight ratios refer to the acid form.
[0061] Preferably, the at least one α,β-ethylenically unsaturated carboxylic acid is used in unneutralized form for polymerization.
[0062] More preferably, component A) is selected from acrylic acid, methacrylic acid and mixtures thereof.
[0063] More particularly, exclusively acrylic acid is used as component A).
[0064] Component A) is preferably used in an amount of 50% to 100% by weight, more preferably 60% to 100% by weight, based on the total weight of the monomer composition M).
[0065] In a preferred embodiment, the monomer composition M) consists to some extent of at least 80% by weight, preferably to some extent at least 90% by weight, especially to some extent at least minus 95% by weight, based on the total weight of the monomers used, of acrylic acid. Crosslinker B)
[0066] The inventive polymer composition comprises essentially uncrosslinked polymers. The monomer composition M) used for preparing the inventive polymer composition therefore comprises only small amounts, if any, of crosslinking monomers B). Crosslinkers in the context of the invention are compounds having two or more than two polymerizable ethylenically unsaturated double bonds per molecule.
[0067] Preferably, crosslinkers B) are used in an amount of 0% to 0.1% by weight, more preferably 0% to 0.05% by weight, based on the total weight of the monomer composition M). In a specific embodiment, the monomer composition M) does not comprise any crosslinking monomers B) having two or more than two polymerizable α,β-ethylenically unsaturated double bonds per molecule.
Suitable crosslinkers B) are, for example, acrylic esters, methacrylic esters, allylic esters or vinyl esters of at least dihydric alcohols. The OH groups of the precursor alcohols can be fully or partially etherified or esterified; however, crosslinkers comprise at least two ethylenically unsaturated groups.
[0069] Examples of precursor alcohols are dihydric alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3- butanediol, 1,4-butanediol, but-2-ene-1,4-diol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, neopentyl glycol, 3-methylpentane-1,5-diol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol , 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-bis(hydroxymethyl)cyclohexane, hydropivalic acid neopentyl glycol monoester, 2,2-bis(4-hydroxyphenyl)propane, 2.2 -bis[4-(2-hydroxypropyl)phenyl]propane, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 3-thiopentane-1,5-diol and polyethylene glycols, polypropylene glycols and polytetra- hydrofurans each having molecular weights from 200 to 10,000 g/mol. Apart from homopolymers of ethylene oxide and propylene oxide, it is also possible to use block copolymers of ethylene oxide or propylene oxide or copolymers which incorporate ethylene oxide and propylene oxide groups. Examples of precursor alcohols having more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, triethoxycyanuric acid, sorbitan, sugars such as sucrose, glucose, mannose. Polyhydric alcohols, of course, can also be used after reaction with ethylene oxide or propylene oxide, in the form of the corresponding ethoxylates and propoxylates respectively. Polyhydric alcohols can also be first converted to the corresponding glycidyl ethers by reaction with epichlorohydrin.
Further suitable crosslinkers B) are vinyl esters or esters of unsaturated monohydric alcohols with ethylenically unsaturated C3-C6 carboxylic acids, eg acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. Examples of such alcohols are allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octen-3-ol, 9-decen-1-ol, dicyclopentenyl alcohol, 10-undecen-1- ol, cinnamyl alcohol, citronellol, crotyl alcohol or cis-9-octadecen-1-ol. It is also possible to esterify monohydric unsaturated alcohols with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
[0071] Additional suitable crosslinkers B) are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.
[0072] Suitable crosslinkers B) are also straight or branched chain hydrocarbons, linear or cyclic, aliphatic or aromatic having at least their double bonds which, in the case of aliphatic hydrocarbons, should not be conjugated, for example, divinylbenzene, divinyltoluene, octa-1,7-diene, deca-1,9-diene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes having molecular weights from 200 to 20,000 g/mol.
[0073] Also suitable as crosslinkers B) are acrylamides, methacrylamides and N-allylamines of at least bifunctional amines. Such amines are, for example, 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine, piperazine, diethylenetriamine or isophoronediamine . Also suitable are allylamine amides and unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids as described above.
[0074] Also suitable as crosslinkers B) triallylamine and triallylmonoalkylammonium salts, for example, triallylmethylammonium chloride or methyl sulfate.
[0075] Also suitable are N-vinyl compounds of urea derivatives, at least bifunctional amides, cyanurates or urethanes, for example from urea, ethylene urea, propyleneurea or tartaramide, for example N,N'-divinylethyleneurea or N, N'-divinylpropyleneurea.
Additional suitable crosslinkers B) are divinyldioxane, tetraallylsilane or tetravinylsilane. Unsaturated sulfonic or phosphonic acids C)
[0077] The monomer composition M) may comprise at least one unsaturated sulfonic acid or phosphonic acid C) instead of component A). The monomer composition M) may also additionally comprise at least one unsaturated sulfonic acid or phosphonic acid as component C).
[0078] Component C) is preferably selected from 2-acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloyloxypropylsulfonic acid , 2-hydroxy-3-methacryloyloxypropylsulfonic acid, styrenesulfonic acid, vinylphosphonic acid, allylphosphonic acid and mixtures thereof.
[0079] A preferred component C) is 2-acrylamido-2-methylpropanesulfonic acid.
[0080] The C) monomers also include the salts of the aforementioned acids, especially the sodium, potassium and ammonium salts and also the salts with amines. C) monomers can be reused as they are or as mixtures with each other. All weight ratios refer to the acid form.
[0081] Preferably, the monomer composition M) consists to some extent of at least 80% by weight, preferably to some extent at least 90% by weight, especially to some extent at least 95% by weight, based on the total weight of the monomer composition M), of monomers A) and C). When the monomer composition M) comprises at least one monomer C), this is preferably used in an amount of from 0.1 to 50% by weight, more preferably from 1% to 25% by weight, based on the total weight of the composition. of monomer M). Monomer containing ether groups D)
[0082] The monomer composition M) may additionally comprise at least one monomer D) selected from compounds of the general formulas (Ia) and (Ib)
where the sequence of the alkylene oxide units is arbitrary, kel are each independently an integer from 0 to 1000, where the sum of kel is at least 2, preferably at least 5, R1 is hydrogen or alkyl -C1-C8, R2 is hydrogen, C1-C30-alkyl, C2-C30-alkenyl or C5-C8-cycloalkyl, X is O or a group of the formula NR3 wherein R3 is H, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
[0083] In formulas I.a) and I.b), k is preferably an integer from 1 to 500, more preferably from 2 to 400, especially from 3 to 250. Preferably, 1 is an integer from 0 to 100.
Preferably, R1 in formulas I.a) is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, especially hydrogen, methyl or ethyl.
Preferably, R2 in formulas Ia) and Ib) is n-octyl, 1,1,3,3-tetramethylbutyl, ethylhexyl, n-nonyl, n-decyl, n-undecyl, tridecyl, myristyl, pentadecyl, palmityl, heptadecyl, octadecyl, nonadecyl, arachinyl, behenyl, lignoceryl, kerotinyl, melissyl, palmitoleyl, oleyl, linoleyl, linolenyl, stearyl, lauryl.
[0086] Preferably, X in formulas I.a) is O or NH, especially O.
Suitable polyether acrylates I.a) are, for example, the polycondensation products of the α,β-ethylenically unsaturated mono- and/or dicarboxylic acids already mentioned and the acid chlorides, acid amides and acid anhydrides of these with polyetherols. Suitable polyetherols can be readily prepared by reacting ethylene oxide, 1,2-propylene oxide and/or epichlorohydrin with an initiator molecule, such as water or a short-chain alcohol R2-OH. Alkylene oxides can be used individually, alternately in succession or as a mixture. The polyether acrylates I.a) can be used alone or in mixtures for preparing the polymers used according to the invention.
Suitable allyl alcohol alkoxylates I.b) are, for example, the etherification products of allyl chloride with suitable plyetherols. Suitable polyetherols can be readily prepared by reacting ethylene oxide, 1,2-propylene oxide and/or epichlorohydrin with an alcohol initiator R2-OH. Alkylene oxides can be used singly, alternatively in succession or as a mixture. Allyl alcohol alkoxylates or allyl alcohol alkoxylates I.b) can be used alone or in mixtures for the preparation of polymers used according to the invention.
The monomers D) used are especially methyl diglycol acrylate, methyl diglycol methacrylate, ethyl diglycol acrylate or ethyl diglycol methacrylate. Preference is given to ethyl diglycol acrylate.
[0090] The monomer composition M) preferably comprises from 0% to 50% by weight, more preferably from 0% to 25% by weight, especially 0% to 10% by weight, based on the total weight of the monomer composition M ), of at least one monomer containing ether group D). When the monomer composition M) comprises at least one monomer D), then preferably in an amount from 0.1% to 50% by weight, more preferably from 1% to 25% by weight, especially from 1.5% to 10 % by weight, based on the total weight of the monomer composition M). Additional monomers E) to O)
[0091] The monomer composition M) may additionally comprise at least one additional monomer other than monomers A) to D). Preferably, the monomer composition M) further comprises at least one comonomer selected from E) vinylaromatics, F) C2-C8 monoolefins, non-aromatic hydrocarbons having at least two conjugated double bonds, G) mono and dicarboxylic acid esters α,β- ethylenically unsaturated with C1-C20 alkanols, H) compounds having an α,β-ethylenically polymerizable free radical double bond and at least one cationic and/or cationic group per molecule, I) esters of vinyl alcohol or allyl alcohol with C1 monocarboxylic acids -C30, K) monomers containing amide groups, L) esters of α,β- ethylenically unsaturated mono and dicarboxylic acids with C2-C30 alkanediols, α,β-ethylenically unsaturated mono and dicarboxylic acid amides with C2-C30 amino alcohols having a primary amino group or secondary amino group, M) α,β-ethylenically unsaturated nitriles, N) vinyl halides, vinylidene halides, O) monomers having urea groups, and mixtures thereof.
[0092] The monomer composition M) may comprise each of the additional monomers E) to O) in an amount from 0% to 50% by weight, more preferably from 0% to 25% by weight, especially from 0% to 10 % by weight, based on the total weight of the monomer composition M). When the monomer composition M) comprises at least one monomer E) to O), then preferably each in an amount of 0.1% to 50% by weight, more preferably 1% to 25% by weight, especially 1 .5% to 10% by weight, based on the total weight of the monomer composition M). In a specific embodiment, the monomer composition M) does not comprise any additional monomers E) to O). Monomer E)
Preferred vinylaromatics E) are styrene, 2-methylstyrene, 4-methylstyrene, 2-(n-butyl)styrene, 4-(n-butyl)styrene, 4-(n-decyl)styrene and mixtures thereof. Particular preference is given to styrene and 2-methylstyrene, especially styrene. Monomer F)
[0094] The preferred monomers F) are ethene, propene, butene, isobutene, di-isobutene, isoprene, 1,3-butadiene and mixtures thereof. Monomer G)
Suitable α,β-ethylenically unsaturated mono- and dicarboxylic acid esters with C1-C30 alkanols are, for example, methyl (meth)acrylate, methyl ethacrylate, ethyl (meth)acrylate, ethyl ethacrylate, n-propyl (meth) )acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate, tert-butyl(meth)acrylate, tert-butyl ethacrylate, n-pentyl(meth)acrylate, n-hexyl(meth)acrylate, n-heptyl ( meth)acrylate, n-octyl(meth)acrylate, 1,1,3,3-tetramethylbutyl(meth)acrylate, ethylhexyl(meth)acrylate, n-nonyl(meth)acrylate, n-decyl(meth)acrylate, n-undecyl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, pentadecyl (meth)acrylate, palmityl (meth)acrylate, heptadecyl (meth)acrylate, nonadecyl (meth)acrylate, araquinyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, cerotinyl (meth)acrylate, melissil (meth)acrylate, palmitoleyl (meth)acrylate, oleyl (meth)acrylate, linoleyl (meth)acrylate, linolenyl (meth)acrylate, stearyl ( meth)acrylate, lauryl (meth)acrylate and mixtures thereof. Monomer H)
[0096] The cationic and/or cationic groups of component H) are preferably nitrogen-containing groups such as primary, secondary and tertiary amino groups and quaternary ammonium groups. Preferably, the nitrogen containing groups are tertiary amino groups or quaternary ammonium groups. Charged cationic groups can be produced from amine nitrogens by protonation or by quaternization with acids or alkylating agents. Examples of these include carboxylic acids such as lactic acid or mineral acids such as phosphoric acid, sulfuric acid and hydrochloric acid and examples of alkylating agents include C1-C4 alkyl halides or sulfates such as ethyl chloride, bromide ethyl, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. A protonation or quaternization can, in general, proceed or follow polymerization.
[0097] Preferably, component H) is selected from α,β-ethylenically unsaturated mono- and dicarboxylic acid esters with amino alcohols that can be mono- or dialkylated on the amine nitrogen, α,β-ethylenically unsaturated mono- and dicarboxylic acid amides with diamines having at least one primary or secondary amino group, N,N-diallylamine, N,N-diallyl-N-alkylamines and derivatives thereof, vinyl and allyl substituted nitrogen heterocycles, vinyl and allyl substituted heteroaromatic compounds and mixtures of the same.
[0098] The preferred monomers H) are the esters of α,β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols. Preferred amino alcohols are C2-C12 amino alcohols with C1-C8 mono- or dialkylation at the amine nitrogen. Suitable acid components of these esters are, for example, acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, maleic anhydride, monobutyl maleate and mixtures thereof. The acid components used are preferably acrylic acid, methacrylic acid and mixtures thereof.
Preferred monomers H) are N-methylaminoethyl (meth)acrylate, N-ethylaminoethyl (meth)acrylate, N-(n-propyl)aminoethyl (meth)acrylate, N-(tert-butyl)aminoethyl (meth)acrylate , N,N-dimethylaminomethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminomethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate , N,N-diethylaminopropyl (meth)acrylate and N,N-dimethylaminocyclohexyl (meth)acrylate.
[00100] Suitable monomers H) are, in addition, the amides of the α,β-ethylenically unsaturated mono- and dicarboxylic acids already mentioned with diamines having at least one primary or secondary amino group. Preference is given to diamines having a tertiary amino group and a primary or secondary amino group.
Examples of preferred H) monomers are N-[tert-butylaminoethyl](meth)acrylamide, N-[2-(dimethylamino)ethyl]acrylamide, N-[2-(dimethylamino)ethyl]methacrylamide, N-[ 3-(dimethylamino)propyl]acrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-[4-(dimethylamino)butyl]acrylamide, N-[4-(dimethylamino)butyl]methacrylamide, N-[2- (diethylamino)ethyl]acrylamide, N-[4-(dimethylamino)cyclohexyl]acrylamide and N-[4-(dimethylamino)cyclohexyl]methacrylamide.
[00102] In a suitable embodiment, component H) comprises, as the vinyl substituted heteroaromatic compound, at least one N-vinylimidazole compound. In a specific embodiment, component H) is selected from N-vinylimidazole compounds and mixtures comprising at least one N-vinylimidazole compound.
[00103] Suitable N-vinylimidazole compounds are compounds of formula (III)
wherein R3 to R5 are each independently hydrogen, C1-C4-alkyl or phenyl. Preferably, R1 to R3 are hydrogen.
[00104] Additionally, N-vinylimidazole compounds of the general formula (IV) are suitable
wherein R3 to R5 are each independently hydrogen, C1-C4-alkyl or phenyl.
[00105] Examples of compounds of the general formula (IV) are given in the table below: Table
Me = methyl Ph = phenyl
[00106] Preferred H) monomers are 1-vinylimidazole (N-vinylimidazole) and mixtures comprising N-vinylimidazole.
[00107] Suitable H) monomers are also compounds obtainable by protonation or quaternization of the aforementioned N-vinylimidazole compounds. Examples of such charged H) monomers are quaternized vinylimidazoles, in particular 3-methyl-1-vinylimidazolium chloride, methosulfate and ethosulfate. Suitable acids and alkylating agents are those listed above. Preference is given to a protonation or quaternization after polymerization.
Suitable H) monomers are additionally other vinyl or allyl substituted nitrogen heterocycles other than vinylimidazoles, such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine and the salts thereof. Monomer I)
[00109] Suitable vinyl alcohol esters with C1-C30 monocarboxylic acids are, for example, methyl vinyl ester, ethyl vinyl ester, n-propyl vinyl ester, isopropyl vinyl ester, n-butyl vinyl ester, tert-butyl vinyl ester, n-pentyl vinyl ester, n-hexyl vinyl ester, n-heptyl vinyl ester, n-octyl vinyl ester, 1,1,3,3-tetramethylbutyl vinyl ester, ethylhexyl vinyl ester, n-nonyl vinyl ester, n- decyl vinyl ester, n-undecyl vinyl ester, tridecyl vinyl ester, myristyl vinyl ester, pentadecyl vinyl ester, palmityl vinyl ester, heptadecyl vinyl ester, octadecyl vinyl ester, nonadecyl vinyl ester, aralkyl vinyl ester, behenyl vinyl ester, lignoceryl vinyl ester, ceroyl vinyl ester, melysyl vinyl ester, palmitoleyl vinyl ester, oleyl vinyl ester, linoleyl vinyl ester, linolenyl vinyl ester, stearyl vinyl ester, lauryl vinyl ester and mixtures thereof. Monomer K)
[00110] Suitable monomers containing amide groups K) are the compounds of general formula (V)
where one of the radicals R6 to R8 is a group of the formula CH2=CR9- where R9 = H or C1-C4-alkyl and the other radicals R6 to R8 are each independently H, alkyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl , where R6 and R7 together with the amide group to which they are attached may also be a lactam having from 5 to 8 ring atoms, where R7 and R8 together with the nitrogen atom to which they are attached may also be a 5-heterocycle. to 7 members.
[00111] Preferably, the compounds of component K) are selected from primary amides of α,β-ethylenically unsaturated monocarboxylic acids, N-vinylamides of saturated monocarboxylic acids, N-vinylactams, N-alkyl- and N,N-dialkylamides of acids α,β-ethylenically unsaturated monocarboxylic and mixtures thereof.
[00112] Preferred K) monomers are N-vinylactams and derivatives thereof which may have, for example, one or more C1-C6-alkyl substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec -butyl, tert-butyl, etc. These include, for example, N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl- 2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, etc.
[00113] Particular preference is given to the use of N-vinylpyrrolidone and/or N-vinylcaprolactam.
[00114] Suitable K) monomers are additionally acrylamide and methacrylamide.
[00115] Suitable N-alkyl- and N,N-dialkylamides of α,β-ethylenically unsaturated monocarboxylic acids are, for example, methyl(meth)acrylamide, methylethacrylamide, ethyl(meth)acrylamide, ethyl(meth)acrylamide, n-propyl(meth) )acrylamide, isopropyl(meth)acrylamide, n-butyl(meth)acrylamide, tert-butyl(meth)acrylamide, tert-butyl(meth)acrylamide, n-pentyl(meth)acrylamide, n-hexyl(meth)acrylamide, n-heptyl(meth) )acrylamide, n-octyl(meth)acrylamide, 1,1,3,3-tetramethylbutyl(meth)acrylamide, ethylhexyl(meth)acrylamide, n-nonyl(meth)acrylamide, n-decyl(meth)acrylamide, n - undecyl(meth)acrylamide, tridecyl(meth)acrylamide, myristyl(meth)acrylamide, pentadecyl(meth)acrylamide, palmityl(meth)acrylamide, heptadecyl(meth)acrylamide, nonadecyl(meth)acrylamide, araquinyl(meth)acrylamide, behenyl (meth)acrylamide, lignoceryl(meth)acrylamide, kerotyl(meth)acrylamide, melissil(meth)acrylamide, palmitoleyl(meth)acrylamide, oleyl(meth)acrylamide, linoleyl(meth)acrylamide, linolenyl(meth)acrylamide, stearyl(meth) )acrylamide, lauryl(meth)acryl lamide, N-methyl-N-(n-octyl)(meth)acrylamide, N,N-di-(n-octyl)(meth)acrylamide and mixtures thereof.
Suitable open chain N-vinylamide compounds as monomer K) are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl- N-ethylacetamide, N-vinylpropionamide, N-vinyl-N-methylpropionamide, N-vinylbutyramide and mixtures thereof. Preference is given to the use of N-vinylformamide. Monomer L)
Suitable α,β-ethylenically unsaturated mono- and dicarboxylic acid esters with C2-C30 alkanediols are 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3- hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxy-hexyl acrylate, 6-hydroxy-hexyl methacrylate, 3-hydroxy-2-ethyl- hexyl acrylate, 3-hydroxy-2-ethyl-hexyl methacrylate, etc.
Suitable amides of α,β-ethylenically unsaturated mono and dicarboxylic acids with C2-C30 amino alcohols having a primary or secondary amino group are 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide, 2-hydroxyethylethacrylamide, 2-hydroxypropylacrylamide, 2-hydroxypropylmethacrylamide , 3-hydroxypropylacrylamide, 3-hydroxypropylmethacrylamide, 3-hydroxybutylacrylamide, 3-hydroxybutylmethacrylamide, 4-hydroxybutylacrylamide, 4-hydroxybutylmethacrylamide, 6-hydroxyhexylmethacrylamide, 6-hydroxyhexylmethacrylamide, 3-hydroxy-2-ethylhexylacrylamide and 3-hydroxy -2-ethylhexylmethacrylamide. Monomer M)
[00119] Suitable α,β-ethylenically unsaturated nitriles are acrylonitrile or methacrylonitrile. Monomer N)
[00120] Suitable vinyl halides and vinylidene halides are vinyl chloride, vinylidene chloride, vinylidene fluoride, vinylidene fluoride and mixtures thereof. Monomer O)
Suitable O) monomers having urea groups are N-vinylurea, N-allylurea or imidazolidin-2-one derivatives. These comprise N-vinyl- and N-allylimidazolidin-2-one, N-vinyloxyethylimidazolidin-2-one, N-(2-(meth)acrylamidoethyl)imidazolidin-2-one, N-(2-(meth)acryloyloxyethyl)imidazolidin -2-one (i.e., 2-ureido(meth)acrylate), N-[2-((meth)acryloyloxyacetamido)ethyl]imidazolidin-2-one, etc. Polyether PE component)
Suitable PE components are polyetherols having a number average molecular weight of at least 200 g/mol and the mono- and di(C1-C6-alkyl ethers) thereof.
Suitable polyetherols and the mono- and di(C 1 -C 6 -alkyl ethers) thereof may be linear or branched, preferably linear. Suitable polyetherols and the mono- and di(C 1 -C 6 -alkyl ethers) thereof generally have a number average molecular weight in the range of about 200 to 100,000, preferably 300 to 50,000, more preferably 500 to 40,000. Suitable polyetherols are, for example, water-soluble or water-dispersible nonionic polymers having alkylene oxide repeating units. Preferably, the proportion of alkylene oxide repeating units is at least 30% by weight, based on the total weight of the compound. Suitable polyetherols are polyalkylene glycols, such as polyethylene glycols, polypropylene glycols, polytetrahydrofurans and alkylene oxide copolymers. Suitable alkylene oxides for the preparation of alkylene oxide copolymers are, for example, ethylene oxide, propylene oxide, epichlorohydrin, 1,2- and 2,3-butylene oxide. Suitable examples are copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide, and copolymers of ethylene oxide, propylene oxide and at least one butylene oxide. The alkylene oxide copolymers can comprise the alkylene oxide copolymerized units in random distribution or in the form of blocks. Preferably, the proportion of repeating units derived from ethylene oxide in the ethylene oxide/propylene oxide copolymers is from 40% to 99% by weight. Particularly preferred polyether components PE) are ethylene oxide homopolymers and ethylene oxide/propylene oxide copolymers.
Suitable polyether PE components are additionally the mono- and di(C 1 -C 2 alkyl ethers) of the polyetherols described above. Preference is given to polyalkylene glycol monomethyl ethers and polyalkylene glycol dimethyl ethers.
[00125] Suitable polyether PE components are additionally surfactants containing polyether groups. In general, non-ionic and ionic surfactants having at least one non-polar group and at least one polar group and comprising a polyether group are suitable.
[00126] The surfactants containing polyether groups PE) are preferably selected from alkyl polyoxyalkylene ethers, aryl polyoxyalkylene ethers, alkylaryl polyoxyalkylene ethers, alkoxylated animal and/or vegetable fats and/or oils, fatty amine alkoxylates, fatty acid amide alkoxylates, fatty acid diethanolamide alkoxylates, polyoxyethylene sorbitan fatty acid esters, alkyl polyether sulfates, aryl polyether sulfates, alkylaryl polyether sulfates, alkyl polyether sulfonates, aryl polyether sulfonates, alkylaryl polyether sulfonates, alkyl polyether phosphates, polyether phosphates, aryl phosphates , glyceryl ether sulfonates, glyceryl ether sulfates, monoglyceride (ether) sulfates, amide ether fatty acid sulfates, polyoxyalkylene sorbitan fatty acid esters and mixtures thereof.
[00127] Preferred nonionic surfactants containing polyether groups PE) are, for example: - alkyl polyoxyalkylene ethers which are derived from low molecular weight C3C6 alcohols or from C7-C30 fatty alcohols. The ether component here can be derived from ethylene oxide units, propylene oxide units, 1,2-butylene oxide units, 1,4-butylene oxide units and random copolymers and block copolymers thereof. Suitable non-ionic surfactants comprise, inter alia, surfactants of the general formula (VI)
wherein R10 is a linear or branched alkyl radical having from 6 to 22 carbon atoms, R11 and R12 are each independently hydrogen or a linear or branched alkyl radical having from 1 to 10 carbon atoms or H, where R12 is preferably methyl ex and y are each independently 0 to 300. Preferably, x = 1 to 100 and y = 0 to 30.
[00128] These especially also include fatty alcohol alkoxylates and oxo alcohol alkoxylates such as isotridecyl alcohol polyoxyethylene ethers and oleyl alcohol polyoxyethylene ethers. - surfactants containing hydroxyl groups of the general formula (VII)
where the sequence of the alkylene oxide units in the compounds of formula (VII) is arbitrary, 5, t, u and v are each independently an integer from 0 to 500, where the sum of s, t, u and v is > 0, R13 and R15 are each independently a straight or branched chain saturated C1-C40 alkyl radical or a mono or polyunsaturated C2-C40 alkenyl radical and R14 is selected from methyl, ethyl, n-propyl, isopropyl and n-butyl.
In the compounds of the general formula (VII), the sum of s, t, u and v is preferably a value from 10 to 300, more preferably from 15 to 200 and especially from 20 to 150.
[00130] Preferably, t and u are each 0. In that case, the sum of s and v is preferably a value from 10 to 300, more preferably of 15 to 200 and especially from 20 to 150.
In the compounds of the general formula (VII), R13 and R15 are preferably each independently a straight or branched chain saturated C2-C30 alkyl radical. At the same time, R13 and R15 can also be mixtures of different alkyl radicals.
In the compounds of the general formula (VII), R14 is preferably methyl or ethyl, especially methyl.
[00133] A preferred embodiment are surfactants containing hydroxyl groups of the general formula (VII.1)
where the sequence of the units -(CH2CH2O)- and (CH2CH(CH3)O)- is arbitrary, sev are each independently an integer from 0 to 500, where the sum of sev is > 0 and R13 and R15are each independently a straight-chain saturated C1-C30-alkyl radical or a branched saturated C2-C30-alkyl radical or a mono- or polyunsaturated C2-C30-alkenyl radical.
In the compounds of the general formula (VII.1), the sum of s and v is preferably a value from 10 to 300, more preferably from 15 to 200 and especially from 20 to 150.
[00135] The group of these nonionic surfactants include, for example, mixed hydroxy ethers of the general formula (C1-22-alkyl)-CH(OH)CH2O-(EO)20-120-(C2-26-alkyl). - polyoxyalkylene alcohol esters of the general formula (VIII)
where the sequence of the alkylene oxide units in the compounds of formula (VIII) is arbitrary, p and q are each independently an integer from 0 to 500, where the sum of p and q is > 0, R16 and R18 are each independently , independently a straight or branched chain saturated C 1 -C 40 alkyl radical or a mono or poly unsaturated C 2 -C 40 alkenyl radical and R 17 is selected from methyl, ethyl, n-propyl, isopropyl and n-butyl.
In the compounds of the general formula (VIII), the sum of p and q is preferably a value from 10 to 300, more preferably of 15 to 200 and especially from 20 to 150.
In the compounds of the general formula (VIII), R16 and R18 are preferably each independently a straight or branched chain saturated C4-C30 alkyl radical. At the same time, R16 and R18 can also be mixtures of different alkyl radicals.
In the compounds of the general formula (VIII), R17 is preferably methyl or ethyl, especially methyl.
[00139] These include, for example, lauric alcohol polyoxyethylene acetate. - alkylaryl alcohol polyoxyethylene ethers, for example, octylphenol polyoxyethylene ethers, - alkoxylated animal and/or vegetable fats and/or oils, for example corn oil ethoxylates, castor oil ethoxylates, tallow fat ethoxylates, - alkylphenol, for example isooctyl-, octyl- or nonylphenol, tributylphenol polyoxyethylene ether ethoxylate, - fatty amine alkoxylates, fatty acid amide and fatty acid diethanolamide alkoxylates, especially ethoxylates thereof, - polyoxyalkylene sorbitan fatty acid esters
[00140] An example of an alkyl polyether sulfate is sodium dodecyl poly(oxyethylene) sulfate (sodium lauryl ether sulfate, SLES). A preferred commercially available commercially available polyglycol ether modified fatty alcohol is a polyethylene oxide terminated by CxH2x+1/CyH2y+1 at each end and having a free OH group and x,y = 6-14. Solvent S)
[00141] The free radical polymerization in step b) can be carried out in the presence of a solvent S) selected from water, C1C6 alkanols, polyols other than PE), the mono- and dialkyl ethers thereof and mixtures thereof. Suitable polyols and the mono- and dialkyl ethers thereof also comprise alkylene glycol mono(C1-C4 alkyl ethers), alkylene glycol di(C1-C4 alkyl) ethers, oligoalkylene glycols having a number average molecular weight of less than 200 g /mol and the mono(C1-C4-alkyl ethers) and di(C1-C4-alkyl ethers) thereof.
[00142] Solvent S) is preferably selected from water, methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, ethylene glycol mono(C1-C4-alkyl ethers), ethylene glycol di(C1-alkyl- C4) ethers, 1,2-propylene glycol, 1,2-propylene glycol mono(C1-C4 alkyl ethers), 1,2-propylene glycol di(C1-C4 alkyl ethers), glycerol, polyglycerols, oligoalkylene glycols having a number average molecular weight of less than 200 g/mol and mixtures thereof.
Suitable oligoethylene glycols are commercially available under the CTFA designations PEG-6, PEG-8, PEG-12, PEG-632, PEG-20, PEG-150, PEG-7M, PEG-12M and PEG-115M. These especially include BASF SE's Pluriol E ® products. Suitable alkyl polyalkylene glycols are the corresponding Pluriol A ...E ® products of BASF SE.
[00144] Solvent S) is more preferably selected from water, ethanol, n-propanol, isopropanol, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,2-dipropylene glycol and mixtures thereof.
[00145] In a specific embodiment, the solvent S) used is selected from water and a mixture of water and at least one solvent S) other than water, selected from ethanol, n-propanol, isopropanol, ethylene glycol, diethylene glycol, 1 ,2-propylene glycol, 1,2-dipropylene glycol and mixtures thereof.
[00146] In a specific embodiment, the free radical polymerization in step c) is carried out in the presence of a solvent S) consisting to some extent of at least 50% by weight, preferably to some extent of at least 75% by weight, especially to some extent at least 90% by weight, based on the total weight of solvent S), of water. More particularly, the free radical polymerization in step c) is carried out in the presence of a solvent S) consisting entirely of water. Preparation of inventive polymer compositions
[00147] The preparation of the inventive polymer compositions comprises a free radical polymerization of the monomer composition M) in the presence of at least one PE polyether component). This is preferably conducted in a feeding method. In general, this involves measuring at least the monomers in liquid form in a reaction mixture. Liquid monomers under the measurement conditions can be fed into the reaction mixture without the addition of a solvent S); otherwise the monomers are used as a solution in a suitable solvent S).
[00148] Preferably, the free radical polymerization in step b) is carried out in feed mode, in which case the feeds comprising at least one α,β-ethylenically unsaturated carboxylic acid do not comprise any solvent S).
[00149] The metering rates of the monomer feeds and any additional feeds (initiator, chain transfer agent, etc.) are preferably chosen such that the polymerization is maintained at the desired conversion rate. Individual feeds can be added continuously, periodically, with constant or varying measuring rate, and essentially simultaneous or time-compensated. Preferably, all feeds are continuously added to a reaction mixture.
[00150] The weight ratio of the monomeric mixture M) to the PE component) is preferably in the range of 1:10 to 10:1.
[00151] If the polymer composition is prepared using an S) solvent, the weight ratio of PE component) to S component) is preferably in the range of 0.3:1 to 5:1, more preferably in the range from 0.5:1 to 3:1.
[00152] Preferably, the free radical polymerization in step b) is carried out at a temperature in the range from 20 to 95°C, more preferably from 30 to 90°C, especially from 40 to 80°C.
[00153] Preferably, the free radical polymerization comprises, in step b) of the process according to the invention, b1) providing an initial charge comprising at least a portion of the polyether component PE), optionally at least a portion of the agent chain transfer CTA) and if the polymerization is carried out in the presence of a solvent S), optionally at least a portion of S); b2) adding the monomer composition M) to one or more feeds and adding a feed comprising the free radical initiator FRI), dissolved in a portion of the at least one polyether component PE) and/or the solvent S) and optionally by adding a feed comprising the amount of the chain transfer agent CTA) which is not used in the initial charge, b3) optionally continuing the polymerization of a reaction mixture obtained in step b2).
[00154] Typically, the initial charge is heated to polymerization temperature before adding the feeds while stirring.
[00155] Preferably, the individual reactants are added simultaneously in separate feeds, in which case the flow rates of the feeds are generally kept very substantially constant over an addition period.
[00156] The addition of the feeds in step b2) is carried out in a period that is advantageously selected such that the heat of reaction that arises in the exothermic polymerization can be removed without any great technical complexity, for example, without the use of a condenser. reflux. Typically, feeds are added over a period of 1 to 10 hours. Preferably, the feeds are added over a period of 2 to 8 hours, more preferably for 3 to 5 hours.
[00157] During free radical polymerization, the optionally used solvent and/or any condensation products, in general, are not removed. In other words, during polymerization, there is typically only minor mass transfer with the environment within the realm of technical possibility, if any.
[00158] Polymerization can generally be carried out at ambient pressure or reduced or elevated pressure. Preferably, the polymerization is carried out at ambient pressure.
[00159] Polymerization is generally carried out at constant temperature, but can also be varied during polymerization if required. Preferably, the polymerization temperature is kept very substantially constant throughout the entire reaction period, i.e. of steps b2) and b3). According to what feed stocks are used in the process according to the invention, the polymerization temperature typically varies within a range of 20 to 95°C. Preferably, the polymerization temperature ranges within the range of 30 to 90°C and especially within the range of 40 to 80°C. If the polymerization is not conducted under elevated pressure and at least one optional solvent S) is added to the reaction mixture, the solvent or solvent mixture will determine the maximum reaction temperature via corresponding boiling temperatures.
[00160] Polymerization can be carried out in the absence or presence of an inert gas. Typically, polymerization is carried out in the presence of an inert gas. Inert gas is generally understood to mean a gas which, under the given reaction conditions, does not enter into any reaction with the reactants, reactants or solvents involved in the reaction or products formed.
[00161] If the polymerization is carried out in the presence of a solvent, this will be selected from the solvents S) described above.
[00162] To prepare the polymers, the monomers can be polymerized with the aid of free radical formation initiators, also referred to below as free radical initiators or initiators. Useful free radical initiators (initiators) for free radical polymerization in principle include all free radical initiators which are essentially soluble in the reaction medium when as they exist at the time of addition thereof and have sufficient activity at the given reaction temperatures to start polymerization. It is possible to use a simple free radical initiator or a combination of at least two free radical initiators in the process according to the invention. In the latter case, the at least two free radical initiators can be used in a mixture or, preferably, separately, simultaneously or successively, for example, at different periods in the course of the reaction.
[00163] The free radical initiators used for free radical polymerization can be the usual peroxo and/or azo compounds for this purpose, for example, alkali metal or ammonium peroxodisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di -tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl peroxy-2-ethyl-hexanoate, tert-butyl permaleate, cumene hydroperoxide, diisopropyl peroxodicarbamate, bis(o-tolyl) peroxide, didecanoyl peroxide , dioctanoyl peroxide, tert-butyl peroctoate, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl hydroperoxide, 2,2'-azobisisobutyronitrile, azobis(2-amidinopropane) dihydrochloride, azobis (2,4-dimethylvaleronitrile) or 2,2'-azobis(2-methylbutyronitrile).
Initiator mixtures or redox initiator systems are also suitable, for example ascorbic acid/iron(II) sulphate/sodium peroxodisulfate, tert-butyl hydroperoxide/sodium bisulfite, tert-butyl hydroperoxide/sodium hydroxymethanesulfinate, H2O2/CuI .
[00165] In the process according to the invention, the amount of initiator system (initiator) used varies within the range of 0.01% to 10% by weight, preferably within the range of 0.1% to 5% by weight, more preferably within the range of 0.2% to 2% by weight and especially within the range of 0.3% to 1.5% by weight.
[00166] In the process according to the invention, the free radical initiator is generally provided as a solution in a solvent comprising at least one of the solvents S) already mentioned.
[00167] The amount of the chain transfer agent typically used in the process according to the invention is 1 to 40 pphm ("parts per hundred of monomer", i.e. parts by weight based on a hundred parts in weight of monomeric composition). Preferably, the amount of chain transfer agent used in the process according to the invention is within the range of 3 to 30 pphm, more preferably in the range of 5 to 25 pphm.
[00168] Typically, the chain transfer agent is continuously added to the polymerization mixture in step b2) entirely via one of the feeds. However, it is also possible to add the chain transfer agent fully to the initial charge, ie before the actual polymerization or only a portion of the chain transfer agent is included in the initial charge and the rest is continuously added to the polymerization in step b2) by means of one of the feeds. The chain transfer agent can be added in each case with or without solvent S).
[00169] The amount of the chain transfer agent and the manner in which it is added to the reaction mixture has a strong influence on the average molecular weight of the polymer composition. When less chain transfer agent is used and/or when addition is predominantly carried out before polymerization, this generally leads to higher average molecular weights of the formed polymer. If, in contrast, larger amounts of chain transfer agent are used and/or the addition of chain transfer agent takes place for the most part during polymerization (step b2)), this in general leads to a molecular weight medium smaller. 1st variant: Preparation of a polymer composition for films
[00170] The process according to the invention serves, in a first preferred embodiment, for the preparation of a polymer composition suitable for the supply of films, especially transparent films.
[00171] In the 1st variant, the amount of polyether PE component) in the initial charge (step b1)) is preferably from 30% to 100% by weight, more preferably from 65% to 100% by weight and especially 80% to 100% by weight, based on the total weight of the polyether PE component) used for the polymerization.
[00172] In the 1st variant, the ratio of the polyether component PE) used to prepare the polymer composition to a monomer composition M) used is typically in the range of 1.0:0.8 to 1.0:5, preferably in the range of range from 1.0:1.0 to 1.0:2.5.
[00173] In this embodiment, the solvent content in the first fraction is typically no more than 70% by weight, based on the total weight of the feed stocks present in the first fraction. Preferably, the solvent content in the first fraction is not greater than 40% by weight, especially not more than 35% by weight, based on the total weight of the feed stocks present in the first fraction. The amount of solvent generally only changes by a few percent by weight over the entire course of the process. Typically, solvents S) having a boiling point at standard pressure (1 bar) below 240°C are used. In general, the S solvents used in this first preferred embodiment are water, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, ethylene glycol mono(C1-C4-alkyl ethers), ethylene glycol di(C1-C4-alkyl) ethers), 1,2-propylene glycol, 1,2-propylene glycol mono(C1-C4-alkyl ethers), 1,2-propylene glycol di(C1-C4-alkyl ethers), dipropylene glycols or mixtures thereof. Solvents S) preferably used in this first preferred embodiment are water, ethanol, n-propanol, isopropanol, n-butanol or mixtures thereof.
[00174] In a specific variant of this modality, the initial charge does not comprise any solvent. This is only added in step b2) via at least one of the feeds. In a specific variant of this modality, no solvent is initially loaded and no solvent is added over the entire course of the process.
[00175] In this first preferred embodiment, the polymeric compositions obtained after the polymerization has ended (step b3)) are transferred to a suitable container and optionally cooled directly to room temperature (20°C).
[00176] The polymeric compositions obtained in this way have a firm consistency and are transparent, meaning that they are transparent and have a transparency (TL) of at least 85%, especially at least 90%, based on the transparency of water. These are suitable for the production of films, for example as a wrapper for a liquid dishwashing, washing or cleaning composition. The production of films and wrappings based on these is described in detail below. 2nd variant: Preparation of a polymer composition for coatings
[00177] The process according to the invention serves, in a second preferred embodiment, for the preparation of a polymer composition suitable for providing solid coatings on a substrate.
[00178] In the 2nd variant, the amount of polyether PE component) in the initial charge (step b1)) is preferably from 30% to 100% by weight, more preferably from 65% to 100% by weight and especially 80% to 100% by weight, based on the total weight of the polyether PE component) used for the polymerization.
[00179] In the 2nd variant, the ratio of the polyether component PE) used to prepare the polymer composition to a monomer composition M) used is typically in the range of 1.0:0.8 to 1.0:5, preferably in the range of 1.0:1.0 to 1.0:2.5.
[00180] In this embodiment, the solvent content in the first fraction is typically not more than 70% by weight, based on the total weight of the feed stocks present in the first fraction. Preferably, the solvent content in the first fraction is not greater than 40% by weight, especially not more than 35% by weight, based on the total weight of the feed stocks present in the first fraction. The amount of solvent generally only changes by a few percent by weight over the entire course of the process. Typically, solvents S) having a boiling point at standard pressure (1 bar) below 240°C are used. In general, the S solvents used in this first preferred embodiment are water, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, ethylene glycol mono(C1-C4-alkyl ethers), ethylene glycol di(C1-C4-alkyl) ethers), 1,2-propylene glycol, 1,2-propylene glycol mono(C1-C4-alkyl ethers), 1,2-propylene glycol di(C1-C4-alkyl ethers), dipropylene glycols or mixtures thereof. Solvents S) preferably used in this first preferred embodiment are water, ethanol, n-propanol, isopropanol, n-butanol or mixtures thereof.
[00181] In a specific variant of this modality, the initial charge does not comprise any solvent. This is just added in step b2) via o of at least one of the feeds. In a very specific variant of this modality, no solvent is initially loaded and no solvent is added over the entire course of the process.
[00182] In this first preferred embodiment, the polymeric compositions obtained after the polymerization has ended (step b3)) are transferred into a suitable container and, optionally, directly cooled to room temperature (20°C).
[00183] The polymeric compositions obtained in this way are suitable for producing solid coatings on a substrate, for example, and a dishwashing, washing or cleaning composition tablet. The production of such coatings is described in detail below. 3rd variant: Preparation of solid compositions
[00184] The process according to the invention serves, in a third preferred modality, for the supply of solid polymer compositions, especially particulates.
[00185] In this third preferred embodiment of the process according to the invention, the amount of polyether PE component) in the initial charge (step b1)) is typically 40% to 100% by weight, preferably 90% to 100% by weight and especially 95% to 100% by weight, based on the total weight of the polyether PE component) used for the polymerization. Specifically, the polyether component PE) is initially fully charged prior to polymerization.
[00186] In this third preferred embodiment, the solvent content in the initial charge is 25% to 70% by weight, based on the total weight of all feed stocks present in the first fraction. Preferably, the solvent content in the first fraction is 30% to 65% by weight, especially 35% to 60% by weight, based on the total weight of all feed stocks present in the first fraction. Solvents S) used are preferably water or C1-C6 alkanols, more preferably water, methanol, ethanol, n-propanol, isopropanol, n-butanol, especially water or isopropanol and mixtures thereof.
[00187] The ratio of the polyether component PE) used for the preparation of the polymeric composition to a monomer composition M) used in this second embodiment is typically in the range of 1:1 to 1:10.
[00188] In this third preferred embodiment, the polymeric compositions obtained after the polymerization has ended (step b3)) are transferred to a suitable container and optionally cooled directly to room temperature (20°C). In general, the polymeric compositions obtained in the second preferred embodiment are immediately sent to a drying and/or grinding process, as described below.
[00189] The polymeric compositions prepared by the process according to the invention, after polymerization, can be subjected to additional processing steps. These include, for example, melting processes, forming processes, drying processes, grinding processes, purification processes or combinations thereof.
[00190] In a suitable modality, the reaction product obtained in step b) is subjected to formation. Preferably this gives a particulate product. The polymer composition can be provided in a particle size ranging from powdery particles to granule size. A preferred embodiment is the particulate polymer composition having a particle size within a range of about 100 µm to 10 mm.
[00191] Preferably, the formation of the prepolymer comprises a plasticization, for example, by extrusion and a pelletizing operation, roller forming operation and/or grinding operation. Suitable processes for pelletizing, rolling and grinding polymers are known to those skilled in the art. In a suitable embodiment, the polymer composition is first formed into one or more filaments for formation. For this purpose, mechanisms known to those skilled in the art can be used. Suitable mechanisms are, for example, perforated plates, nozzles or matrix plates. In a suitable embodiment, the polymeric composition formed for filaments is subjected in free-flowing form to a grinding to give polymeric particles. In an alternative embodiment, the polymeric composition formed into filaments is solidified and subjected to grinding to give polymeric particles. Suitable mills for grinding prepolymers are, for example, hammer mills, roller mills, ball mills, etc.
[00192] In a first reprocessing variant, the inventive transparent polymer compositions are first converted to a free-flowing state by heating. These compositions can then be subjected, in a further step, to a wide variety of different forming processes, for example, spreading on a solid carrier material to produce transparent films or melting of casings, sleeves or other hollow bodies suitable for filling. . After formation, the films or hollow bodies are typically dried at a temperature of 50 to 110°C over a period of 12 to 72 hours.
[00193] In a second further reprocessing variant, the solvent optionally present in the inventive polymer compositions is distilled off under reduced pressure. The polymeric solid thus obtained is subsequently crushed to give a pelletized material or converted to a powder by crushing. In this reprocessing variant, the inventive polymer compositions can also be processed directly after polymerization and cooling to room temperature to give a pelletized material or powder, if the latter has a firm film consistency. In general, the inventive polymer compositions of the second preferred embodiment of the process according to the invention are advantageously suitable for this reprocessing variant. These can generally be used to obtain firm free-flowing powders and/or granules.
[00194] None, some or all of the acid groups of the inventive polymer composition can be neutralized. Preferably none or only some of the acid groups in the inventive polymer composition are neutralized.
[00195] The bases used for neutralization can be alkaline metal bases, such as sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate and earth metal bases alkaline, such as calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate and ammonia or amines. Suitable amines are, for example, C1-C6-alkyl amines, preferably n-propylamine and n-butylamine, dialkylamines, preferably diethylpropylamine and dipropylmethylamine, trialkylamines, preferably triethylamine and triisopropylamine. Preference is given to amino alcohols, for example trialkanolamines such as triethanolamine, alkyldialkanolamines such as methyl- or ethyldiethanolamine and dialkylalkanolamines such as dimethylethanolamine and also 2-amino-2-methyl-1-propanol. Neutralization of acid groups can also be carried out with the aid of mixtures of two or more bases. The base is most preferably selected from NaOH, KOH, 2-amino-2-methyl-1-propanol, triethylamine, diethylaminopropylamine, diethanolamine, triethanolamine, triisopropanolamine and mixtures thereof. Characterization of polymer composition
The inventive polymer composition preferably has an acid group content of more than 1 mmol/g, more preferably more than 1.3 mmol/g auf. The inventive polymer composition preferably has an acid group content of not more than 15 mmol/g. The inventive polymer composition especially has an acid group content of 1.5 mmol/g to 15 mmol/g.
[00197] A polymer composition in the form of a solid substance preferably has an acid group content of 1.5 mmol/g to 15 mmol/g.
[00198] In a first preferred embodiment, up to 80% by mole of the acid groups, more preferably up to 70% by mole of the acid groups, especially up to 20% by mole of the acid groups, in the inventive polymer composition are in neutralized form.
[00199] In a second preferred embodiment, the acid groups of the inventive polymer composition are in unneutralized form.
Preferably, the polymer composition has a solubility in water at 40°C and a pH of 8 of at least 5 g/l.
[00201] The weight average molecular weight Mw of the inventive polymer composition, determined by means of gel permeation chromatography (GPC) using neutralized polyacrylic acid as the standard polymer, is preferably 1000 to 150,000 daltons. Composition containing surfactant
[00202] The inventive polymer composition is particularly advantageously suitable for formulating compositions containing surfactant. More particularly, these are compositions containing aqueous surfactant. The inventive polymer composition is notable for its good compatibility with a multitude of surfactants.
The surfactant-containing compositions comprising the inventive polymer composition preferably have a total surfactant content from 0.1% to 75% by weight, more preferably from 0.5% to 60% by weight, especially from 1% to 50 % by weight, based on the total weight of the surfactant-containing composition.
[00204] Suitable additional surfactants are anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and mixtures thereof.
[00205] Typical examples of anionic surfactants are soaps, alkyl sulfonates, alkylbenzene sulfonates, olefin sulfonates, methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, carboxylic acid soaps, and and salts thereof, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids, for example, acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglycoside sulfates, alkyl glucose carboxylates, acid protein condensates fatty and alkyl (ether) phosphates.
[00206] Suitable soaps are, for example, alkali metal, alkaline earth metal and fatty acid ammonium salts such as potassium stearate.
Suitable olefin sulfonates are obtained, for example, by adding SO3 to olefins of the formula R15-CH=CH-R16 and subsequent hydrolysis and neutralization, where R15 and R16 are each independently H or alkyl radicals having 1 to 20 carbon atoms, with the proviso that R15 and R16 together have at least 6 and preferably 8 to 20, especially 10 to 16, carbon atoms. With respect to preparation and use, reference may be made to the review article "J. Am. Oyl. Chem. Soc.", 55, 70 (1978). Olefin sulfonates can be present as alkali metal, alkaline earth metal, ammonium, alkyl ammonium, alkanol ammonium or glucammonium salts. Preferably, the olefin sulfonates are present as sodium salts. The hydrolyzed alpha-olefin sulfonate product, i.e., alpha-olefin sulfonates, are composed of about 60% by weight of alkane sulfonates and about 40% by weight of hydroxyalkane sulfonates; for example 80% to 85% by weight of it are monosulfonates and 15% to 20% by weight are disulfonates.
Preferred methyl ester sulfonates (MES) are obtained by sulphonation of methyl ester fatty acids from vegetable or animal fats or oils. Preference is given to methyl ester sulphonates from vegetable fats and oils, eg rapeseed oil, sunflower oil, soybean oil, palm oil, coconut oil, etc.
[00209] Preferred alkyl sulfates are fatty alcohol sulfates of the general formula R17-O-SO3Y wherein R17 is a linear or branched, saturated or unsaturated hydrocarbon radical having from 6 to 22 carbon atoms and Y is an alkali metal, the equivalent of a monovalent charge of an alkaline earth metal, ammonium, mono-, di-, tri- or tetra-alkylammonium, alkanolammonium or glucoammonium. Suitable fatty alcohol sulfates will preferably be obtained by the sulfation of natural fatty alcohols or synthetic oxo alcohols and subsequent neutralization. Typical examples of fatty alcohol sulfates are the sulfation products of caproic alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauric alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol , oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linoleyl alcohol, linolenyl alcohol, behenyl alcohol and eleostearyl alcohol and also their salts and mixtures. Preferred salts of fatty alcohol sulfates are sodium and potassium salts, especially sodium salts. Preferred blends of fatty alcohol sulphates are based on technical grade alcohol blends obtained, for example, from the high pressure hydrogenation of technical grade methyl esters based on fats and oils or from the hydrogenation of aldehydes from the oxo process or in the dimerization of unsaturated fatty alcohols. For the preparation of alkyl sulfates, preference is given to the use of fatty alcohols and fatty alcohol mixtures having from 12 to 18 carbon atoms and especially from 16 to 18 carbon atoms. Typical examples of these are technical grade alcohol sulfates based on raw plant materials.
Preferred sarcosinates are sodium lauroyl sarcosinate or sodium stearoyl sarcosinate.
The preferred fatty acid protein condensates are wheat-based vegetable products.
[00212] Preferred alkyl phosphates are alkyl mono and diphosphates.
[00213] Suitable acyl glutamates are compounds of formula (I)
where COR18 is a linear or branched acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and X is hydrogen, an alkali metal, the monovalent charge equivalent of alkaline earth metal, ammonium, alkylammonium , alkanolammonium or glucoammonium. Acyl glutamates are prepared, for example, by Schotten-Baumann acylation of clutamic acid with fatty acids, fatty acid esters or fatty acid halides. Acyl glutamates are commercially available, for example, from Clariant AG, Frankfurt, Germany or Ajinomoto Co. Inc., Tokyo, Japan. A review of the preparation and properties of acyl glutamates can be found in M. Takehara et al. in J. Am. Soc. 49 (1972) 143. Typical acyl glutamates suitable as component b) are preferably derived from fatty acids having from 6 to 22 and particularly preferably from 12 to 18 carbon atoms. In particular, acyl glutamate mono or dialkali metal salts are used. These include, for example, (brand names of Ajinomoto, USA in parentheses): sodium cocoylglutamate (Amisoft CS-11), disodium cocoylglutamate (Amisoft ECS-22SB), triethanolammonium cocoylglutamate (Amisoft CT-12), triethanolammonium lauroylglutamate (Amisoft LT -12), sodium myristoylglutamate (Amisoft MS-11), sodium stearoylglutamate (Amisoft HS-11 P) and mixtures thereof.
[00214] Additional nonionic surfactants include, for example: - glyceryl esters, eg glyceryl monostearate, - sugar surfactants, sorbitol esters, eg sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters, alkyl polyglycosides, N-alkyl gluconamides, - alkyl methyl sulfoxides, - alkyldimethylphosphine oxides, for example tetradecyldimethylphosphine oxides.
Suitable amphoteric surfactants are, for example, alkyl betaines, alkylamidopropyl betaines, alkyl sulphobetaines, alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates or amphopropionates, alkyl amphodiacetates or alkyl amphodipropionates. For example, it is possible to use cocodimethylsulfopropyl betaine, lauryl betaine, cocamidopropyl betaine, sodium cocamphopropionate or tetradecyldimethylamine oxide.
Cationic surfactants include, for example, quaternized ammonium compounds, especially alkyltrimethylammonium halides and dialkyldimethylammonium halides, and alkyl sulfates and also pyridine and imidazoline derivatives, especially alkylpyridinium halides. For example, it is possible to use beheyl- or cetyltrimethylammonium chloride. Washing, cleaning and dish washing compositions
[00217] The inventive polymer composition is advantageously suitable for use in washing and cleaning compositions, in dishwashing composition and rinsing aids.
[00218] Washing compositions in the context of the present invention are understood to mean those compositions which are used to clean flexible materials having high absorbance, for example materials having a textile character, whereas cleaning compositions in the context of the present invention are understood to mean those compositions which are used to clean materials having a closed surface, that is, having a surface which has only a few pores and very small, if any, and consequently has zero or only low absorbance.
[00219] Examples of flexible materials having high absorbance are those that comprise or consist of natural, synthetic or semi-synthetic fiber materials and that, consequently, in general, have at least some textile character. Fibrous materials or materials consisting of fibers can, in principle, be present in any form that occurs in use or in manufacturing and processing. For example, the fibers can be present in unordered form, in pile or aggregate form, in the ordered form of fibers, yarns, filaments or in the form of three-dimensional structures, such as nonwovens, lodens or felt, fabrics, knits, in every conceivable connection type. Fibers can be raw fibers or fibers in any processing stages. Examples are natural protein or cellulose fibers such as wool, silk, cotton, sisal, hemp or coconut fibers or synthetic fibers, for example polyester, polyamide or polyacrylonitrile fibers.
[00220] Examples of materials having only a few pores and small, if any, and having zero or only low absorbance are metal, glass, enamel or ceramic. Typical objects made from these materials are, for example, metal sinks, cutting instruments, glass or porcelain dishes, bathtubs, sinks, tiles, slates, cured synthetic resins, for example, decorative melamine resin surfaces on furniture. kitchen or painted metal surfaces, for example, refrigerators and bodies, printed circuit boards, microchips, sealed or painted wood, for example, parquet or wall cladding, window frames, doors, plastic coverings, such as floor coverings made of PVC or hard rubber or rigid or flexible foams having substantially closed surfaces.
[00221] Examples of cleaning compositions comprising the inventive polymer composition comprise washing and cleaning compositions, dishwashing compositions such as hand dishwashing compositions or machine dishwashing compositions (= a washing composition from dishes to dish washer machines), metal degreasers, glass cleaners, floor cleaners, all-purpose cleaners, high pressure cleaners, neutral cleaners, alkaline cleaners, acid cleaners, spray degreasers, daily cleaners kitchen cleaners commercial in the industry, especially in the chemical industry, car wash cleaners and also all-purpose household cleaners.
[00222] A first embodiment are washing and cleaning and dishwashing compositions which comprise the inventive polymer composition and are solid at room temperature (20°C). A second embodiment is washing and cleaning and dish washing compositions comprising an inventive non-polymeric composition in the form of a liquid or gel at room temperature (20°C) and comprising an inventive polymer composition in the shell or coating of the wash composition, cleaning or washing dishes or at least one of their components. A more specific embodiment are washing and cleaning and dishwashing compositions comprising an inventive polymer composition in the shell or coating, said shell or coating further comprising at least one active ingredient. The at least one active ingredient is then released in a controlled manner in the course of the washing and cleaning or dishwashing operation.
[00223] Solid washing and cleaning compositions can be powdered or tableted products ("tabs"). In a specific execution, these are products on tablets ("tabs"). In a particularly preferred first embodiment, these are then tablet washing compositions. In a further particularly preferred embodiment, these are then tablet dishwashing compositions, especially machine dishwashing compositions.
[00224] Tablet dishwashing compositions can be simple tablets or even so-called "2 in 1", "3 in 1", "5 in 1" or "7 in 1" products (multifunctional products). Further details of these formulations can be found in Hermann G. Hauthal, G. Wagner (eds.), Reinigungs- und Pflegemittel im Haushalt [Domestic Cleaning and Care Products], Verlag für chemische Industrie, H. Ziolkowsky GmbH, Augsburg 2003, Kapitel 4.2 , pages 161-184. The "2 in 1" products comprise, as well as the usual components of machine dishwashing detergents, additionally a rinsing aid. The "3 in 1" products also comprise a water softener. The "5 in 1" products in general also comprise a glass protector and a rinse power enhancer. The "7 in 1" products also comprise a stainless steel brightener and a descaling agent. In these tablet dish washing compositions, the inventive polymer composition may be present in the rinse aid core or is present in solid form in the tablet dish washing composition.
[00225] The inventive polymer composition is further suitable for the production and a wrapper comprising washing, cleaning or dishwashing compositions solid or liquid or in the form of gel or at least one of the components thereof. The inventive polymer composition is further suitable for producing a coating on a solid washing, cleaning or dishwashing composition or on at least one solid component thereof.
[00226] The inventive polymer composition has the particular feature of excellent action as a coformer, surfactant or dirt release polymer. When used in the rinse cycle of the dishwasher, it also acts as a scale inhibitor. The constituents of the polymeric composition also support the cleaning performance of the total formulation, loosening and dispersing dirt.
[00227] The inventive dish washing, cleaning and washing composition preferably comprises the following constituents: a) at least one inventive polymer composition; b) at least one builder (also referred to as sequestrant, builder material, complexing agent, chelator, chelating agent or softener); c) optionally at least one enzyme; d) optionally at least one bleach and e) optionally at least one additional additive, preferably selected from the following additives other than a): surfactants, bases, corrosion inhibitors, defoamers, pigments, fragrances, fillers, tabletting aids, disintegrants , thickeners, solubilizers, organic solvents, electrolytes, pH modifiers, perfume carriers, fluorescers, hydrotropes, anti-redeposition agents, optical brighteners, graying inhibitors, shrinkage inhibitors, wrinkle inhibitors, pigment transfer inhibitors, antimicrobial ingredients actives, antioxidants, corrosion inhibitors, anti-aesthetics, ironing aids, hydrophobizing and impregnating agents, swelling and anti-slip agents, UV and water absorbers. Washing and cleaning compositions
[00228] Preferably, the inventive washing and cleaning compositions comprise: a) at least one inventive polymer composition: from 0.1% to 20% by weight; b) at least one former: from 5% to 80% by weight; c) at least one enzyme: from 0% to 8% by weight; d) at least one bleach: from 0% to 30% by weight and e) at least one additional additive: from 0% to 50% by weight.
[00229] The weight percentages are each based on the total weight of the washing and cleaning composition. The weights from a) to e) total up to 100% by weight.
[00230] More preferably, the inventive washing and cleaning composition comprises at least one enzyme.
[00231] More preferably, the constituents mentioned above are present in an inventive washing and cleaning composition in the following ratios: a) at least one inventive polymer composition: from 0.1% to 10% by weight; b) at least one former: from 20% to 80% by weight; c) at least one enzyme: from 0.1% to 6% by weight; d) at least one bleach: from 0% to 30% by weight and e) at least one additional additive: from 0% to 50% by weight.
The weight percentages are each based on the total weight of the washing and cleaning composition. The weights from a) to e) total up to 100% by weight.
Even more preferably, the inventive washing and cleaning composition also comprises at least one bleach.
[00234] Even more preferably, the constituents mentioned above are present in an inventive washing and cleaning composition in the following ratios: a) at least one inventive polymer composition: from 0.1% to 10% by weight; b) at least one former: from 20% to 80% by weight; c) at least one enzyme: from 0.1% to 6% by weight; d) at least one bleach: from 5% to 25% by weight and e) at least one additional additive: from 0% to 50% by weight.
[00235] The weight percentages are each based on the total weight of the washing and cleaning composition. The weights from a) to e) total up to 100% by weight.
[00236] With respect to suitable and preferred inventive polymer compositions, reference is made to the above details. Dishwashing Compositions
[00237] The inventive polymer compositions described above are particularly advantageously suitable for use in dishwashing compositions, especially for machine washing processes (automatic dishwashing, ADW). The inventive polymer composition is effective as both a surfactant and a coformer. Examples of inventive formulations comprising the polymeric dishwashing composition, in this way, comprise machine dishwashing detergents, rinse aids and machine dishwashing detergents with rinse aid function. The formulations are present especially at room temperature (20°C).
[00238] Machine dish washing processes in the domestic and commercial sector comprise a plurality of successive steps, the first comprising the mechanical removal of loosely adhering food residues, the second actual cleaning operation with the aid of the machine dishwasher and the third usually consists of a rinse step, which is followed by drying the clean dishes. These operations are carried out in more or less automated form, the central unit used being a dish washing machine in which at least the cleaning step and, in general, also the subsequent rinsing step and/or the drying step are carried out.
[00239] In dish washing machines for the domestic sector, dirty dishes are generally cleaned in a simple chamber and the treatment steps already mentioned proceed successively in a controlled program. Fresh water passes through the softener unit to the pump sump and is sprayed by means of movable spray members onto the dishes to be rinsed. Substances insoluble in rinsed water are filtered in the pump reservoir. In the second rinse cycle, a generally alkaline cleaning composition is added to the rinse water, heated to a fixed temperature and distributed over the dishes to be rinsed. In the last rinsing cycle, a rinsing aid is added to the treatment liquid, which reduces surface tension, as a result of which the treatment liquid flows more easily from the crockery. After the last rinse cycle, the contents are dried. Components used in the rinse cycle, such as water treatment agents, cleaning compositions, rinse aids, etc., can be used in the form of individual components or in multi-component formulations. Multifunctional detergents of this type comprise rinsing surfactants and a water softening polymer. In that case, it is unnecessary to separately dispense a rinsing aid and a salt for softening the water in the dishwasher.
[00240] Commercial dish washing machines basically consist of stationary bath tanks from which an essentially aqueous cleaning solution is blasted or sprayed onto the crockery, which moves after these baths on a conveyor belt, such that the solution used flow back to the bath tanks again. The water enters the last bathing tank, flows through the overflow in a cascade fashion through all the other tanks and leaves the machine through the overflow of the first tank. The application of a cleaning solution in general that is highly alkaline in general takes place with the aid of nozzles provided for it or with a specific spray system normally arranged in the middle region of the machine.
[00241] The inventive machine dishwashing formulations are especially notable for excellent deposit inhibiting action when used in the rinse cycle of a dishwashing machine (ie, acts as a scale inhibitor). These have an inhibiting action with respect to both organic and inorganic deposits. Inorganic deposits are especially calcium and magnesium phosphate, calcium and magnesium carbonate, calcium and magnesium silicate and/or calcium and magnesium phosphonate, which arise from calcium and magnesium salts present in water and builders present in washing detergents of standard dishes. Organic deposits are especially dirty constituents of the rinse liquid, eg protein, starch and fat deposits. The inventive machine wash and dish formulations are also effective against transfer deposits, which originate from the residual water at the bottom of the dish washing machine and comprise, inter alia, residues from the dish washing composition and possibly also residues of dirt from the dishwasher's prewash cycle.
[00242] The inventive formulation for machine dishwashing preferably comprises the following constituents: a) at least one inventive polymer composition, b) at least one builder (also referred to as sequestrant, builder material, complexing agent, chelating agent, agent chelator or softener), c) optionally at least one enzyme, d) optionally at least one bleach, e1) water, e2) optionally at least one thickener and e3) optionally at least one additional additive, preferably selected from the following additives other than a): surfactants, bases, corrosion inhibitors, defoamers, pigments, fragrances, fillers, solubilizers and organic solvents.
[00243] The inventive formulation for machine dishwashing comprises, based on the total weight of the formulation, preferably: a) 0.1% to 50% by weight of at least one inventive polymer composition, b) 5% to 90% by weight of at least one former and/or coformer, c) 0% to 8% by weight of at least one enzyme, d) 0% to 30% by weight of at least one bleach, e1) 0.1% to 90% by weight of water, e) ) 0% to 8% by weight of at least one thickener, f) ) 0% to 25% by weight of at least one additional additive,
[00244] With the proviso that the weights of components a) to e) total up to 100% by weight.
In a preferred embodiment, the inventive machine dishwashing formulation comprises at least one enzyme.
[00246] The inventive formulation for machine dishwashing comprises, based on the total weight of the formulation, preferably: a) 2% to 40% by weight of at least one inventive polymer composition, b) 5% to 80% by weight of at least one former and/or coformer, c) 0.1% to 6% by weight of at least one enzyme, d) 0% to 30% by weight of at least one bleach, e1) 0.1% to 80% by weight of water, e) ) 0% to 6% by weight of at least one thickener, f) ) 0% to 25% by weight of at least one additional additive,
[00247] With the proviso that the weights of components a) to e) total up to 100% by weight.
[00248] More preferably, the inventive machine dishwashing formulation comprises, based on the total weight of the formulation: a) 0.12% to 30% by weight of at least one inventive polymer composition, b) 5% to 75% by weight of at least one former and/or coformer, c) 0.1% to 6% by weight of at least one enzyme, d) 0% to 25% by weight of at least one bleach, e1) 0 .1% to 80% by weight of water, e2) 0.1% to 5% by weight of at least one thickener, e3) 0% to 25% by weight of at least one additional additive, with the proviso that the weights of components a) to e) total up to 100% by weight.
[00249] The polymer composition a) may be incorporated into the formulation or may be present in the total formulation in a separate region as a clear gel component separately from the other components (eg, divided by a film, for example, of a composition inventive polymer or polyvinyl alcohol).
[00250] Dish cleaning formulations can be in the form of tablets or all-liquid formulations. However, it is also possible that containers produced with formed films or bodies, having 1 to 6 individual sections of equal or equivalent size, are present. These can be independently filled with powders, pellets, solids or liquids. The polymer composition a) is preferably dispensed in a compartment. The polymer composition a) can be further thickened or colored. Component a)
[00251] With respect to suitable inventive polymer compositions and preferred as component a), reference is made to the above details. Component b)
The inventive washing and cleaning and dish washing compositions preferably comprise at least one former.
[00253] The formers, which are sometimes referred to as sequestrants, building materials, complexing agents, chelating agents, chelating agents, or softeners, bind alkaline earth metals and other water-soluble metal salts without precipitation. They help to break down dirt, disperse dirt components, help loosen dirt, and in some cases have a washing effect on their own. Furthermore, when these are solid and are used in powdery formulations, they keep the powder free flowing.
[00254] Suitable builders can be organic or inorganic in a natural state. Examples are aluminosilicates, carbonates, phosphates and polyphosphates, polycarboxylic acids, polycarboxylates, hydroxycarboxylic acids, phosphonic acids, for example hydroxyalkylphosphonic acids, phosphonates, aminopolycarboxylic acids and salts thereof and polymeric compounds containing carboxylic acid groups and salts thereof.
[00255] Suitable inorganic builders are, for example, crystalline or amorphous aluminosilicates having ion exchange properties, such as zeolites. Various types of zeolites are suitable, especially zeolites A, X, B, P, MAP and HS in the sodium form of these or in forms where Na has been partially replaced by other cations such as Li, K, Ca, Mg or ammonium. Suitable zeolites are described, for example, in US-A-4604224. Crystalline silicates suitable as builder are, for example, disilicate or sheet silicates, for example 5-Na2Si2O5 or B-Na2Si2O5 (SKS 6 or SKS 7). Silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as sodium, lithium and magnesium silicates. Amorphous silicates, for example sodium metasilicate having a polymeric structure or amorphous disilicate (Britesil® H 20, manufacturer: Akzo), are also usable. Among these, preference is given to sodium disilicate.
[00256] Suitable inorganic builder substances based on carbonate are carbonate hydrogen carbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preference is given to the use of sodium, lithium and magnesium carbonates or sodium, lithium and magnesium hydrogen carbonates, especially sodium carbonate and/or sodium hydrogen carbonate.
[00257] The usual phosphates used as inorganic builders are alkali metal orthophosphates and/or polyphosphates, eg pentasodium triphosphate.
Suitable organic builders are, for example, C4-C30-di-, -tri- and -tetracarboxylic acids, for example succinic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and alkyl- and alkenylsuccinic acids having alkyl radicals - or alkenyl-C2-C20.
[00259] Suitable organic builders are also hydroxycarboxylic acids and polyhydroxycarboxylic acids (sugar acids). These include C4-C20-hydroxycarboxylic acids, eg malic acid, tartaric acid, gluconic acid, mucic acid, lactic acid, glutaric acid, citric acid, tartronic acid, glucoheptonic acid, lactobionic acid and sucrosemono-,-di - and tricarboxylic. Among these, preference is given to citric acid and its salts.
[00260] Suitable organic builders are also phosphonic acids, eg hydroxyalkylphosphonic acids, aminophosphonic acids and the salts thereof. These include, for example, phosphonobutanetricarboxylic acid, aminotris(methylenephosphonic acid), ethylenediaminetetraethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, morpholinomethanediphosphonic acid, 1-hydroxy-C1- to C10-alkyl-1,1-diphosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic. Among these, preference is given to 1-hydroxyethane-1,1-diphosphonic acid and its salts.
[00261] Suitable organic builders are additionally aminopolycarboxylic acids, such as nitrilotriacetic acid (NTA), nitrilomonoacetic acid dipropionic acid, nitrilotripropionic acid, β-alaninediacetic acid (β-ADA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, acid 1 ,3-propylenediaminetetraacetic acid, 1,2-propylenediaminetetraacetic acid, N-(alkyl)ethylenediaminetriacetic acid, N(hydroxyalkyl)ethylenediaminetriacetic acid, ethylenediaminetriacetic acid, cyclohexylene-1,2-diaminetetraacetic acid, iminodisuccinic acid, ethylenediaminedisuccinic acid , serinediacetic acid, isoserinediacetic acid, L-asparaginodiacetic acid, L-glutaminodiacetic acid, methylglycinediacetic acid (MGDA) and the aforementioned aminopolycarboxylic acid salts. Among these, preference is given to L-glutaminodiacetic acid, methylglycinediacetic acid and salts thereof.
[00262] Suitable organic builders are additionally polymeric compounds containing carboxylic acid groups, such as acrylic acid homopolymers. These preferably have a number average molecular weight in the range from 800 to 70,000 g/mol, more preferably from 900 to 50,000 g/mol, particularly from 1000 to 20,000 g/mol, especially 1000 to 10,000 g/mol. The term "acrylic acid homopolymer" also comprises polymers in which some or all of the carboxylic acid groups are in neutralized form. These include acrylic acid homopolymers in which some or all of the carboxylic acid groups are in the form of alkali metal salts or ammonia salts. Preference is given to acrylic acid homopolymers in which the carboxylic acid groups are protonated or in which some or all of the carboxylic acid groups are in the form of the sodium salts.
Suitable polymeric compounds containing carboxylic acid groups are also oligomaleic acids, as described, for example, in EP-A 451 508 and EP-A 396 303.
[00264] Suitable polymeric compounds containing carboxylic acid groups are also terpolymers of unsaturated C4-C8-dicarboxylic acids, where polymerized comonomers may include monoethylenically unsaturated monomers from group (i) specified below in amounts of up to 95% by weight , from group (ii) in amounts of up to 60% by weight and from group (iii) in amounts of up to 20% by weight. Suitable unsaturated C4-C8-dicarboxylic acids in this context are, for example, maleic acid, fumaric acid, itaconic acid and citraconic acid. Preference is given to maleic acid. Group (i) comprises monoethylenically unsaturated C3-C8-monocarboxylic acids, for example acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. From group (i), preference is given using acrylic acid and methacrylic acid. Group (ii) comprises C2-C22-monoethylenically unsaturated olefins, vinyl alkyl ethers having C1-C8-alkyl groups, styrene, vinyl esters of C1-C8-carboxylic acids, (meth)acrylamide and vinylpyrrolidone. From group (ii), preference is given using C2-C6 olefins, vinyl alkyl ethers having C1-C4-alkyl groups, vinyl acetate and vinyl propionate. If the group (ii) polymers comprise vinyl esters in polymerized form, these may also be present partially or fully hydrolyzed to vinyl alcohol structural units. Suitable co- and terpolymers are known, for example, from US-A 3887806 and DE-A 4313909. Group (iii) comprises (meth)acrylic esters of C1-C8 alcohols, (meth)acrylonitrile, (meth)acrylamides of C1-C8 amines, N-vinylformamide and N-vinylimidazole.
[00265] Suitable polymeric compounds containing carboxylic acid groups are also homopolymers of monoethylenically unsaturated C3-C8-monocarboxylic acids, for example, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, especially of acrylic acid and methacrylic acid, copolymers of dicarboxylic acids, eg copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95:5, more preferably those in a weight ratio of 30:70 to 90:10 with molar masses of 1000 to 150 000; terpolymers of maleic acid, acrylic acid and a vinyl ester of a C1-C3-carboxylic acid in a weight ratio of 10 (maleic acid):90 (acrylic acid + vinyl ester) to 95 (maleic acid):10 (acrylic acid + vinyl ester), where the weight ratio of acrylic acid to vinyl ester can vary within the range of 30:70 to 70:30; copolymers of maleic acid with C2-C8 olefins in a molar ratio of 40:60 to 80:20, particular preference being given to copolymers of maleic acid with ethylene, propylene or isobutene in a molar ratio of 50:50.
[00266] Suitable polymeric compounds containing carboxylic acid groups are also copolymers of 50% to 98% by weight of the weakly ethylenically unsaturated carboxylic acids with 2% to 50% by weight of the ethylenically unsaturated sulfonic acids, as described, for example, in EP-A-0877002. Suitable ethylenically unsaturated weak carboxylic acids are especially C3-C6-monocarboxylic acids, such as acrylic acid and methacrylic acid. Suitable ethylenically unsaturated sulfonic acids are 2-acetylamidomethyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethylacrylamide, sulfomethylmethacrylamide and salts of the same acids. The copolymers may also comprise, in copolymerized form, 0 to 30% by weight of ethylenically unsaturated C4-C8-dicarboxylic acids, such as maleic acid and 0 to 30% by weight of at least one monomer which is copolymerizable with the aforementioned monomers . The latter are, for example, C1-C4-alkyl esters of (meth)acrylic acid, C1-C4-hydroxyalkyl esters of (meth)acrylic acid, acrylamide, alkyl substituted acrylamide, N,N-dialkyl substituted acrylamide, acid vinylphosphonic, vinyl acetate, allylic alcohols, sulphonated allylic alcohols, styrene and other vinylaromatics, acrylonitrile, N-vinylpyrrolidone, N-vinylformamide, N-vinylimidazole or N-vinylpyridine. The weight average molecular weight of these copolymers is within the range of 3000 to 50,000 daltons. Particularly suitable copolymers are those with about 77% by weight of at least one ethylenically unsaturated C3-C6-monocarboxylic acid and about 23% by weight of at least one ethylenically unsaturated sulfonic acid.
[00267] Graft polymers of unsaturated carboxylic acids on low molecular weight carbohydrates or hydrogenated carbohydrates (cf. US-A 5227446, DE-A 4415623 and DE-A 4313909) are equally suitable. Suitable unsaturated carboxylic acids in this context are, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid and also mixtures of acrylic acid and maleic acid, which are grafted in quantities 40% to 95% by weight, based on the component to be grafted. For modification, it is additionally possible for up to 30% by weight, based on the component to be grafted, of the additional monoethylenically unsaturated monomers to be present in the polymerized form. Suitable modifying monomers are the above-mentioned monomers of groups (ii) and (iii). Suitable graft bases are degraded polysaccharides, e.g. acidically or enzymatically degraded starches, inulin or cellulose, protein hydrolysates and reduced degraded polysaccharides (hydrogenated or hydrogenatedly amino), e.g., mannitol, sorbitol, aminosorbitol and N-alkylglucamine, such as are polyalkylene glycols with molar masses of up to Mw = 5000, for example polyethylene glycols, ethylene oxide/propylene oxide or ethylene oxide/butylene oxide or ethylene oxide/propylene oxide/butylene oxide block copolymers and alkoxylated C1-C22 mono- or polyhydric alcohols (cf. US-A-5756456).
[00268] Also suitable are polyglyoxylic acids, as described, for example, in EP-B 001004, US-A-5399286, DE-A-4106355 and EP-A-656914. The end groups of polyglyoxylic acids can have different structures.
[00269] Further suitable are polyamidocarboxylic acids and modified polyamidocarboxylic acids; these are, for example, known from EP-A-454126, EP-B-511037, WO-A-94/01486 and EP-A-581452.
Polyaspartic acids or co-condensates of aspartic acid with additional amino acids, C4-C25 mono- or dicarboxylic acids and/or C4-C25 mono- or -diaminos can also be used as polymeric compounds containing carboxylic acid groups. Particular preference is given using polyaspartic acids which have been prepared in the phosphorous acids and have been modified with C6-C22 mono- or dicarboxylic acids or with C6-C22 mono- or -diaminos.
[00271] Among polymeric compounds containing carboxylic acid groups, polyacrylic acids are preferred, including in partially or fully neutralized form.
Suitable organic builders are also iminodisuccinic acid, oxydisuccinic acid, aminopolycarboxylates, alkyl polyaminocarboxylates, aminopolyalkylenephosphonates, polyglutamates, hydrophobically modified citric acid, e.g. agaric acid, poly-α-hydroxyacrylic acid, N-acylethylenediamino triacetates such as N-acylethylenediamino triacetates lauroylethylenediamino triacetate and ethylenediaminetetraacetic acid alkylamides such as tallow amide EDTA.
[00273] In addition, it is also possible to use oxidized starches as organic reinforcers.
[00274] Preference is given to use as component b), a mixture of different reinforcers.
[00275] The mixture of the different reinforcers preferably comprises at least two of the following constituents: at least one carbonate (eg sodium carbonate), at least one silicate (eg sodium disilicate), at least one polymer compound containing carboxylic acid groups or at least one polymer compound containing carboxylic acid groups all or some of which are present in neutralized form (eg polyacrylic acid), at least one (poly)hydroxycarboxylic acid or a salt thereof (eg , citric acid or a citrate), at least one aminopolycarboxylic acid or a salt thereof (for example methylglycinediacetic acid or a salt thereof, for example a sodium salt thereof), at least one phosphonic acid (for example 1-hydroxyethane -1- (1,1-diphosphonic acid); HEDP), at least one phosphate. More preferably, the mixture comprises at least one carbonate, at least one silicate and at least one optionally (partially) neutralized polymeric compound containing carboxylic acid groups and optionally at least one of the following constituents: at least one (poly)hydroxycarboxylic acid or one salt thereof, at least one phosphonic acid, at least one phosphate. The mixture especially comprises at least one carbonate, at least one silicate, at least one optionally (partially) neutralized polymeric compound containing carboxylic acid groups, at least one (poly)hydroxycarboxylic acid or a salt thereof and at least one phosphonic acid and optionally at least one phosphate.
[00276] In such a mixture, the constituents are preferably present in the following amounts: b1) at least one carbonate: 10% to 50% by weight; b2) at least one silicate: 1% to 10% by weight; b3) at least one optionally (partially) neutralized polymeric compound containing carboxylic acid groups: 5% to 20% by weight; b4) at least one (poly)hydroxycarboxylic acid or a salt thereof: 0% to 50% by weight; b5) at least one aminopolycarboxylic acid or a salt thereof: 0% to 60% by weight; b6) at least one phosphonic acid: 0.2% to 1% by weight; b7) at least one phosphate: 0% to 60% by weight.
[00277] The weight percentages are each based on the total weight of the trainer. The weights from b1) to b7) increase up to 100% in weight. Component c)
The inventive washing and cleaning and dishwashing compositions preferably comprise at least one enzyme.
[00279] Suitable enzymes are those as typically used as industrial enzymes. These include both enzymes having very favorable activity in the neutral to alkaline pH range and enzymes having very favorable activity in the acidic pH range.
The enzymes are preferably selected from aminopeptidases, amylases, arabinases, carbohydrases, carboxypeptidases, catalases, cellulases, chitinases, cutinases, cyclodextrin glycosyltransferases, deoxyribonucleases, esterases, galactanases, alpha-galactosidases, alpha-amylas-glucans betaglucosidases, haloperoxidases, hydrolases invertases, isomerases, keratinases, laccases, lipases, mannanases, mannosidases, oxidases, pectinolytic enzymes, peptidoglutaminases, peroxidases, peroxygenases, phytases, polyphenol oxidases, transglu- riboses and x-transferasyl mixtures, proteolytic enzymes, transferases, transferases.
The enzymes are specially selected from hydrolases, such as proteases, esterases, glucosidases, lipases, amylases, cellulases, mannanases, other glycosyl hydrolases and mixtures of the aforementioned enzymes. All of these hydrolases contribute to dissolving and removing dirt from the stain-containing protein, grease or starch. It is also possible to use oxidoreductases for bleaching. Of particular good suitability are enzymatic active ingredients obtained from bacterial or fungal stains such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens.
[00282] Preferred enzymes are described in detail below: Proteases:
[00283] Suitable proteolytic enzymes (proteases) can in principle be of animal, vegetable or microbial origin. Preference is given to proteolytic enzymes of microbial origin. These too include chemically or genetically modified mutants.
Preferred proteases are serine proteases, metalloproteases or trypsin-like proteases. Preference is given using an alkaline microbial protease. Examples of alkaline proteases are subtilisins, especially those derived from Bacillus, for example subtilisin Novo, subtilisin Carlsberg, subtilisin 309, subtilisin 147 and subtilisin 168 (described in WO 89/06279). Examples of trypsin-like proteases are trypsin (e.g. porcine or bovine) and the Fusarium protease described, e.g., in WO 89/06270.
Preferred commercially available proteases include those proteases available under the following brand names: Alcalase™, Savinase™, Primase™, Durazym™, Esperase™, Neutrase™ from Novozymes A/S (Denmark), products sold by DuPont/Genencor under the brand names Maxatase™, Maxacal™, Maxapem™, PREFERENZ™ P, EXCELLENZ™ P Properase™, Purafect™ and Purafect™ OXP and products sold by Solvay Enzymes under the brands Opticlean™ and Optimase™.
[00286] The inventive compositions preferably comprise at least one protease in an amount from 0.00001% by weight to 30% by weight of the enzyme protein, more preferably from 0.0001% by weight to 15% by weight of the enzyme protein , especially 0.001% by weight to 10% by weight of the enzyme protein, especially 0.001% by weight to 5% by weight of the enzyme protein, based on the total weight of the inventive polymer composition.
[00287] More particularly, the inventive composition is in the form of a film containing the enzyme. In that case, the inventive composition preferably comprises at least one protease in an amount of from 0.00001% by weight to 30% by weight of the enzyme protein, more preferably from 0.0001% by weight to 15% by weight of the enzyme protein , especially 0.001% by weight to 10% by weight of the enzyme protein, especially 0.001% by weight to 5% by weight of the enzyme protein, based on the total weight of the film containing the enzyme. Lipases:
[00288] Suitable lipases can originate in principle from bacteria or fungi. These also include chemically or genetically modified mutants.
Examples of suitable lipases are Humicola lanuginosa lipase, described, for example, in EP 258 068 and EP 305 216, Rhizomucor miehei lipase, described, for example, in EP 238 023, Candida lipase, such as C. Lipase antarctica , for example, C. antarctica lipases A or B as described in EP 214 761, Pseudomonas lipase such as P. alcaligenes and P. pseudoalcaligenes lipase, described, for example, in EP 218 272, P. cepacia lipase, described, by P. cepacia lipase, described by for example, in EP 331 376, P. stutzeri lipase, described for example in GB 1,372,034, P. fluorescens lipase, Bacillus lipase, for example a B. subtilis lipase (Dartois et al., (1993), Biochemica et Biophysica acta 1131, 253-260), lipase B. stearothermophilus (JP 64/744992) and lipase B. pumilus (WO 91/16422).
Furthermore, the multitude of cloned lipases is suitable, comprising Penicillium camembertii lipase described by Yamaguchi et al., (1991), Gene 103, 61-67), Geotricum candidum lipase (Schimada, Y. et al., ( 1989), J. Biochem., 106, 383-388) and various Rhizopus lipases, such as lipase R. delemar (Hass, M.J et al., (1991), Gene 109, 117-113), lipase R. niveus (Kugimiya et al., (1992), Biosci. Biotech. Biochem. 56, 716-719) and lipase R. oryzae.
Furthermore, it is possible to use other types of lipolytic enzymes, such as cutinases, e.g. a cutinase derived from Pseudomonas mendocina, as described, e.g., in WO 88/09367, or a cutinase derived from Fusarium soIani pisi ( as described, for example, in WO 90/09446).
Especially suitable lipases are Ml Lipase™, Luma Fast™ and Lipo-max™ (Genencor), Lipoclean™, Lipex™, Lipolex™ Lipolase™ and Lipolase Ultra™ (Novozymes A/S) and Lipase P "Amano" (Amano Pharmaceutical Co. Ltd.).
[00293] The inventive compositions preferably comprise at least one lipase in an amount from 0.00001% by weight to 30% by weight of the enzyme protein, more preferably from 0.0001% by weight to 15% by weight of the enzyme protein , especially 0.001% by weight to 10% by weight of the enzyme protein, especially 0.001% by weight to 5% by weight of the enzyme protein, based on the total weight of the inventive polymer composition.
[00294] More particularly, the inventive composition is in the form of a film containing the enzyme. In that case, the inventive composition preferably comprises at least one lipase in an amount of from 0.00001% by weight to 30% by weight of the enzyme protein, more preferably from 0.0001% by weight to 15% by weight of the enzyme protein , especially 0.001% by weight to 10% by weight of the enzyme protein, especially 0.001% by weight to 5% by weight of the enzyme protein, based on the total weight of the film containing the enzyme. Amylases:
[00295] In principle, all α- and/or β amylases are suitable. Suitable amylases can originate in principle from bacteria or fungi. These also include chemically or genetically modified mutants.
Examples of suitable amylases are α-amylases obtained from a specific spot of B. amyloliquefaciens or B. licheniformis, described in detail in GB 1,296,839. Further suitable amylases comprise structures known as SP707 from Bacillus sp, AP1378, BSG B. stearothermophilus alpha-amylase, SP690, SP722 and AA560 from Bacillus sp. Suitable commercially available amylases are Stainzyme™, Stainzyme Plus™, Natalase™, Duramil™, Termamil™, Fungamil™ and BAN™ (available from Novozymes A/S) and Rapidase™, PREFERENZ™ S, EXCELLENZ™ S and Maxamil P™ (available from Genencor).
[00297] The inventive compositions preferably comprise at least one amylase in an amount from 0.00001% by weight to 30% by weight of the enzyme protein, more preferably from 0.0001% by weight to 15% by weight of the enzyme protein , especially 0.001% by weight to 10% by weight of the enzyme protein, especially 0.001% by weight to 5% by weight of the enzyme protein, based on the total weight of the inventive polymer composition.
[00298] More particularly, the inventive composition is in the form of a film containing the enzyme. In that case, the inventive composition preferably comprises at least one amylase in an amount of from 0.00001% by weight to 30% by weight of the enzyme protein, more preferably from 0.0001% by weight to 15% by weight of the enzyme protein , especially 0.001% by weight to 10% by weight of the enzyme protein, especially 0.001% by weight to 5% by weight of the enzyme protein, based on the total weight of the film containing the enzyme. Cellulases:
[00299] In principle, all cellulases are suitable. Suitable cellulases can originate in principle from bacteria or fungi. These also include chemically or genetically modified mutants.
[00300] Suitable cellulases are described in US 4,435,307. These are fungal cellulases produced from Humicola insolens. Cellulases having color care properties are especially suitable. Examples of such cellulases are described in EP 0 495 257.
Suitable commercially available cellulases comprise Celluzyme™ produced from the strain of Humicola insolens, Carezyme™, Celluclean™, Endolase™, Whitezyme™ (Novozymes A/S), REVITALENZ™ (DuPont), Biotouch C™ (AB Enzymes) and KAC-500(B)™ (Kao Corporation).
[00302] The inventive compositions preferably comprise at least one cellulase in an amount from 0.00001% by weight to 30% by weight of the enzyme protein, more preferably from 0.0001% by weight to 15% by weight of the enzyme protein , especially 0.001% by weight to 10% by weight of the enzyme protein, especially 0.001% by weight to 5% by weight of the enzyme protein, based on the total weight of the inventive polymer composition.
[00303] More particularly, the inventive composition is in the form of a film containing the enzyme. In that case, the inventive composition preferably comprises at least one cellulase in an amount of from 0.00001% by weight to 30% by weight of the enzyme protein, more preferably from 0.0001% by weight to 15% by weight of the enzyme protein , especially 0.001% by weight to 10% by weight of the enzyme protein, especially 0.001% by weight to 5% by weight of the enzyme protein, based on the total weight of the film containing the enzyme. Peroxidases/oxidases:
Suitable peroxidases/oxidases can originate in principle from plants, bacteria or fungi. These also include chemically or genetically modified mutants.
[00305] Peroxidase enzymes are used in combination with hydrogen peroxide or a source of hydrogen peroxide (eg a percarbonate, perborate or persulfate). Oxidase enzymes are used in combination with oxygen. Both types of enzyme are used for "solution bleaching" to prevent the transfer of pigment from the colored fabric to another fabric when these are washed together in a liquid. These can preferably be used together with the action enhancers described, for example, in WO 94/12621 and WO 95/01426.
[00306] The inventive compositions preferably comprise at least one peroxidase or oxidase in an amount from 0.00001% by weight to 30% by weight of the enzyme protein, more preferably from 0.0001% by weight to 15% by weight of the protein of enzyme, especially 0.001% by weight to 10% by weight of the enzyme protein, especially 0.001% by weight to 5% by weight of the enzyme protein, based on the total weight of the inventive polymer composition.
[00307] More particularly, the inventive composition is in the form of a film containing the enzyme. In that case, the inventive composition preferably comprises at least one peroxidase or oxidase in an amount of from 0.00001% by weight to 30% by weight of the enzyme protein, more preferably from 0.0001% by weight to 15% by weight of the protein of enzyme, especially 0.001% by weight to 10% by weight of the enzyme protein, especially 0.001% by weight to 5% by weight of the enzyme protein, based on the total weight of the film containing the enzyme. Liases:
[00308] In principle, all aliases are suitable. Suitable lyases can originate in principle from bacteria or fungi. These also include chemically or genetically modified mutants.
[00309] Suitable lyases are pectin lyases. Suitable commercially available lyases comprise XPect™ (Novozymes A/S) and PREFERENZ™ F (DuPont).
[00310] The inventive compositions preferably comprise at least one lyase in an amount from 0.00001% by weight to 30% by weight of the enzyme protein, more preferably from 0.0001% by weight to 15% by weight of the enzyme protein , especially 0.001% by weight to 10% by weight of the enzyme protein, especially 0.001% by weight to 5% by weight of the enzyme protein, based on the total weight of the inventive polymer composition.
[00311] More particularly, the inventive composition is in the form of a film containing the enzyme. In that case, the inventive composition preferably comprises at least one lyase in an amount of from 0.00001% by weight to 30% by weight of the enzyme protein, more preferably from 0.0001% by weight to 15% by weight of the enzyme protein , especially 0.001% by weight to 10% by weight of the enzyme protein, especially 0.001% by weight to 5% by weight of the enzyme protein, based on the total weight of the film containing the enzyme.
The inventive compositions may comprise the additional enzymes encompassed by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectinylases (= pectinases), pectin esterases, xyloglycanases (= xylanases), pullulanases and β-glucanases.
[00313] The inventive compositions preferably comprise at least one hemicellulase in an amount from 0.00001% by weight to 30% by weight of the enzyme protein, more preferably from 0.0001% by weight to 15% by weight of the enzyme protein , especially 0.001% by weight to 10% by weight of the enzyme protein, especially 0.001% by weight to 5% by weight of the enzyme protein, based on the total weight of the inventive polymer composition.
[00314] More particularly, the inventive composition is in the form of a film containing the enzyme. In that case, the inventive composition preferably comprises at least one hemicellulase in an amount of from 0.00001% by weight to 30% by weight of the enzyme protein, more preferably from 0.0001% by weight to 15% by weight of the enzyme protein , especially 0.001% by weight to 10% by weight of the enzyme protein, especially 0.001% by weight to 5% by weight of the enzyme protein, based on the total weight of the film containing the enzyme.
The inventive washing, cleaning and dishwashing composition preferably comprises at least one enzyme selected from proteases, amylases, mannanases, cellulases, lipases, pectin lyases and mixtures thereof.
The inventive dish washing, cleaning and washing composition preferably comprises at least one protease and/or amylase.
The inventive washing, cleaning and dish washing composition preferably comprises at least one enzyme mixture. Preference is given, for example, to enzyme mixtures comprising or consisting of the following enzymes: - protease and amylase, - protease and lipase (or lipolytic enzymes), - protease and cellulase, - amylase, cellulase and lipase (or lipolytic enzymes) , - protease, amylase and lipase (or lipolytic enzymes), - protease, lipase (or lipolytic enzymes) and cellulase.
[00318] Enzymes can be adsorbed on carrier substances in order to protect from premature breakdown.
[00319] Optionally, the inventive washing, cleaning and dishwashing composition may also comprise enzyme stabilizers. Examples of these include calcium propionate, sodium formate, boric acids, boronic acids and salts thereof such as 4-formylphenylboronic acid, peptides and peptide derivatives, for example peptide aldehydes, polyols such as 1,2 propane -diol, and mixtures thereof. Component d)
The bleaches d) are preferably bleaching systems which, as well as bleaches, possibly also comprise bleach activators, bleach catalysts and/or bleach stabilizers.
Suitable bleaches are, for example, percarboxylic acids, for example, diperoxododecanedicarboxylic acid, phthalimidopercaproic acid or monoperoxophthalic acid or terephthalic acid, salts of percarboxylic acids, for example, sodium percarbonate, hydrogen peroxide adducts in inorganic salts, for example, sodium perborate monohydrate, sodium perborate tetrahydrate, sodium carbonate perhydrate or sodium phosphate perhydrate, hydrogen peroxide adducts in organic compounds, for example urea perhydrate, or from inorganic peroxo salts, for example alkali metal persulfates or peroxodisulfates.
Suitable bleaching activators are, for example, polyacylated sugars, for example pentaacetylglucose; acyloxybenzenesulfonic acids and their alkali earth metal and alkali metal salts, for example, sodium p-nonanoyloxybenzenesulfonate or sodium p-benzoyloxybenzenesulfonate; - N,N-diacylated and N,N,N',N'-tetra-acylated amines, for example, N,N,N',N'-tetra-acetylmethylenediamino and -ethylenediamino (TAED), N,N-diacetylaniline , N,N-diacetyl-p-toluidine or diacylated 1,3-hydantoins such as 1,3-diacetyl-5,5-dimethylhydantoin; N-alkyl-N-sulfonylcarbonamides, for example N-methyl-N-mesylacetamide or N-methyl-N-mesylbenzamide; N-acylated cyclic hydrazides, acylated triazoles or urazoles, for example monoacetyl maleic hydrazide; O,N,N-trisubstituted hydroxylamines, for example O-benzoyl-N,N-succinylhydroxylamine, O-acetyl-N,N-succinylhydroxylamine or O,N,N-triacetylhydroxylamine; N,N'-diacylsulfurylamides, for example N,N'-dimethyl-N,N'-diacetylsulfurylamide or N,N'-diethyl-N,N'-dipropionylsulfurylamide; acylated lactams, for example acetylcaprolactam, octanoylcaprolactam, benzoylcaprolactam or carbonylbiscaprolactam; anthranyl derivatives, for example 2-methylanthranyl or 2-phenylanthrani; triacyl cyanurates, for example triacetyl cyanurate or tribenzoyl cyanurate; oxime esters and bisoxime esters, for example, O-acetylacetone oxime or bisisopropyl iminocarbonate; carboxylic anhydrides, for example acetic anhydride, benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride; enol esters, for example isopropenyl acetate; 1,3-diacyl-4,5-diacyloxyimidazolines, for example 1,3-diacetyl-4,5-diacetoxyimidazoline; tetraacetylglycoluril and tetrapropionylglycoluril; diacylated 2,5-diketopiperazines, for example, 1,4-diacetyl-2,5-diketopiperazine; ammonium substituted nitriles, for example N-methylmorpholinioacetonitrile methylsulfate; acylating products of propylenediurea and 2,2-dimethylpropylenediurea, for example tetraacetylpropylenediurea; α-acyloxypolyacylmalonamides, for example α-acetoxy-N,N'-diacetylmalonamide; diacyldioxo-hexahydro-1,3,5-triazines, for example 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine; benz-(4H)-1,3-oxazin-4-ones with alkyl radicals, eg methyl, or aromatic radicals, eg phenyl, in position 2.
[00323] A bleaching system composed of the bleaches and bleach activators may optionally also comprise bleach catalysts. Suitable bleaching catalysts are, for example, quaternized imines or sulfonimines, described, for example, in US-A 5 360 569 and EP-A 453 003. Particularly effective bleach catalysts are manganese complexes, described, for example, in WO -A 94/21777. In the case that these are used in washing and cleaning compositions, such compounds are mostly incorporated in amounts up to 1.5% by weight, especially up to 0.5% by weight and in the case of very active manganese complexes in amounts up to 0 .1% by weight. In addition to the described bleaching system composed of bleaches, bleach activators and optionally bleach catalysts, it is also possible to use enzymatic peroxide release systems or photoactivated bleaching systems for inventive washing and cleaning compositions. Component e)
The inventive washing, cleaning and dish washing compositions may comprise water as additive e) (= component e1). In a specific embodiment, the inventive washing, cleaning and dish washing compositions comprise 0.1% to 80% by weight of water.
[00325] The inventive washing, cleaning and dish washing compositions generally already have advantageous rheological properties because of the polymer compositions present in the form of the especially aqueous liquid composition.
[00326] In order to impart the desired viscosity to the liquid and especially aqueous conditions of the inventive washing, cleaning and dishwashing compositions, it is additionally possible to use at least one thickener (= component e2) as component e).
[00327] In principle, any known thickeners (rheology modifiers) are suitable, as long as they do not exert any adverse effect on the action of the washing and cleaning composition. Suitable thickeners can be of natural origin or synthetic in nature.
[00328] Examples of thickeners of natural origin are xanthan, carob seed meal, guar meal, carrageenan, agar, tragacanth, gum arabic, alginates, modifying starches such as hydroxyethyl starch, starch phosphate esters or acetates of starch, dextrins, pectins and cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, methyl cellulose and others.
[00329] The thickeners of natural origin are also inorganic thickeners, such as polysilic acids and clay minerals, for example, lamina silicates and also the silicates specified by the reinforcers.
[00330] Examples of synthetic thickeners are polyacrylic and polymethacrylic compounds, such as homopolymers crosslinked (partially) of acrylic acid, for example, with an allyl ether of sucrose or pentaerythritol or homopolymers of acrylic acid crosslinked with propylene (carbomer), for example , Carbopol® products from BF Goodrich (eg Carbopol® 676, 940, 941, 934 and others) or Poligel® products from 3V Sigma (eg Poligel® DA), copolymers of ethylenically unsaturated mono- or dicarboxylic acids , for example, terpolymers of acrylic acid, methacrylic acid or maleic acid with methyl or ethyl acrylate and a (meth)acrylate which is derived from long chain ethoxylated alcohols, for example the Acusol® products from Rohm & Haas (for example , Acusol® 820 or 1206A), copolymers of two or more monomers, which are selected from acrylic acid, methacrylic acid and their C1-C4-alkyl esters, eg methacrylic acid copolymers, bu acrylate butyl and methyl methacrylate or butyl acrylate and methyl methacrylate, eg the products Aculyn® and Acusol® from Rohm & Haas (eg Aculyn® 22, 28 or 33 and Acusol® 810, 823 and 830), or copolymers of cross-linked high molecular weight acrylic acid, e.g. copolymers, cross-linked with an allyl ether of sucrose or pentaerythritol, of C10-C30-alkyl acrylates with one or more comonomers that are selected from acrylic acid, methacrylic acid and their C1-C4-alkyl esters (eg Carbopol® ETD 2623, Carbopol® 1382 or Carbopol® AQUA 30 from Rohm & Haas).
[00331] Examples of synthetic thickeners are also reaction products of maleic acid polymers with ethoxylated long-chain alcohols, for example, the Surfonic L series from Texaco Chemical Co. or Gantrez AN-119 from ISP; polyethylene glycols, polyamides, polyimines and polycarboxylic acids.
[00332] Mixtures of the aforementioned thickeners are also suitable.
The preferred thickeners are xanthans and the aforementioned polyacrylic and polymethacrylic compounds.
The inventive washing, cleaning and dish washing compositions may comprise at least one additional additive as additive e).
[00335] The surfactants from group e3) other than component a) can be cationic, anionic, zwitterionic or non-ionic. Suitable surfactants are those mentioned above by surfactant systems.
[00336] Suitable organic solvents e3) are selected from mono- or polyhydric alcohols, alkanolamines and glycol ethers. These are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane- or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or monoethyl ether, diisopropylene glycol monomethyl or monoethyl ether, methoxy, ethoxy or butoxytriglycol, i-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of the same solvents.
Foam inhibitors or defoamers useful for component e3) include, for example, soaps, paraffins or silicone oils, which can optionally be applied to the carrier materials.
[00338] Suitable bases for component e3) are alkali metal hydroxides, alkali earth metal hydroxides, alkali metal carbonates, alkali earth metal carbonates, ammonium carbonate, alkali metal hydrogencarbonates, alkali earth metal hydrogencarbonates, alkali hydrogencarbonate ammonium and mixtures thereof. Preference is given using sodium, lithium or magnesium carbonates or sodium, lithium and magnesium hydrogen carbonates, especially sodium carbonate and/or sodium hydrogen carbonate.
[00339] In addition, the inventive washing, cleaning or dish washing compositions may further comprise additives e) that further improve performance and/or aesthetic properties. In general, preferred compositions comprise, in addition to the aforementioned components, at least one additional additive selected from electrolytes, pH modifiers, perfume carriers, fluorescent agents, hydrotropes, anti-redeposition agents, optical brighteners, graying inhibitors, graying inhibitors. shrinkage, wrinkle inhibitors, dye transfer inhibitors, antimicrobial active ingredients, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, hydrophobizing and impregnating agents, swelling and antiskid agents, UV absorbers.
[00340] In order to improve the aesthetic impression of the compositions for washing, cleaning or washing inventive dishes, this can be colored with the appropriate pigments. The preferred pigments, the selection of which does not present difficulty independent of the person skilled in the art, have a high storage stability and insensitivity towards other ingredients of the compositions and to light and do not have any marked substantivity towards the textile fibers, in order not to stain them. Cleaners I & I
[00341] The inventive polymer compositions are especially suitable for industrial and institutional cleaners (I & I cleaners). Industrial and institutional cleaners are typically wash compositions, all-purpose cleaners, foam cleaners, gel cleaners, CIP (clean in place) cleaners for professional and generally automated cleaning operations, for example, in industrial laundries, dairy, breweries, the food and beverage industry, the pharmaceutical formulation or pharmaceutical industry, or sanitary cleaners.
[00342] Cleaners can be strongly basic with an electrolyte content and, if required, comprise bleaches (such as hydrogen peroxide, sodium hypochlorite) or disinfectants and defoamers (eg in bottle cleaning). It is also possible for the aforementioned standard enzymes to be present in industrial and institutional cleaners. There is a wide variety in terms of the types of cleaning for which the inventive formulations are suitable. Examples include cleaning baths (fixed or mobile), spray cleaning, ultrasound cleaning, steam jet cleaning and high pressure cleaning, optionally in combination with mechanical cleaning, for example by means of rotating brushes.
[00343] Said cleaning formulations include those for industrial transport, transport, commerce and industry and for the private sector. Specific examples include: professional laundries, professional cleaning businesses, ore processing industry, metal industry and metalworking, automotive and automotive supply industry, electrical industry, electronics industry, photographic industry and business, leisure industry and business , building material industry, fermented beverage manufacturing industry and business; food industry (eg processing and production of meat, poultry, dairy and fish products), animal nutrition industry, cosmetic industry, pharmaceutical industry, agrochemical industry, health sector, workshops and public transport. Examples of objectives to be cleaned are institutional laundry, hospital laundry, laundry collection laundry, buildings containing common spaces, office spaces or commercial spaces and a wide variety of different types and sanitary spaces, warehouses, breweries, businesses small ones, such as bakeries, slaughterhouses and supermarkets; hospitals, nursing homes, homes for the elderly, administration buildings, factory buildings, medical practices and also motor vehicles (cars and trucks), buses, road tankers (indoor and outdoor), rail tank cars, passenger vehicles and vehicles of goods and planes and ships and also building facades, tiled or painted walls, wooden walls (parquet, planks) with textile or plastic coverings, signaling and lighting installations, furniture, railings, suspended signage, other signage, safety reflectors , delineator markers, tanks, china, glass panels, roads and paths, external paving, road and railway tunnels. Film Applications
[00344] The invention further provides a process for producing an inventive polymer composition in the form of a film, wherein a polymer obtained by the process according to the invention, optionally after addition of at least one active ingredient and/or at least an additive, is subjected to a film forming operation, preferably selected from blow molding, thermoforming, melting and calendering.
[00345] With respect to the preferred and suitable polymer compositions for films, reference is made to the above remarks in total.
[00346] As explained above, for use in the form of a film, preference is given using the inventive flexible polymer compositions having a low glass transition temperature TG. Preferably, the inventive polymer compositions for use in the form of a film have a glass transition temperature TG in the range from 0 to 50°C, preferably from 5 to 20°C.
[00347] A specific embodiment is a process for producing an inventive polymer composition in the form of a film comprising at least one active ingredient. Suitable active ingredients are those already mentioned above as components b) to e), which reference is made here in full. The active ingredient is preferably selected from enzymes, enhancers, bleaches, surfactants, bases, corrosion inhibitors, defoamers, pigments, fragrances, fillers, tabletting aids, disintegrants, thickeners, solubilizers, organic solvents, electrolytes, pH modifiers, perfume carriers, fluorescent agents, hydrotropes, anti-redeposition agents, optical brighteners, graying inhibitors, shrinkage inhibitors, wrinkle inhibitors, dye transfer inhibitors, active antimicrobial ingredients, antioxidants, corrosion inhibitors, antistatic agents, ironing, hydrophobizing and impregnating agents, swelling and non-slip agents, UV absorbers and mixtures thereof.
[00348] A more specific embodiment is a process for producing an inventive polymer composition in the form of a film comprising at least enzyme. Suitable enzymes are those mentioned above as components c), which reference is made here in full.
[00349] For film production, additives can be added to the inventive polymer composition before and/or during film production. Additives for producing an inventive film are preferably selected from plasticizers, agents for modifying gas permeability and water vapor permeability, antistatics, lubricants, glidants, dissolution aids, dyes, pigments and mixtures thereof. In a specific execution, at least one plasticizer is added to the polymer material, which imparts permanent flexibility to the film and casing produced from these. Suitable plasticizers are alkylene glycols, oligoalkylene glycols, other polyols, alkyleneimines, oligoalkyleneimines and mixtures thereof. The plasticizer is preferably selected from glycerol, propylene glycol, diethylene glycol, triethylene glycol, sorbitol, diethyleneimine, triethyleneimine, and mixtures thereof.
[00350] In principle, the film production process is not subjected to any particular restrictions and the person skilled in the art, using a suitable inventive polymer composition, can use any desired production process known from the expert's knowledge. The same applies to the production of casings based on an inventive film. Extrusion processes and melting processes are particularly suitable.
[00351] In the production of films by extrusion, for example, a polymer composition obtained by the process according to the invention, optionally after addition of at least one active ingredient and/or at least one additive, is extruded, insufflated to a film in an insufflation process, or formed to a film in a thermoforming process, and the film thus obtained is optionally carried out in the appropriate form by wrapping the washing composition, dishwashing composition or portions of the cleaning composition.
[00352] In the production of films by melting, for example, a polymer composition obtained by the process according to the invention, optionally after addition of at least one additive, is melted or dissolved in a suitable solvent or solvent mixture, the composition of free-flowing polymer thus obtained is melted to form a film and the solvent or solvent mixture is optionally removed by evaporation.
[00353] Suitable solvents and solvent mixtures are those described above as component S), which reference is made here in full. The solvent is most preferably selected from water, ethanol, n-propanol, isopropanol, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,2-dipropylene glycol and mixtures thereof. In a specific embodiment, the solvent used is selected from water and a mixture of water and at least one solvent other than water, selected from ethanol, n-propanol, isopropanol, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,2-dipropylene glycol and mixtures thereof.
The inventive polymer compositions are generally thermoplastic and can be subjected to formation by thermoforming (i.e. heat formation, deep draw or deep vacuum draw). A process for producing the water-soluble film packages by a thermoforming process, which comprises a heat forming or deep draw-off step, is described in WO 00/55044.
[00355] For the production of the film portions, the film material can be processed in a suitable manner, for example, by cutting to a desired size and/or folding to form compartments. Subsequently the ends can be closed by common sealing processes such as heat sealing, liquid sealing or pressure sealing. Coatings
[00356] The invention further provides a process for producing an inventive polymer composition in the form of a coating on a substrate, wherein a polymer obtained by the process according to the invention, optionally after addition of at least one active ingredient and/ or at least one additive and/or at least one solvent and optionally while heating, is converted to a free-flowing form, applied to a substrate and allowed to solidify.
[00357] With respect to preferred polymer compositions suitable for coatings on a substrate, reference is made to the above remarks in full.
[00358] As explained above, for use in the form of a coating, preference is given using flexible inventive polymer compositions having a low glass transition temperature TG. Preferably, the inventive polymer compositions for use in the form of a coating have a glass transition temperature TG in the range from 0 to 50°C, preferably from 5 to 20°C.
[00359] A specific embodiment is a process for producing an inventive polymer composition in the form of a coating on a substrate, comprising at least one active ingredient. Suitable active ingredients are those already mentioned above as components b) to e), which reference is made here in full. The active ingredient is preferably selected from enzymes, enhancers, bleaching agents, surfactants, bases, corrosion inhibitors, defoamers, dyes, fragrances, fillers, tabletting aids, disintegrants, thickeners, solubilizers, organic solvents, electrolytes, oil modifiers pH, perfume carriers, fluorescent agents, hydrotropes, anti-redeposition agents, optical brighteners, graying inhibitors, shrinkage inhibitors, wrinkle inhibitors, dye transfer inhibitors, antimicrobial active ingredients, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, hydrophobizing and impregnating agents, swelling and non-slip agents, UV absorbers and mixtures thereof.
[00360] A more specific embodiment is a process for producing an inventive polymer composition in the form of a coating on a substrate, comprising at least one enzyme. Suitable enzymes are those mentioned above as components c), which reference is made here in full.
[00361] The additives for the production of the coatings can be added to the inventive polymer composition before and/or during the production of the coating. Additives for producing an inventive coating are preferably selected from those mentioned above for film formation. Reference is made to this in total.
[00362] Suitable solvents and solvent mixtures for the production of coatings are those described above as component S), which reference is made here in full. The solvent is most preferably selected from water, ethanol, n-propanol, isopropanol, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,2-dipropylene glycol and mixtures thereof. In a specific embodiment, the solvent used is selected from water and a mixture of water and at least one solvent other than water, selected from ethanol, n-propanol, isopropanol, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,2-dipropylene glycol and mixtures thereof.
[00363] The inventive polymer composition is suitable for producing coatings on substrates, such as washing, cleaning or dish washing tablet composition. The coatings obtained are soluble in water under the conditions of use. The linings are not brittle and generally mouthfeel pleasurable.
[00364] For applying the coating to a substrate, the inventive polymer composition can be used in molten form or dissolved in a solvent or a solvent mixture. Suitable application processes are known in principle to those skilled in the art and comprise common spray and dip application processes. Preference is given to spray application. In that case, the polymer composition can be used in molten form. Preferably, the polymer composition for spray application is in dissolved form in a solvent or solvent mixture. Finally, the solvent or solvent mixture can be removed by evaporation. Adhesive composition
[00365] The inventive polymer composition is suitable for the production of adhesive compositions that are adhesives, meaning that these are capable of bonding substrates, without any visible change in the substrates themselves, the coherence of the bonded substrates being determined by the adhesive forces (attractive forces between adhesive and substrate) and cohesion (internal cohesion of the adhesive).
[00366] Polymer compositions for preparing an adhesive composition are obtained by free radical polymerization of a monomer composition M) comprising at least one α,β-ethylenically unsaturated carboxylic acid A) as defined above. Preferred monomers A) are selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid. Acid groups can be in protonated form or in the form of their salts. Preferably, the monomer composition comprises 0.5% to 15% by weight, more preferably 1% to 10% by weight, based on the total weight of the monomer composition, of at least one α,β-ethylenically unsaturated carboxylic acid A ). Particular preference is given to acrylic acid.
Suitable comonomers are, for example, alkyl (meth)acrylates having a C1-C10-alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and ethyl acrylate. hexyl. In particular, mixtures of alkyl (meth)acrylates are also suitable. Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for example, vinyl laurate, vinyl stearate, vinyl propionate, vinyl versatate and vinyl acetate. Useful vinylaromatic compounds include vinyltoluene, α- and p-methylstyrene, α-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and, preferably, styrene. Examples of nitriles are acrylonitrile and methacrylonitrile. Vinyl halides are ethylenically unsaturated compounds substituted by chlorine, fluorine or bromine, preferably vinyl chloride and vinylidene chloride. Examples of vinyl ethers include vinyl methyl ether or vinyl isobutyl ether. Preference is given to the vinyl ethers of alcohols comprising 1 to 4 carbon atoms. Suitable hydrocarbons having 4 to 8 carbon atoms and two olefinic double bonds are, for example, butadiene, isoprene and chloroprene. Additional monomers are, for example, also monomers comprising hydroxyl groups, especially C1-C10-hydroxyalkyl (meth)acrylates or (meth)acrylamide. Additional monomers additionally include phenyloxyethyl glycol mono(meth)acrylate, glycidyl(meth)acrylate, aminoalkyl(meth)acrylates, for example, 2-aminoethyl(meth)acrylate. Alkyl groups preferably have 1 to 20 carbon atoms. Additional Monomers also include crosslinking monomers.
[00368] Preferred polyether components (PE) are the aforementioned polyetherols and especially polyethylene glycols.
[00369] The type and quantity of the monomers and the ratios of the different comonomers to one another are such that the glass transition temperature is within the aforementioned range.
[00370] The inventive adhesive compositions may comprise at least one solvent or dispersant. The solvent or dispersant in the adhesive composition may consist solely of water or mixtures of water and liquids miscible therewith, such as methanol or ethanol. Preference is given using water only. The pH of the adhesive composition is preferably adjusted to a pH greater than 4.5, especially a pH between 5 and 9.5.
[00371] The adhesive compositions may consist solely of the solvent and the polymer composition. The adhesive composition may, however, also comprise additional additives, for example fillers, pigments, leveling agents, thickeners (preferably associative thickeners), defoamers, pigments, wetting agents or thickeners (thickening resins). For better wetting of surfaces, adhesives may comprise wetting aids, for example, fatty alcohol ethoxylates, alkylphenol ethoxylates, nonylphenol ethoxylates, polyoxyethylenes, polyoxypropylenes or sodium dodecylsulfonate. The amount of the additives is generally 0.05 to 5 parts by weight, especially 0.1 to 3 parts by weight, per 100 parts by weight of polymer composition (solid).
[00372] In one embodiment, the adhesive composition is essentially free of plasticizers. Plasticizers are additives that decrease adhesive strength. "Essentially plasticizer free" means that the compositions comprise less than 1% by weight, preferably less than 0.5% by weight, based on the total composition, of the plasticizers and more preferably comprise no plasticizers at all.
[00373] The inventive adhesive composition is preferably a pressure sensitive adhesive. A pressure sensitive adhesive is a viscoelastic adhesive that sets to form a film at room temperature (20°C) that remains permanently tacky and adhesive in the dry state. Adhesion to substrates is effected immediately by light pressure.
[00374] The inventive adhesive composition can be used to bond at least two substrates or to produce self-adhesive articles. The self-adhesive substrates or articles to be bonded are at least partially coated with the pressure sensitive adhesive. Preferably, the self-adhesive articles are reseparable after bonding. Self-adhesive articles can, for example, be films, tapes or labels. Suitable carrier materials are, for example, paper, polymer films and metal foils. The inventive self-adhesive tapes can be tapes of the above substances coated on one or both sides. The inventive self-adhesive labels can be labels made of paper or a thermoplastic film. Useful thermoplastic films include, for example, polyolefin films (eg, polyethylene, polypropylene), polyolefin copolymers, polyester films (eg, polyethylene terephthalate) or polyacetate. The surfaces of thermoplastic polymer films have preferably been corona treated. Labels were coated with adhesive on one side. Preferred substrates for self-adhesive articles are paper and polymer films. The preferred self-adhesive items are paper labels.
[00375] The articles were at least partially coated with an inventive adhesive composition on at least one surface. The adhesive can be applied to articles by common methods such as coating or knife dispersing. The amount applied is preferably 0.1 to 20 g, more preferably 2 to 15 g, of solid per m2. Application may be followed by a drying step to remove water or solvents. Substrates which are bonded to one another or on which self-adhesive articles can be advantageously applied may, for example, be metal, wood, glass, paper or plastic. Self-adhesive articles are especially suitable for bonding to packaging surfaces, cardboard boxes, plastic packaging, books, windows, bodies, or body parts. Self-adhesive articles of the specific modalities can be removed from the articles again manually, without any adhesive residue remaining on the article. Adherence to articles is good; however, it is easily possible to remove the films, tapes and labels. Cosmetic and Pharmaceutical Compositions
[00376] The inventive polymer compositions are preferably suitable for formulating cosmetic and pharmaceutical products, especially aqueous cosmetic and pharmaceutical products.
[00377] The invention further provides a cosmetic or pharmaceutical preparation comprising a) at least one inventive polymer composition as defined above, b) at least one cosmetically or pharmaceutically acceptable active ingredient and c) optionally at least one cosmetically or pharmaceutically acceptable auxiliary other than which components a) and b).
[00378] Preferably, component c) comprises at least one cosmetically or pharmaceutically acceptable carrier.
[00379] Preferably, carrier component c) is selected from i) water, ii) water miscible organic solvents, preferably C2-C4 alkanols, especially ethanol, iii) oils, fats, waxes, iv) esters, other than iii ), C6-C30-monocarboxylic acids with mono-, di- or trihydric alcohols, v) cyclic and saturated acyclic hydrocarbons, vi) fatty acids, vii) fatty alcohols, viii) propellant gases, and mixtures thereof.
[00380] Suitable hydrophilic components c) are the aforementioned organic solvents, oils and fats.
Especially suitable cosmetically acceptable oil and fat components c) are described in Karl-Heinz Schrader, Grundlagen und Rezepturen der Kosmetika, 2nd edition, Verlag Hüthig, Heidelberg, p. 319-355, which is therefore incorporated by reference.
The inventive cosmetic compositions can be skin cosmetics, hair cosmetics, dermatological, pharmaceutical or hygiene products. The inventive polymer composition is also especially suitable for formulating the gels.
The inventive products are preferably in the form of a gel, foam, spray, ointment, cream, emulsion, suspension, lotion, milk or paste. If desired, it is also possible to use liposomes or microspheres. The inventive polymer composition is especially suitable for formulating gels.
[00384] The inventive cosmetic compositions may additionally comprise active and effective cosmetic and/or dermatological substances. Preferably, the inventive cosmetic compositions comprise at least one inventive polymer composition as defined above, at least one carrier C) as defined above and at least one different constituent preferably selected from cosmetic active ingredients, emulsifiers, surfactants, preservatives, perfume oils , additional thickeners, hair polymers, hair and skin conditioners, graft polymers, water-soluble or water-dispersible silicone-containing polymers, light stabilizers, bleaches, gel builders, care agents, paints, tanning agents, dyes, pigments, regulators consistency, humectants, regreasing agents, collagen, protein hydrolysates, lipids, antioxidants, defoamers, antistatics, emollients and softeners.
[00385] In addition to the inventive polymer compositions, cosmetic compositions may comprise at least one conventional thickener. These include, for example, polysaccharides and organic lamina minerals such as Xanthan Gum® (Kelzan® from Kelco), Rhodopol® 23 (Rhone Poulenc) or Veegum® (from R.T. Vanderbilt) or Attaclay® (from Engelhardt). Suitable thickeners are also natural organic thickeners (agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polioses, guar flour, carob seed flour, starch, dextrins, gelatin, casein) and inorganic thickeners (polysilicic acids , clay minerals such as montmorillonites, zeolites, silicas). Additional thickeners are polysaccharide gums, e.g. gum arabic, agar, alginates, carrageenans and salts thereof, guar, guaran, tragacanth, gellan, ramsan, dextran or xanthan, and derivatives thereof, e.g., propoxylated guar, and mixtures thereof. same. Other polysaccharide thickeners are, for example, starches from a wide variety of different origins and starch derivatives, for example, hydroxyethyl starch, starch phosphate esters or starch acetates, or carboxymethyl cellulose or the sodium salt thereof, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose or hydroxyethyl methyl cellulose, or cellulose acetate. The thickeners used can additionally be sheet silicates. These include, for example, magnesium or sodium-magnesium lamina silicates obtained under the trade name Laponite ® from Solvay Alkali and magnesium silicates from Süd-Chemie.
[00386] The cosmetically and/or dermatologically active ingredients are, for example, skin and hair pigmentation agents, tanning agents, bleaches, keratin hardening substances, antimicrobials, light filtering agents, repelling agents, hyperemic agents, keratolytic agents or keratoplastics, anti-dandruff agents, antiphlogistic agents, keratinizing agents, antioxidant and free radical scavengers, skin unitizers or moisturizers, regreasing agents, deodorizing agents, sebostatic agents, plant extracts, anti-erythematous or anti-inflammatory active ingredients allergy sufferers and mixtures thereof.
[00387] Suitable artificial tanning agents for tanning the skin without natural or artificial irradiation with UV rays are, for example, dihydroxyacetone, alloxane and walnut shell extract. Suitable keratin hardening substances are generally active ingredients as used also in antiperspirants, eg potassium aluminum sulphate, aluminum hydroxychloride, aluminum lactate, etc. Antimicrobials are used to destroy microorganisms or to inhibit their development and thus be both a preservative and a deodorant that reduces the formation or intensity of body odor. These include, for example, common preservatives known to a person skilled in the art, such as p-hydroxybenzoic esters, imidazolidinyl urea, formaldehyde, sorbic acid, benzoic acid, salicylic acid, etc. Such deodorizing substances are, for example, zinc ricinoleate, triclosan, undecylenic acid alkylamides, triethyl citrate, chlorhexidine etc. Suitable light filtering agents are substances that absorb UV rays in the UV-B and/or UV-A region. Suitable UV filters are those mentioned above. Further suitable are p-aminobenzoic esters, cinnamic esters, benzophenones, camphor derivatives and pigments which interrupt UV rays such as titanium dioxide, talc and zinc oxide. Suitable repellent agents are compounds capable of repelling or scaring certain animals, particularly insects, away from humans. These include, for example, 2-ethyl-1,3-hexanediol, N,N-diethyl-m-toluamide etc. Suitable substances with hyperemic activity in which it stimulates blood flow through the skin are, for example, essential oils such as dwarf pine, lavender, rosemary, juniper berry, roasted chestnut extract, birch leaf extract, grass seed, ethyl acetate, camphor, menthol, peppermint oil, rosemary extract, eucalyptus oil, etc. Suitable keratolytic and keratoplastic substances are, for example, salicylic acid, calcium thioglycolate, thioglycolic acid and its salts, sulfur, etc. Suitable anti-dandruff agents are, for example, sulfur, sulfur monooleate polyethylene glycol sorbitan, polysulfur polyethoxylate ricinol, zinc pyrithione, aluminum pyrithione, etc. Suitable antiphlogistic agents, which neutralize skin irritations, are, for example, allantoin, bisabolol, Dragosantol, chamomile extract, panthenol, etc.
[00388] The inventive cosmetic compositions may comprise, as a cosmetically active ingredient (and also optionally as an auxiliary), at least one cosmetically or pharmaceutically acceptable polymer. These include, in very general terms, anionic, cationic, amphoteric and uncharged polymers.
[00389] Examples of anionic polymers are copolymers of acrylic acid and acrylamide and salts thereof; sodium salts of polyhydroxycarboxylic acids, water-dispersible or water-soluble polyesters, polyurethanes, eg Luviset PUR® from BASF and polyureas. Particularly suitable polymers are copolymers of t-butyl acrylate, ethyl acrylate, methacrylic acid (eg Luvimer® 100P), copolymers of ethyl acrylate and methacrylic acid (eg Luvimer® MAE), N-tert copolymers -butylacrylamide, ethyl acrylate, acrylic acid (Ultrahold® 8, strong), vinyl acetate copolymers, crotonic acid and optionally additional vinyl esters (eg Luviset® products), maleic anhydride copolymers, optionally reacted with alcohol, polysiloxanes anionics, eg carboxy-functional, t-butyl acrylate, methacrylic acid (eg Luviskol® VBM), copolymers of acrylic acid and methacrylic acid with hydrophobic monomers, eg C4-C30-alkyl esters of acid (meth )acrylic, C4-C30-alkyl vinyl ethers, C4-C30-alkyl vinyl ethers and hyaluronic acid. Another example of an anionic polymer is the methyl methacrylate/methacrylic acid/acrylic acid/urethane acrylate copolymer obtained under the name Luviset® Shape (INCI name: Polyacrylate-22). Additional examples of anionic polymers are vinyl acetate/crotonic acid copolymers, as commercially available, for example, under the names Resyn® (National Starch) and Gafset® (GAF) and vinylpyrrolidone/vinyl acrylate copolymers obtained, for example , under the trade name Luviflex® (BASF). Additional suitable polymers are vinylpyrrolidone/acrylate terpolymer available under the name Luviflex® VBM-35 (BASF) and polyamides containing sodium sulphonate or polyesters containing sodium sulphonate. Further suitable are vinylpyrrolidone/ethyl methacrylate/methacrylic acid copolymers as sold by Stepan under the names Stepanhold-Extra and -R1 and the Carboset® products from BF Goodrich.
[00390] Suitable cationic polymers are, for example, cationic polymers having the name Polyquaternium INCI, for example vinylpyrrolidone/N-vinylimidazolium salts copolymers (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviset Clear®, Luviquat Supreme®, Luviquat® Care), N-vinylpyrrolidone/dimethylaminoethyl methacrylate copolymers, quaternized with diethyl sulfate (Luviquat® PQ 11), N-vinylcaprolactam/N-vinylpyrrolidone/N-vinylimidazolium salts (Luviquat® Hold) copolymers ; cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-7) and chitosan. Suitable cationic polymers (quaternized) are also Merquat® (polymer based on dimethyldiallylammonium chloride), Gafquat® (quaternary polymers that form through the reaction of polyvinylpyrrolidone with quaternary ammonium compounds), polymer JR (hydroxyethyl cellulose with cationic groups) and vegetable-based cationic polymers, eg guar polymers such as Jaguar® products from Rhodia.
Particularly very suitable polymers are uncharged polymers such as polyvinylpyrrolidones, copolymers of N-vinylpyrrolidone and vinyl acetate and/or vinyl propionate, polysiloxanes, polyvinylcaprolactam and other copolymers with N-vinylpyrrolidone, polyethyleneimines and salts thereof, polyvinylamines and salts thereof, cellulose derivatives, polyaspartic salts and derivatives. Examples of these include Luviflex® Swing (partially hydrolyzed copolymer of polyvinyl acetate and polyethylene glycol, from BASF).
Suitable polymers are also non-ionic water-dispersible or water-soluble polymers or oligomers, such as polyvinylcaprolactam, for example, Luviskol® Plus (BASF SE), or polyvinylpyrrolidone and copolymers thereof, especially with vinyl esters such as acetate. vinyl, for example Luviskol® VA 37, VA 55, VA 64, VA 73 (BASF SE); polyamides, for example, based on itaconic acid and aliphatic diamines, as described, for example, in DEA-43 33 238.
[00393] Suitable polymers are also amphoteric or zwitterionic polymers, such as copolymers of octyl acrylamide/methyl methacrylate/tert-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate obtained under the names Amphomer® (National Starch) and zwitterionic polymers such as disclosed, for example, in German Patent Applications DE 39 29 973, DE 21 50 557, DE 28 17 369 and DE 37 08 451. Copolymers of acrylamidopropyltrimethylammonium chloride/acrylic acid or methacrylic acid and alkali metal and ammonia salts thereof zwitterionic polymers are preferred. Additional suitable zwitterionic polymers are methacryloylethyl betaine/methacrylate copolymers, commercially available under the name Amersette® (AMERCHOL) and copolymers of hydroxyethyl methacrylate, methyl methacrylate, N,N-dimethylaminoethyl methacrylate and acrylic acid (Jordapon®).
[00394] Suitable polymers are also water-dispersible or water-soluble polymers containing non-ionic siloxane, for example polyethersiloxanes such as Tegopren® (Goldschmidt) or Belsil® (Wacker).
[00395] In a specific embodiment, the inventive compositions comprise at least one polymer that acts as a thickener.
[00396] Suitable polymeric thickeners are, for example, optionally modified polymeric natural substances (carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and hydroxypropyl cellulose and others) and synthetic polymeric thickeners (polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers , polyimines, polyamides). These include polyacrylic and polymethacrylic compounds, some of which have already been mentioned above, for example high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, especially an allyl ether of sucrose, pentaerythritol or propylene (INCI name: Carbomer) . Polyacrylic acids of this group are obtained, inter alia, from BF Goodrich under the trade name Carbopol ®, for example, Carbopol 940 (molecular weight about 4,000,000 daltons), Carbopol 941 (molecular weight about 1250,000 daltons) or Carbopol 934 (molecular weight about 3,000,000 daltons). These additionally include acrylic acid copolymers obtained, for example, from Rohm & Haas under the trade names Aculyn ® and Acusol ®, for example the non-ionic non-associative polymers Aculyn 22, Aculyn 28, Aculyn 33 (crosslinked), Acusol 810, Acusol 823 and Acusol 830 (CAS 25852-37-3). Also particularly suitable are associative thickeners, for example based on modified polyurethanes (HEUR) or hydrophobically modified acrylic or methacrylic acid copolymers (HASE thickeners, High Alkaline Swellable Emulsion).
[00397] In a preferred embodiment, the inventive product is a skin cleanse.
[00398] Skin purifiers are soaps of liquid to gel consistency, such as clear soaps, luxury soaps, deodorant soaps, cream soaps, baby soaps, skin protection soaps, abrasive soaps and syndets, pasty soaps, soaps greasy and wash pastes, liquid wash, shower and bath preparations such as wash lotions, shower baths and gels, bubble baths, oil baths and scrub preparations, having foams, lotions and creams.
[00399] Still in a preferred embodiment, the inventive products are cosmetic compositions for skin care and protection, nail care products or preparations for decorative cosmetics.
[00400] Suitable skin cosmetic compositions are, for example, facial tonics, facial masks, deodorants and other cosmetic lotions. Products for use in decorative cosmetics include, for example, corrective sticks, makeup in stages, eye mask and shadow, lipsticks, eyeliners, blushes, powders and eyebrow pencils.
[00401] Furthermore, the inventive polymer compositions can be used in nasal strips for cleaning pores, in anti-acne compositions, repellents, having compositions, hair removal compositions, intimate care compositions, foot care compositions and in care with the baby.
[00402] More particularly, inventive skin care products are skin creams W/O or O/W, daily and night creams, eye creams, facial creams, anti-wrinkle creams, moisturizing creams, whitening creams, vitamin creams, skin lotions, care lotions and moisturizing lotions.
[00403] Dermatological and skin cosmetic products based on the inventive polymer compositions described above show the advantageous effects. One effect of polymers is to contribute to moisturizing and conditioning the skin and to an improvement in skin feel. Through the addition of the inventive polymers, it is possible in certain formulations to achieve a considerable improvement in skin compatibility.
[00404] Dermatological and skin cosmetic products preferably comprise at least one inventive polymer composition in a proportion of about 0.001 to 30% by weight, preferably 0.01 to 20% by weight, more preferably 0.1 to 12% by weight, based on the total weight of the product.
[00405] According to the field of use, the inventive compositions can be applied in a form suitable for skin care, for example, in the form of a cream, foam, gel, stick, mousse, milk, spray (spray by pump or spray containing propellant) or lotion.
[00406] As well as inventive polymer compositions and suitable carriers, skin cosmetic preparations may also comprise additional active ingredients and auxiliaries common in skin cosmetics as described above. These preferably include emulsifiers, preservatives, perfume oils, cosmetic active ingredients such as phytantriol, vitamin A, E and C, retinol, bisabolol, panthenol, light stabilizers, bleaches, tanning agents, collagen, protein hydrolysates, stabilizers, pH regulators , pigments, salts, thickeners, gel builders, consistency regulators, silicones, humectants, regreasing agents and additional common additives.
[00407] The preferred fat oil components of dermatological and skin cosmetic products are the aforementioned mineral and synthetic oils, for example, paraffins, silicone oils and aliphatic hydrocarbons having more than 8 carbon atoms, animal and vegetable oils , for example, sunflower oil, coconut oil, avocado oil, olive oil, lanolin, or waxes, fatty acids, fatty acid esters, for example, C6-C30 fatty acid triglycerides, wax esters, for example , jojoba oil, fatty alcohols, petroleum jelly, hydrogenated lanolin and acetylated lanolin, and mixtures thereof.
[00408] It is also possible to combine the inventive polymer composition with conventional polymers as described above, if specific properties will be established.
[00409] To establish particular properties, for example, improving tactile properties, expansion characteristics, water resistance and/or binding of active and auxiliary ingredients, such as pigments, dermatological and cosmetic skin preparations can also further comprise conditioning substances based on silicone compounds. Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or silicone resins.
[00410] Dermatological or cosmetic preparations are produced by the common methods known to that person skilled in the art.
[00411] Preferably, dermatological and cosmetic products are in the form of emulsions, especially water-in-oil (W/O) or oil-in-water (O/W) emulsions. However, it is also possible to choose other types of formulation, for example, hydrodispersions, gels, oils, oleogels, multiple emulsions, for example, in the form of W/O/W or O/W/O emulsions, anhydrous ointments or ointment bases , etc.
[00412] Emulsions are produced by known methods. As well as at least one inventive polymer composition, emulsions generally comprise customary constituents such as fatty alcohols, fatty acid esters and especially fatty acid triglycerides, fatty acids, lanolin and derivatives thereof, natural or synthetic oils, or waxes and emulsifiers in the presence of water. The selection of additives specific to the type of emulsion and the production of suitable emulsions is described, for example, in Schrader, Grundlagen und Rezepturen der Kosmetika, Hüthig Buch Verlag, Heidelberg, 2nd edition, 1989, part three, which is therefore explicitly incorporated by reference.
[00413] A suitable emulsion, for example by a skin cream etc., generally comprising an aqueous phase which has been emulsified by means of a suitable emulsifier system into an oil phase or grease phase.
The preferred fatty components that may be present in the grease phase of emulsions are: hydrocarbon oils such as paraffin oil, purcellin oil, perhydrosqualene and solutions of the microcrystalline waxes in these oils; animal or vegetable oils such as sweet almond oil, avocado oil, calophylum oil, lanolin and derivatives thereof, castor oil, sesame oil, olive oil, jojoba oil, shea oil, hoplostethus oil; mineral oils having an initial boiling point under atmospheric pressure of about 250°C and a final boiling point of 410°C, for example petroleum jelly; esters of saturated or unsaturated fatty acids, such as alkyl myristates, for example isopropyl, butyl or cetyl myristate, hexadecyl stearate, ethyl or isopropyl palmitate, octanoic or decanoic acid triglycerides and cetyl ricinoleate.
[00415] The grease phase can also comprise silicone oils soluble in other oils, such as dimethylpolysiloxane, methylphenylpolysiloxane and the copolymer of silicone glycol, fatty acids and fatty alcohols.
[00416] It is also possible to use waxes, for example, carnauba wax, candililla wax, beeswax, microcrystalline wax, ozokerite wax and Ca, Mg and Al oleates, myristates, linoleates and stearates.
[00417] Furthermore, an inventive emulsion can take the form of an O/W emulsion. Such an emulsion typically comprises an oil phase, emulsifiers which stabilize the oil phase in the aqueous phase and an aqueous phase which is usually in thick form. Useful emulsifiers are preferably O/W emulsifiers, such as polyglyceryl esters, sorbitan esters or partially esterified glycerides.
[00418] Still in a preferred embodiment, the inventive products are a shower gel, a shampoo formulation or a shower preparation.
[00419] The formulations of this group comprise at least one inventive polymer composition and typically anionic surfactants as base surfactants and amphoteric and/or nonionic surfactants as cosurfactants. Further suitable active ingredients and/or auxiliaries are generally selected from lipids, perfume oils, pigments, organic acids, preservatives and antioxidants as well as thickeners/gel builders, skin conditioners and humectants.
These formulations preferably comprise 2% to 50% by weight, preferably 5% to 40% by weight, more preferably 8% to 30% by weight, of surfactants, based on the total weight of the formulation.
[00421] In washing, shower and bath preparations, it is possible to use any of the anionic, uncharged, amphoteric or cationic surfactants commonly used in personal care products.
[00422] Suitable surfactants are those mentioned above.
[00423] In addition, shower gel/shampoo formulations may comprise additional thickeners, for example, sodium chloride, PEG-55, propylene glycol oleate, PEG-120 methylglucose dioleate and others and also preservatives, additional active ingredients and auxiliaries and water.
[00424] In another preferred embodiment, the inventive product is a hair care product.
[00425] The inventive hair care compositions preferably comprise at least one inventive polymer composition in an amount ranging from about 0.1% to 30% by weight, preferably from 0.5% to 20% by weight, based on the total weight of the product.
Preferably, the inventive hair care compositions are in the form of a fixative foam, hair mousse, hair gel, shampoo, hair spray, hair foam, tip fluid, permanent wave neutralizer or hot oil treatment. Depending on the area of application, hair cosmetic preparations can be applied in the form of spray (aerosol), foam (aerosol), gel, gel spray, cream, lotion or wax. Capillary sprays encompass both aerosol sprays and pump sprays without propellant gas. Capillary foams include both aerosol foams and non-propellant gas pump foams. Hair sprays and hair foams preferably comprise predominantly or exclusively water-soluble or water-dispersible components. If the compounds used in the inventive capillary sprays and capillary foams are water dispersible, they can be used in the form of aqueous microdispersions having particle diameters of typically 1 to 350 nm, preferably 1 to 250 nm. The solids contents of those preparations are typically within a range of about 0.5% to 20% by weight. These microdispersions, in general, do not require any emulsifiers or surfactants for their stabilization.
[00427] In a preferred embodiment, the inventive hair cosmetic formulations comprise a) 0.05% to 5% by weight, preferably 0.1% to 3% by weight, of at least one inventive polymer composition, b) 20% to 99.95% by weight of water and/or alcohol, c) 0% to 50% by weight of at least one propellant gas, d) 0% to 5% by weight of at least one emulsifier, e) 0.05 % to 5% by weight of at least one cosmetically active ingredient and f) 0% to 20% by weight, preferably 0.1% to 10% by weight, of at least one other water-soluble or water-dispersible polymer other than from a) to e) and g), g) 0% to 45% by weight, preferably from 0.05% to 25% by weight, of other constituents, h) of the components from a) to g) add up to 100% by weight .
[00428] "Alcohol" is understood to mean any alcohols customary in cosmetics, eg ethanol, isopropanol, n-propanol.
[00429] "Additional constituents" is understood to mean the usual additives in cosmetics, for example, propellants, defoamers, interface active compounds, i.e. surfactants, emulsifiers, foam enhancers and solubilizers. The active interface compounds used can be anionic, cationic, amphoteric or uncharged. Additional custom constituents can also be, for example, preservatives, perfume oils, opacifiers, active ingredients, UV filters, care substances such as panthenol, collagen, vitamins, protein hydrolysates, alpha- and beta-hydroxycarboxylic acids , stabilizers, pH regulators, pigments, viscosity regulators, gel builders, salts, humectants, regreasing agents, complexing agents and additional custom additives.
[00430] Also included herein are styling polymers and conditioners known in cosmetics that can be used in combination with the inventive polymers, if many specific properties are to be established.
[00431] Suitable conventional hair cosmetic polymers are, for example, the aforementioned cationic, anionic, uncharged, nonionic and amphoteric polymers, which reference is made here.
[00432] To establish certain properties, the preparations can additionally also comprise conditioning substances based on silicone compounds. Suitable silicone compounds are, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes, silicone resins or dimethicone copolyols (CTFA) and aminofunctional silicone compounds such as amodimethicones (CTFA).
[00433] The inventive polymer compositions are especially suitable as thickeners in hair styling formulations, especially hair foams and hair gels.
[00434] The emulsifiers used can be any of the usual emulsifiers used in capillary foams. Suitable emulsifiers can be non-ionic, cationic or anionic or amphoteric.
[00435] The inventive polymer compositions are also suitable for styling gels. The additional gel builders used can be any of the usual cosmetic gel builders. In this regard, reference is made to the conventional thickeners mentioned above.
[00436] The inventive polymer compositions are also suitable for shampoo formulations which additionally comprise customary surfactants.
[00437] In shampoo formulations, particular effects can be achieved using customary conditioners in combination with the inventive polymer compositions. Examples of these include the cationic polymers mentioned above under the name INCI Polyquaternium, especially vinylpyrrolidone/N-vinylimidazolium salts copolymers (Luviquat® FC, Luviquat® HM, Luviquat® MS, Luviquat® Care), N-vinylpyrrolidone/methacrylate copolymers of dimethylaminoethyl, quaternized with diethyl sulfate (Luviquat® PQ 11), N-vinylcaprolactam/N-vinylpyrrolidone/N-vinylimidazolium salts (Luviquat® Hold) copolymers; cationic cellulose derivatives (Polyquaternium-4 and -10), acrylamide copolymers (Polyquaternium-7). Furthermore, it is possible to use protein hydrolysates and conditioning substances based on silicone compounds, for example, polyalkylsiloxanes, polyarylsiloxanes, polyarylalkylsiloxanes, polyethersiloxanes or resins and silicone. Additional suitable silicone compounds are dimethicone copolyols (CTFA) and amino-functional silicone compounds such as amodimethicones (CTFA). In addition, it is possible to use cationic guar derivatives such as guar hydroxypropyltrimonium chloride (INCI).
[00438] The inventive polymer compositions are equally suitable for use in pharmaceutical formulations of any type and in coating such pharmaceutical formulations.
The invention further provides the use of a compound of formula (I) or formula (I.1) as defined above as an aid in pharmacy.
Typical pharmaceutical compositions comprise A) at least one inventive polymer composition as defined above, B) at least one pharmaceutically acceptable active ingredient and C) optionally at least one additional pharmaceutically acceptable auxiliary other than A) and B).
[00441] Pharmaceutically acceptable auxiliaries C) are auxiliaries which are known to be usable in the field of pharmacy, food technology and related fields, especially those listed in the relevant pharmacopoeias (eg DAB, Ph. Eur., BP, NF) and other auxiliaries whose properties do not impede physiological application.
[00442] Suitable auxiliaries C) may be: lubricants, wetting agents, emulsifiers and suspending media, preservatives, antioxidants, anti-irritants, chelating agents, emulsion stabilizers, film reinforcers, gel reinforcers, odor masking agents , resins, hydrocolloids, solvents, solubilizers, neutralizers, permeation accelerators, pigments, quaternary ammonium compounds, regreasing and super-greasing agents, ointment, creamy and oily bases, silicone derivatives, stabilizers, sterilants, propellants, desiccants, opacifiers, additional thickeners, waxes, plasticizers, white oils. This type of configuration is based on expert knowledge, as represented, for example, in Fiedler, HP Lexikon der Hilfsstoffe für Pharmazie, Kosmetik und angrenzende Gebiete [Lexicon of Auxiliaries for Pharmacy, Cosmetics and Related Fields], 4th ed., Aulendorf: ECV-Editio-Kantor-Verlag, 1996.
[00443] To produce the inventive pharmaceuticals, the active ingredients can be mixed or diluted with a suitable excipient. Excipients can be solid, semi-solid, or liquid materials that can serve as a vehicle, carrier or medium for the active ingredient. Additional helpers are added, if desired, in a manner known to a person skilled in the art. More particularly, these are aqueous solutions or solubilized for oral or parenteral administration. Furthermore, the copolymers for use according to the invention are also suitable for use in oral administration forms such as tablets, capsules, powders, solutions. Here, they can provide the poorly soluble drug with increased bioavailability. In the case of parenteral administration, as well as solubilizers, it is also possible to use emulsions, for example, fatty emulsions.
[00444] Pharmaceutical formulations of the type specified above can be obtained by processing the inventive polymer composition with pharmaceutically active ingredients by conventional methods and using conventional methods and using known and new active ingredients.
[00445] Depending on the active ingredient, the content of at least one inventive polymer composition in the pharmaceutical compositions is in the range from 0.01% to 50% by weight, preferably from 0.1% to 40% by weight, particularly preferably 1% to 30% by weight, based on the total weight of the product.
[00446] For the production of inventive pharmaceuticals, all pharmaceutically active ingredients and prodrugs are suitable in principle. These include benzodiazepines, antihypertensives, vitamins, cytostatics, especially taxol, anesthetics, neuroleptics, antidepressants, antibiotics, antimycotics, fungicides, chemotherapeutics, utologics, platelet aggregation inhibitors, sulfonamides, spasmolytics, hormones, immunoglobulins, serums, thyroid therapeutics , psychopharmaceuticals, Parkinson's drugs and other antihyperkinetics, ophthalmics, neuropathy preparations, calcium metabolism regulators, muscle relaxants, narcotics, antilipemics, liver therapeutics, coronary drugs, cardiac drugs, immunotherapeutics, regulatory peptides and their inhibitors, hypnotics , sedatives, gynecological drugs, gout drugs, fibrinolytics, enzyme preparations and transport proteins, enzyme inhibitors, emetics, perfusion promoters, diuretics, diagnostics, corticosteroids, cholinergics, biliary therapeutics, antiasthmatics, broncholytics, blockers of beta-receptors, calcium antagonists, ACE inhibitors, drugs against arteriosclerosis, antiphlogistics, anticoagulants, antihypotensives, antihypoglycemics, antihypertensives, antifibrinolytics, antiepileptics, antiemetics, antidotes, antidiabetics, antiarrhythmics, anti-allergics, anti-allergics, -helminthics, analgesics, analeptics, aldosterone antagonists and weight-loss drugs. Examples of suitable pharmaceutically active ingredients are especially the active ingredients mentioned in paragraphs 0105 to 0131 of US 2003/0157170.
[00447] As well as use in cosmetics and pharmacy, inventive polymer compositions are also suitable in the food and beverage sector. In the context of the present invention, food and beverage preparations are also understood to mean food supplements, for example preparations comprising food and beverage pigments and diet foods and beverages. Furthermore, the inventive polymer compositions are also suitable for nutritional supplements for animal nutrition.
[00448] The inventive polymer compositions are also suitable for the production of food supplement formulations such as water-insoluble vitamins and provitamins such as vitamin A, vitamin A acetate, vitamin D, vitamin E, tocopherol derivatives , such as tocopherol acetate and vitamin K. External coatings for pharmaceutical administration forms
[00449] The polymeric compositions described above are exceptionally suitable for the production of pharmaceutical compositions. These serve, for example, as polymeric film reinforcers, especially for the production of coating films for pharmaceutical administration forms.
The formulation basis for inventive coating films for pharmaceutical administration forms may comprise at least one of the additional pharmaceutically acceptable auxiliaries mentioned above for pharmaceutical formulations.
[00451] Suitable auxiliaries can be: flavorings, flavor enhancers, sweetening agents (sugars, sugar alcohols, sweeteners, for example, aspartame, saccharin-Na, sodium cyclamate), glidants, wetting agents, release agents, plasticizers, anti-adhesives, antioxidants, stabilizers, pore reinforcers, neutralizing agents, brighteners, dyes, pigments, disinfectants or preservatives, thickeners, etc. Substances of this type are described, for example, in Fiedler, H.P. Lexikon der Hilfsstoffe für Pharmazie, Kosmetik und angrenzende Gebiete, 4th edition, Aulendorf: ECV-Editio-Cantor-Verlag, 1996.
The usual amounts of auxiliaries are within a range from 0% to 50% by weight, preferably from 0% to 20% by weight, especially from 0.01% to 10% by weight, based on the total weight of the coating film.
[00453] Coating films can be produced, for example, by intimately mixing an inventive polymer composition with at least one auxiliary. In a particularly preferred embodiment, the inventive polymer composition is used as gels, without prior drying, to produce a coating film. However, it is also possible to first subject an inventive polymer composition to a drying operation and to use the polymer composition thus obtained to produce a coating. The polymer composition can then be used, for example, in powder form or as a melt or solution to produce the coating.
[00454] The invention further provides a coating film comprising such an aqueous polymer composition or a polymer composition obtainable therefrom by drying.
[00455] The invention further provides a pharmaceutical composition comprising A) at least one inventive polymer composition, B) at least one pharmaceutically acceptable active ingredient and C) optionally at least one pharmaceutically acceptable auxiliary.
[00456] The inventive polymer compositions can serve in pharmaceutical compositions, for example, to produce a binder or a coating film. The functional effect here, in general, arises as a result of drying and/or filming of the coating film or binder. This drying and/or film formation can proceed, without regard to the application process, through the energy supply. This can be accomplished through convection (heat), radiation (infrared or microwave) or conduction. The water used as a dispersant for the application evaporates in the process and reduced pressure can also optionally be applied in order to accelerate evaporation.
[00457] The inventive coating film can be used, for example, in powder form or as a melt through pelletizing, melting, spreading or by means of spray application. The inventive coating film may additionally comprise at least one additional polymer component.
[00458] The inventive formulation is suitable for administering basically any desired pharmaceutically active ingredients that can preferably be administered in isolated or protected form, such as antidepressants, beta receptor blockers, antidiabetics, analgesics, antiphlogistics, antirheumatics, antihypotensives, anti- hypertensives, psychopharmaceuticals, tranquilizers, antiemetics, muscle relaxants, glucocorticoids, medicines for the treatment of ulcerative colitis or Crohn's disease, antiallergics, antibiotics, antiepileptics, anticoagulants, antimycotics, antitussives, medicines against arteriosclerosis, diuretics, enzymes, enzyme inhibitors , drugs against gout, hormone and inhibitors thereof, cardiac glycosides, immunotherapeutics and cytokines, laxatives, lipid-lowering agents, gastrointestinal therapeutics, migraine drugs, mineral substance preparations, otologicals, drugs against Parkinson's disease, tera thyroid drugs, spasmolytics, thrombocyte aggregation inhibitors, vitamins, cytostatics and metastasis inhibitors, phytopharmaceuticals, chemotherapeutics, nutraceuticals, vitamins, carotenoids and amino acids.
[00459] The inventive polymer compositions are preferably used for coatings of tablet, extrudates, mini-tablets, capsules, soft capsules, granules, pellets, micropellets, microcapsules, crystals. Coated granules, pellets, micropellets, microcapsules, crystals can be included with suitable auxiliaries and tablets to give tablets which quickly disintegrate in water and release the coated thin moldings. In this way, it is possible to reduce what are called MUPS forms, multiple unit particulate systems. These are tablets which, after being ingested, disintegrate and release the subunits coated with an inventive coating composition. Of particular importance in this context are what are termed oral dispersibles, i.e. tablets which disintegrate in the mouth within a short time and release small molds with masked taste.
[00460] In a specific variant, the inventive polymer compositions are used to pellet the active ingredients, optionally with corresponding auxiliaries, and the pellets are then compressed into tablets.
[00461] The inventive polymer compositions can also be used to produce transdermal active ingredient patches or sprays.
[00462] The inclusion of pellets in polyethylene glycol or lipids is also suitable for the production of suppositories or vaginal drug forms.
[00463] The classes of ingredients and active substances that can often cause a bitter taste and can be advantageously formulated with the inventive film and coating binder are, for example: Analgesics and antirheumatics, such as paracetamol, diclofenac, aceclofenac, ibuprofen, ketoprofen , flubiprofen, acetylsalicylic acid, levacetylmethadol and oxycodone; Psychopharmaceuticals such as promethazine, donepezil, modafinil, nefazodon, reboxetine, sertindole and sertraline; Antibiotics such as erythromycin, roxithromycin, clarithromycin, grepafloxacin, ciprofloxacin, levofloxacin, sparfloxacin, trovafloxacin and nevirapine; Beta blockers such as propranolol, metoprolol, bisoprolol and nebivolol; Antidiabetics such as metformin, miglitol and repaglinide; H1 antihistamines, such as diphenhydramine, fexofenadine and mizolastine; H2 antihistamines, such as cimetidine, famotidine, roxatidine, nizatidine, ticlopidine, cetirizine and ranitidine; Vitamins such as thiamine nitrate and quinidine sulfate, amyloprilose HCl, pseudoephedrine HCl, sildenafil, topiramate, granisetron, rebamipide, quinine HCl, etc.
[00464] The inventive coating films have a low water vapor and oxygen permeability and therefore allow the formulation and stabilization of drugs that are particularly sensitive to water vapor or oxygen, for example, acetylsalicylic acid, enalapril, acetate. cortisone, omeprazole, carotenoids. In this case, the coating is protective.
[00465] In addition, inventive coatings can be used for separation of incompatible active ingredients or auxiliaries in the administration forms by involving one or more constituents and thus avoiding mutual contact.
[00466] The unexpectedly very good application properties of the inventive outer film coatings are enabled by the exceptional homogeneous film formation of the polymer composition, low stickiness of the films and good flexibility or extensibility of the coatings, so that the film coating does not tear even in the expansion of the tablet or pellet core. In this context, the combination of high flexibility with extremely low tackiness is especially surprising since polymers are normally rigid, i.e. not very flexible and not tacky or soft, i.e. flexible but tacky.
[00467] Polymer compositions are low viscosity, meaning that high solids concentrations in the spray suspension and an extremely short spray process can be achieved. The solids concentrations of spray suspensions are typically 10% to 60% by weight, preferably 20% to 50% by weight and especially 25% to 40% by weight. Concentrations based on solid polymer containing amino groups used in accordance with the invention are typically within a range of from 5% to 50% by weight, preferably from 10% to 40% by weight and especially from 20% to 35% by weight . Low viscosities ensure very fine and homogeneous atomization at the spray nozzle, very good expansion at the tablet or granule surface and fast, homogeneous film formation. The incorporation of dyes and pigments is carried out in the standard way, but it is extremely simple and fast and is solvent-free. The simple handling results from the fact that the composition of polymers containing amino groups used according to the invention stabilizes the pigments in the spray suspension. Within about 10 minutes, a ready-to-spray suspension can be prepared in this way.
[00468] The formulation base of the inventive pharmaceutical compositions preferably comprises pharmaceutically acceptable auxiliaries. Pharmaceutically acceptable auxiliaries are auxiliaries which are known for use in the field of pharmacy, food technology and related fields, in particular those listed in the relevant pharmacopoeia (eg DAB, Ph. Eur. BP, USP, JP) and other auxiliaries whose properties they do not prevent physiological application.
[00469] Suitable auxiliaries can be: glidants, wetting agents, emulsifiers and suspending agents, preservatives, antioxidants, anti-irritants, chelating agents, emulsion stabilizers, film formers, gel formers, odor masking agents, resins, hydrocolloids, solvents, solubilizers, neutralizing agents, permeation accelerators, pigments, pigments, stabilizers, disintegrants, drying agents, opacifiers, thickeners, waxes, plasticizers, flavors, sweeteners, aids to decrease permeation etc. This configuration group is based on expert knowledge, as represented, for example, in Fiedler, H.P. Lexikon der Hilfsstoffe für Pharmazie, Kosmetik und angrenzende Gebiete, 4th ed., Aulendorf: ECV-Editio-Kantor-Verlag, 1996.
Particularly suitable plasticizers are, for example: triethyl citrate, tributyl citrate, triacetin, acetyl triethyl citrate, labrasol, glycofurol, polypropylene glycol 400.
[00471] The permeability of outer film coatings can be further decreased by incorporating inorganic solids (pigments, for example, talc, kaolin, titanium dioxide) or lipophilic organic solids such as fats, waxes, glycerides, fatty acids, for example , stearic acid, fatty alcohols, for example stearyl alcohol.
[00472] To produce the inventive pharmaceutical compositions, the active ingredients can be mixed or diluted with suitable auxiliaries (excipients). Auxiliaries can be solid or semi-solid materials that can serve as a vehicle, carrier or medium for the active ingredient. Additional helpers are added, if desired, in a manner known to a person skilled in the art.
[00473] Similarly, it is also possible to produce forms of administration in veterinary medicine, especially forms stable in rumen and also forms of administration containing vitamins, carotenoids, trace elements, nutraceuticals, amino acids and food supplements. Lastly they can also serve as food or supplements.
[00474] The invention further provides the use of an inventive polymer composition, as defined above, for membrane production, in cosmetics, in crop protection, for seed coating, in food and beverage, in animal nutrition, as raw materials adhesives, for paper making, as a binder or auxiliary for leather and fabric, as a microbicide surface coating, in the non-woven industry, in washing and cleaning compositions, for paint production, in the construction industry.
[00475] The invention is illustrated in detail by the figures described below and the examples. At the same time, the figures and examples are not to be understood as restricting the invention.
[00476] In the figures and examples that follow, the following abbreviations are used: EO: ethylene oxide PO: propylene oxide BO: butylene oxide Mn: number average molecular weight Mw: weight average molecular weight PET: polyethylene terephthalate TL: value of transparency na: not determined rad/s: radiant per second pphm: parts by weight per 100 parts by weight of monomer (parts per hundred of monomer). DESCRIPTION OF THE FIGURES Figure 1:
[00477] Figure 1 shows an image of a film based on inventive polymer composition 10 before a white background with black text. EXAMPLES I) Analysis: I.a) Determination of water solubility
[00478] To determine the water solubility, 5 g of the particular polymer composition was introduced into a 1 l beaker and 900 ml of water which had been heated to 40°C previously were added. The mixture was stirred with a magnetic stirrer at 40°C for 20 minutes and the pH was adjusted to 8 with sodium hydroxide solution. The water-soluble polymer gels led to clear or slightly turbid solutions. I.b) Determination of weighted average molecular weight (Mw):
[00479] The weight average molecular weight of the polymer was determined by gel permeation chromatography (GPC). For this purpose, the following chromatography instruments and methods were used: Standard: polyacrylic acid, neutralized Eluent: 0.08 mol/l Tris, pH 7.0, + 0.15 mol/l NaCl + 0.01 mol /l NaN3 in deionized water Flow rate: 0.8 ml/min. Column series: 1 guard column (l = 5 cm), 2 separation columns (l = 30 cm each) Column temperature: 35°C Detector: DRI (refractive index detector) Agilent 1100 Ic) Determination of temperature of glass transition (Tg)
[00480] The glass transition temperature was determined by means of dynamic differential calorimetry (DSC: Differential Scanning Calorimetry) in a manner known per se. The DSC measurement was performed on the thermally conditioned samples that were heated to 100°C and rapidly cooled prior to the actual measurement. The glass transition temperature was determined under nitrogen in open aluminum crucibles at a heating rate and a cooling rate at 20 K/min. I.d) Determination of water content after drying
[00481] The water content of the particulate polymer was determined by coulometric means through Karl Fischer titration. II) Preparation Examples: General Preparation Method
[00482] A glass reactor equipped with three feeds, nitrogen inlet and an anchor stirrer was initially charged with the polyether component (PE), the chain transfer agent (CTA) and the solvent (S) in an amount of per table 1 or table 2, purged with nitrogen for one minute turn on and heated to 75°C. Subsequently, feeds 1-3 were simultaneously added to the initial charge at 75°C and while stirring at 100 revolutions/minute within 4 hours. Feed 1 comprises the monomer (M), feed 2 comprises an initiator (FRI) dissolved in a minor amount of the nonionic surfactant (PE) and/or solvent (S) and feed 3 comprises an additional amount of the chain transfer agent (CTA) and optionally solvent. After addition of feeds 1, 2 and 3, the mixture was stirred at 75°C and at 100 revolutions/minute for an additional hour for continued polymerization. Subsequently, the polymer was poured into a beaker and immediately cooled to room temperature.
[00483] For the production of the inventive polymer compositions, the following feed stocks were used: M1: acrylic acid M2: methacrylic acid PE1: ethylene oxide having CxH2x+1/CyH2y+1 termination at each end and having an OH group free and x, y = 6-14. PE2: C13 oxo alcohol ethoxylate with 20 EO PE3: propoxylated ethylene glycols having an EO content of 50% PE4: polyethylene glycol, molecular weight 400 g/mol PE5: polypropylene glycol, molecular weight 400 g/mol PE6: polyglycoside of alkyl R1: 2-mercaptoethanol S1: water S2: isopropanol FRI1: tert-butyl peroxynodecanoate (purity: 97%) (CAS No. 26748-41-4) FRI2: 2,2'-azobis(2-methylpropionamidine dihydrochloride) ) (CAS No. 2997-92-4)
[00484] The inventive polymer compositions of examples 1 to 15 were prepared by the general preparation method described above. The monomer component (M) used was acrylic acid or methacrylic acid. The (meth)acrylic acid used and the particular polyether (PE) component were added in the stated weight proportions, with highly varied amounts of the solvent (S), the initiator (FRI) and the chain transfer agent (CTA) in the polymer blends. The quantities (in [g]) of feed stocks are summarized in tables 1 and 2 below.
[00485] The polymer composition of examples 1 to 9 was first obtained in the form of gels or solids containing solvents. After synthesis, about 100 g in each case of a polymer composition was poured onto an aluminum disk and further dried in a drying cabinet first at 80°C and standard pressure and then at 50°C and 100 mbar (0 .01 Kpa). The solid polymer material thus obtained was ground in a mortar and pestle. The analytical parameters and consistency of the resulting solid polymer compositions are summarized in table 3 below. Table 1
Table 2
Table 3

na = not determined III) Example for the production of polymer films:
[00486] The polymer composition of example 10 was fully liquefied by heating to 80°C and coated onto a flat Si surface with a 120 μm stir bar. Subsequently, the film was dried at room temperature for 24 hours. A flexible film was obtained, which had good water solubility at pH 8 and 40°C.
[00487] Figure 1 shows an image of a film based on inventive polymer composition 10 before a white background with black text. IV) Example for the production of a polymer film containing active ingredient:
[00488] The polymer composition of example 10 was liquefied by heating to 70°C. Then 1% (w/w) of the Bacillus sp. Protease P3111 (Sigma Aldrich) was added while stirring until a homogeneous mixture formed. The liquid polymer composition was coated onto a Si surface with a 120 µm coating bar and immediately cooled to room temperature. Subsequently, the film was dried at room temperature for 24 hours. A flexible film was obtained, which has good water solubility at pH 8 and 40°C with included enzyme release (measured by the AAPF protease activity method) (AAPF = alanine(A)-alanine(A)-proline( P)-phenylalanine(F)).

权利要求:
Claims (28)
[0001]
1. Process for preparing a polymer composition in the form of a film, in the form of a solid coating on a substrate or in the form of particles, characterized in that a) a monomer composition M) is provided, comprising A) at least an α,β-ethylenically unsaturated carboxylic acid, and B) less than 0.1% by weight, based on the total weight of the monomer composition M), of crosslinking monomers having two or more than two α,β- double bonds polymerizable ethylenically unsaturated per molecule, in which component A) may be partially or fully replaced by C) at least one unsaturated sulfonic acid or unsaturated phosphonic acid, b) the monomer composition M) provided in step a) is subjected to polymerization by free radical in the presence of at least one PE polyether component), which is free of copolymerizable double bond, selected from polyetherols having a number average molecular weight of at least 200 g/mol and mono- and di-(C 1 -alkyl) -Ç 6) ethers thereof, surfactants containing polyether groups and mixtures thereof, and c) the polymer obtained in step b) is converted into a film, into a solid coating on a substrate or into particles, in which the polyether component is PE ) comprises a polyetherol having repeating propylene oxide units or a mono- or di-(C 1 -C 6 -alkyl) ether of a polyetherol having repeating propylene oxide units, and the proportion of these repeating propylene oxide units it is no greater than 10 units per molecule and polyetherols are ethylene oxide homopolymers and ethylene oxide/propylene oxide copolymers.
[0002]
2. Process according to claim 1, characterized in that the free radical polymerization in step b) is additionally carried out in the presence of a solvent S) selected from water, C1-C6 alkanols, polyols other than PE) the mono- and di-alkyl ethers thereof, and mixtures thereof.
[0003]
3. Process according to claim 1 or 2, characterized in that the α,β-ethylenically unsaturated carboxylic acid A) is selected from acrylic acid, methacrylic acid, ethacrylic acid, a-chloroacrylic acid, crotonic acid, maleic acid , itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid and mixtures thereof.
[0004]
4. Process according to any one of the preceding claims, characterized in that the monomer composition M) comprises, as component C), at least one unsaturated sulfonic acid or unsaturated phosphonic acid selected from 2-acrylamido-2-methylpropanesulfonic acid , vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloyloxypropylsulfonic acid, 2-hydroxy-3-methacryloyloxypropylsulfonic acid, styrenesulfonic acid, vinylphosphonic acid, allylphosphonic acid mixtures thereof.
[0005]
5. Process according to any one of the preceding claims, characterized in that the monomer composition M) consists of an extension of at least 80% by weight, based on the total weight of the monomer composition M) of at least an α,β-ethylenically unsaturated acid selected from acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and mixtures thereof.
[0006]
6. Process according to any one of the preceding claims, characterized in that the monomer composition M) consists of an extension of at least 90% by weight, based on the total weight of the monomer composition M) of at least an α,β-ethylenically unsaturated acid selected from acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and mixtures thereof.
[0007]
7. Process according to any one of the preceding claims, characterized in that the monomer composition M) consists of an extension of at least 95% by weight, based on the total weight of the monomer composition M) of at least one α,β- ethylenically unsaturated acid selected from acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and mixtures thereof.
[0008]
8. Process according to any one of the preceding claims, characterized in that the monomer composition M) consists of an extension of at least 80% by weight, based on the total weight of the monomer composition M) of acrylic acid.
[0009]
9. Process according to any one of the preceding claims, characterized in that the monomer composition M) consists of an extension of at least 90% by weight, based on the total weight of the monomer composition M) of acrylic acid.
[0010]
10. Process according to any one of the preceding claims, characterized in that the monomer composition M) consists of an extension of at least 95% by weight, based on the total weight of the monomer composition M) of acrylic acid.
[0011]
11. Process according to any one of the preceding claims, characterized in that the monomer composition M) additionally comprises at least one monomer D) selected from the compounds of general formulas (Ia) and (Ib)
[0012]
12. Process according to claim 11, characterized in that the monomer composition M) additionally comprises at least one monomer D) selected from the compounds of general formulas (Ia) and (Ib)
[0013]
13. Process according to any one of the preceding claims, characterized in that the monomer composition M) additionally comprises at least one comonomer selected from E) vinylaromatics, F) C2-C8-mono-olefins, non-aromatic hydrocarbons having at least two conjugated double bonds, G) esters of α,β-ethylenically unsaturated mono- and di-carboxylic acids with C1-C30-alkanols, H) compounds having a free radical polymerizable α,β-ethylenically unsaturated double bond and at least one cationic and/or cationic group per molecule, I) esters of vinyl alcohol or allyl alcohol with C1-C30-monocarboxylic acids, K) monomers containing amide groups, L) esters of α,β- ethylenically unsaturated mono- and di-carboxylic acids with C2-C30 alkanediols, amides of α,β-ethylenically unsaturated mono- and di-carboxylic acids with C2-C30-amino alcohols having a primary or secondary amino group, M) α,β-ethylenically unsaturated nitriles, N) hal vinyl ogenides, vinylidene halides, O) monomers having urea groups, and mixtures thereof.
[0014]
14. Process according to any one of the preceding claims, characterized in that the polyether PE component) comprises at least one polyetherol having a number average molecular weight in the range of 200 to 100,000 g/mol or a mono- or di- ( C1-C2-alkyl ether) thereof.
[0015]
15. Process according to any one of the preceding claims, characterized in that the polyether component PE) comprises at least one surfactant containing polyether groups, selected from alkyl polyoxyalkylene ethers, aryl polyoxyalkylene ethers, alkylaryl polyoxyalkylene ethers, fats and/or alkoxylated vegetable and/or animal oils, fatty alkoxylated amines, fatty acid alkoxylated amides, fatty acid alkoxylated diethanolamides, fatty acid polyoxyethylene sorbitan esters, alkyl polyether sulfates, polyether aryl sulfates, alkylaryl polyether sulfates, alkyl polyether sulfates polyether sulfonates, alkylaryl polyether sulfonates, alkyl polyether phosphates, aryl polyether phosphates, alkylaryl polyether phosphates, glyceryl ether sulfonates, glyceryl ether sulfates, monoglyceride (ether) sulfates, amide ether sulfates, fatty acid esters and polyoxyalkylene fatty acid esters same.
[0016]
16. Process according to any one of the preceding claims, characterized in that the polyether component PE) comprises at least one surfactant containing polyether groups, selected from: - alkyl polyoxyalkylene ethers of the general formula (VI)
[0017]
17. Process according to any one of the preceding claims for preparing a polymer composition in the form of a film, characterized in that a) a monomer composition M) is provided, comprising A) at least one α,β carboxylic acid -ethylenically unsaturated, and B) less than 0.1% by weight based on the total weight of the monomer composition M), of crosslinking monomers having two or more than two polymerizable α,β-ethylenically unsaturated double bonds per molecule, b ) the monomer composition M) provided in step a) is subjected to a free radical polymerization in the presence of at least one polyether component PE) selected from polyetherols having a number average molecular weight of at least 200 g/mol and the mono- and di-(C 1 -C 6 -alkyl) ethers thereof, surfactants containing polyether groups and mixtures thereof, and c) the polymer obtained in step b), optionally after the addition of at least one active and/or at least one less additive is submitted to a selected film forming operation of blow molding, thermoforming, casting and calendering.
[0018]
18. A process according to any one of claims 1 to 16 for preparing a polymer composition in the form of a solid coating on a substrate, characterized in that a) a monomer composition M) is provided, comprising A) at least one α,β-ethylenically unsaturated carboxylic acid, and B) less than 0.1% by weight, based on the total weight of the monomer composition M), of crosslinking monomers having two or more than two α,β-ethylenically double bonds polymerizable unsaturated compounds per molecule, b) the monomer composition M) provided in step a) is subjected to a free radical polymerization in the presence of at least one polyether PE component) selected from polyetherols having a number average molecular weight of at least 200 g/mol and the mono- and di-(C1-C6-alkyl) ethers, surfactants containing polyether groups and mixtures thereof, and c) the polymer obtained in step b), optionally after the addition of at least one active ingredient and / or at least an ad active and/or at least one solvent and, optionally during heating, is converted into a free-flowing form, applied to a substrate and allowed to solidify.
[0019]
19. Process according to any one of claims 1 to 16 for preparing a polymer composition in particulate form, characterized in that a) a monomer composition M) is provided, comprising A) at least one carboxylic acid α, β-ethylenically unsaturated, and B) less than 0.1% by weight based on the total weight of the monomer composition M), of crosslinking monomers having two or more than two polymerizable α,β-ethylenically unsaturated double bonds per molecule, b) the monomer composition M) provided in step a) is subjected to a free radical polymerization in the presence of at least one polyether component PE) selected from polyetherols having a number average molecular weight of at least 200 g/mol and the mono- and di-(C 1 -C 6 -alkyl) ethers, surfactants containing polyether groups and mixtures thereof, and c) the polymer obtained in step b), optionally after addition of at least one additive and/or at least one solvent and optionally during heating. To this, it is converted into a free-flowing form and a particulate composition is formed from it.
[0020]
20. Polymer composition in solid form, characterized in that it is obtained by a process as defined in any one of claims 1 to 19, and that it is present as a film, as a solid coating on a substrate or as particles.
[0021]
21. Polymer composition in the form of a film, characterized in that it is obtained by a process as defined in any one of claims 1 to 17, and that it is present as a film, as a solid coating on a substrate or as particles .
[0022]
22. Polymer composition in the form of a film according to claim 21 or obtained by a process as defined in any one of claims 1 to 17, characterized in that it comprises at least one active ingredient selected from enzymes, enhancers, agents bleaching agents, surfactants, bases, corrosion inhibitors, defoamers, dyes, fragrances, fillers, tabletting aids, disintegrants, thickeners, solubilizers, organic solvents, electrolytes, pH modifiers, perfume carriers, fluorescent agents, hydrotropes, agents anti-redeposition, optical brighteners, graying inhibitors, shrinkage inhibitors, wrinkling inhibitors, dye transfer inhibitors, antimicrobial active ingredients, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, hydrophobizing and impregnating agents, swelling and anti-slip agents, absorbents of UV and mixtures thereof.
[0023]
23. Polymer composition in the form of a coating on a substrate, characterized in that it is obtained by a process as defined in any one of claims 1 to 16 or 18.
[0024]
24. Polymer composition in the form of a coating on a substrate according to claim 19, or obtained by a process as defined in any one of claims 1 to 16 or 18, characterized in that it comprises at least one selected active ingredient of enzymes, reinforcers, bleaches, surfactants, bases, corrosion inhibitors, defoamers, dyes, fragrances, fillers, tabletting aids, disintegrants, thickeners, solubilizers, organic solvents, electrolytes, pH modifiers, perfume carriers, fluorescent agents , hydrotropes and anti-redeposition, optical brighteners, graying inhibitors, shrinkage inhibitors, wrinkle inhibitors, dye transfer inhibitors, active antimicrobial ingredients, antioxidants, corrosion inhibitors, antistatic agents, ironing agents, hydrophobizing agents and impregnation, swelling and anti-slip agents, absorbs UV vents and mixtures thereof.
[0025]
25. Use of a polymer composition as defined in any one of claims 20 to 24, or obtained by a process as defined in any one of claims 1 to 19, characterized in that it is - in washing and cleaning compositions, - in dishwashing detergents and rinsing aids, - in hygiene products, - in cosmetic compositions, - in pharmaceutical compositions, - in crop protection compositions, - in wetting agents, - in lacquers, coating compositions, adhesives, treatment of leather or compositions for the care of textile articles, - in the development and/or exploitation of mineral oil and/or underground natural gas deposits.
[0026]
26. Use according to claim 25, characterized in that it is in an enzyme-containing washing composition, a cleaning composition or a dishwashing composition.
[0027]
27. Wrap or coating for a washing composition portion, cleaning composition portion or dishwashing composition portion, characterized in that it comprises or consists of a polymer composition as defined in any one of claims 20 to 24, or obtained by a process as defined in any one of claims 1 to 19.
[0028]
28. Adhesive composition, characterized in that it comprises or consists of a polymer composition obtained by a process as defined in any one of claims 1 to 19.

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法律状态:
2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-12-08| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-06-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-07-20| B350| Update of information on the portal [chapter 15.35 patent gazette]|

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2021-08-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/07/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP13174938.4|2013-07-03|

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EP13174938|2013-07-03|

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PCT/EP2014/064084|WO2015000970A1|2013-07-03|2014-07-02|Solid polymer composition obtained by polymerization of an acid group-containing monomer in the presence of a polyether compound|

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