Cleaning compositions containing a polyether amine

专利摘要:
CLEANING COMPOSITIONS CONTAINING A POLYETHER AMINE. The present invention relates generally to cleaning compositions and more specifically to cleaning compositions containing a polyether amine which is suitable for removing stains from soiled materials.
公开号:BR112016002081B1
申请号:R112016002081-2
申请日:2014-08-15
公开日:2022-01-25
发明作者:Frank Hulskotter；Kevin Patrick Christmas；Stefano Scialla；Brian Joseph Loughnane；Amy EICHSTADT WAUN；Darren REES；Sophia Ebert；Bjoern LUDOLPH；Christof WIGBERS；Steffen Maas；Dieter Boeckh
申请人:Basf Se；
IPC主号:

专利说明:

FIELD OF TECHNIQUE
[0001] The present invention relates generally to cleaning compositions and, more specifically, to cleaning compositions containing a polyether amine which is suitable for removing stains from soiled materials. BACKGROUND
[0002] Due to the growing popularity of easy-care fabrics produced from synthetic fibers as well as the ever-increasing energy costs and growing ecological concerns of detergent users, the once popular warm and hot rinses have been replaced by washing the fabrics in cold water (30°C and below). Many commercially available laundry detergents are further disclosed as being suitable for washing fabrics at 15°C or even 9°C. To obtain satisfactory washing results at these low temperatures, results comparable to those obtained with washing in hot water, the demands on low-temperature detergents are especially high.
[0003] It is known to include certain additives in detergent compositions to improve the detergent power of conventional surfactants in order to improve grease/grease stain removal at temperatures of 30°C and below. For example, laundry detergents containing an aliphatic amine compound, in addition to at least one anionic and/or synthetic nonionic surfactant, are known. In addition, the use of linear, alkyl-modified (secondary) alkoxy propylamines in laundry detergents to optimize cleaning at low temperatures is known. These known laundry detergents, however, are unable to achieve satisfactory cleaning in cold temperatures.
[0004] In addition, the use of linear and primary polyoxyalkyleneamines (eg Jeffamine® D-230) to stabilize fragrances in laundry detergents and provide longer lasting aroma is also known. In addition, the use of high molecular weight (molecular weight of at least about 1000), branched and trifunctional primary amines (e.g. Jeffamine® T-5000 polyether amine) to suppress foaming in liquid detergents is known. Additionally, an etheramine mixture containing a monoether diamine (e.g. at least 10% by weight of the etheramine mixture), methods for its production, and its use as a curing agent or as a raw material in polymer synthesis are known. . Finally, the use of compounds derived from reacting diamines or polyamines with alkylene oxides and compounds derived from reacting amine-terminated polyethers with epoxide functional compounds to suppress foam formation is known.
[0005] There is a continuing need for a detergent additive that can improve cleaning performance at low washing temperatures, for example at 30°C or even less, without any interference with the production and quality of laundry detergents. . More specifically, there is a need for a detergent additive that can improve cold water grease/grease cleaning without adversely affecting particulate cleaning. Surprisingly, it has been found that the cleaning compositions of the invention provide enhanced removal of grease (particularly in cold water) by the use of a polyether amine compound derived from certain triols. These polyether amine compounds provide surprisingly effective grease/grease removal. SUMMARY
[0006] The present invention attempts to address one or more of the needs by providing, in one aspect of the invention, a cleaning composition (in liquid, powder, unit dose, small envelope, or tablet form) comprising: of about 1% to about 70% by weight of a surfactant system composition; and from about 0.1% to about 10% by weight of a polyether amine composition of formula (I):
wherein R is selected from H or a C1-C6 alkyl group, each of k1, k2, and k3 is independently selected from 0, 1, 2, 3, 4, 5, or 6, each of A1, A2, A3, A4, A5, and A6 is independently selected from a linear or branched alkylene group having from about 2 to about 18 carbon atoms or mixtures thereof, x >1, y >1, and z >1, and the sum of x+y+z is in the range from about 3 to about 100, and each of Z1, Z2, and Z3 is independently selected from NH2 or OH, where at least two of Z1, Z2, and Z3 are NH2.
[0007] The present invention further relates to a cleaning composition comprising: from about 1% to about 70% by weight of a surfactant system; and from about 0.1% to about 10% by weight of a polyether amine selected from the group consisting of formula A, formula B, formula C and mixtures thereof:
where n average is from about 0.5 to about 5.
[0008] The present invention further relates to a cleaning composition comprising: from about 1% to about 70% by weight of a surfactant system; and from about 0.1% to about 10% by weight of a polyether amine obtainable by: a) reacting a low molecular weight, water-soluble organic triol with C2-C18 alkylene oxide to form an alkoxylated triol, where the molar ratio of the low molecular weight triol to the alkylene oxide is in the range of about 1:3 to about 1:10, and b) amine the alkoxylated triol with ammonia.
[0009] The present invention further relates to methods of cleaning soiled materials. Such methods include pre-treatment of soiled material, which comprises contacting the soiled material with the cleaning compositions of the invention. DETAILED DESCRIPTION
[0010] The features and benefits of the various embodiments of the present invention will become apparent from the following description, which includes examples of specific embodiments designed to provide a broad representation of the invention. Various modifications will be apparent to those skilled in the art from this description and from the practice of the invention. It is not intended to limit the scope to the particular forms disclosed, and the invention encompasses all modifications, equivalents and alternatives that are within the spirit and scope of the invention as defined by the claims.
[0011] As used herein, articles including "the", "the", "a" and "an", when used in a claim or specification, are understood to mean one or more of what is claimed or described .
[0012] As used herein, the terms "include", "includes" and "including" are not intended to be limiting.
[0013] The term "substantially free from" as used herein, refers to the complete absence of an ingredient or a minimal amount thereof merely as an impurity or unintended by-product of another ingredient. In some aspects, a composition that is "substantially free" of a component means that the composition comprises less than 0.1%, or less than 0.01%, or even 0% by weight of the component composition.
[0014] As used herein, the term "dirty material", is used non-specifically and can refer to any type of flexible material that consists of a web of natural or man-made fibers, including natural, man-made, and synthetic fibers, such as, but not limited to, cotton, linen, wool, polyester, nylon, silk, acrylic, and the like, including blends of various fabrics or fibers. Dirty material can also refer to any type of hard surface, including natural, artificial or synthetic surfaces such as, but not limited to, tile, granite, mortar, glass, composite, vinyl, hardwood, metal, kitchen surfaces, plastic, and the like, as well as mixtures and combinations.
[0015] In this description, all concentrations and ratios are based on the weight of the cleaning composition, unless otherwise specified. Composition for cleaning
[0016] As used in the present invention, the term "cleaning composition" or "detergent composition" includes compositions and formulations designed for cleaning soiled material. Such compositions include, but are not limited to, laundry detergents and cleaning compositions, fabric softening compositions, fabric optimizing compositions, fabric renewal compositions, laundry prewash, pretreatment laundry, laundry additives, spray products, dry cleaning composition or agent, laundry rinse additive, laundry additive, post-rinse fabric treatment, ironing aid iron, dish/dishwashing compositions, hard surface cleaning compositions, unit dose formulation, delayed release formulation, detergent contained on or within a porous substrate or a non-woven sheet and other suitable forms which may be evident to one skilled in the art in view of the teachings of the present invention. Such compositions can be used as a laundry pre-treatment, a laundry post-treatment, or they can be added during the wash or rinse cycle of the laundry operation. The cleaning compositions may be in a form selected from liquid, powder, single-phase or multi-phase unit dose, small shell, tablet, gel, paste, bar or flake. polyether amines
[0017] The cleaning compositions described herein may comprise from about 0.1% to about 10%, from about 0.2% to about 5%, or from about 0.5% to about 3% by weight of a polyether amine composition.
[0018] In some aspects, the polyether amine is represented by the structure of formula (I),
wherein R is selected from H or a C1-C6 alkyl group, each of k1, k2, and k3 is independently selected from 0, 1, 2, 3, 4, 5, or 6, each of A1, A2, A3, A4, A5, and A6 is independently selected from a linear or branched alkylene group having from about 2 to about 18 carbon atoms or mixtures thereof, x >1, y >1, and z >1, and the sum of x+y+z is in the range from about 3 to about 100, and each of Z1, Z2, and Z3 is independently selected from NH2 or OH, where at least two of Z1, Z2, and Z3 are NH2.
[0019] In some aspects, R is H or a C1-C6 alkyl group selected from a methyl group, an ethyl group, or a propyl group. In some aspects, R is H or a C1-C6 alkyl group selected from an ethyl group.
[0020] In some respects, each of k1, k2, and k3 is selected independently of 0, 1, or 2. In some respects, each of k1, k2, and k3 is selected independently of 0 or 1. In al- In some respects, at least two of k1, k2, and k3 are 1. In some respects, each of k1, k2, and k3 is 1.
[0021] In some respects, each of Z1, Z2, and Z3 is NH2.
[0022] A1, A2, A3, A4, A5, and A6 can be the same or different. At least two of A1-A6 can be the same, at least two of A1-A6 can be different, or each of A1-A6 can be different from each other. Each of A1, A2, A3, A4, A5, and A6 can be independently selected from a linear or branched alkylene group having from about 2 to about 10 atoms, or from about 2 to about 6 atoms. carbon atoms, or from about 2 to about 4 carbon atoms. In some aspects, at least one, or at least one three, of A1-A6 is a linear or branched butylene group. In some aspects, each of A4, A5, and A6 is a straight or branched butylene group. In some aspects, each of A1-A6 is a linear or branched butylene group.
[0023] In some respects, x, y and/or z are independently equal to 3 or more, which means that the polyether amine of formula (I) can have more than one [A1 - O] group, more than one group [A2 - O] and/or more than one group [A3 - O]. In some aspects, A1 is selected from ethylene, propylene, butylene or mixtures thereof. In some aspects, A2 is selected from ethylene, propylene, butylene or mixtures thereof. In some aspects, A3 is selected from ethylene, propylene, butylene or mixtures thereof.
[0024] In some aspects, [A1 - O] is selected from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof. In some respects, [A2 - O] is selected from ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof. In some aspects, [A3 - O] is selected from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof.
[0025] When A1, A2 and/or A3 are mixtures of ethylene, propylene and/or butylene, the resulting alkoxylate may have a block structure or a random structure.
[0026] For a non-limiting illustration, when x = 7 in the polyether amine according to formula (I), then the polyether amine comprises six [A1 - O] groups. If A1 comprises a mixture of ethylene groups and propylene groups then the resulting polyether amine would comprise a mixture of ethoxy (EO) groups and propoxy (PO) groups. These groups can be arranged in a random structure (eg EO-EO-PO-EO-PO-PO) or a block structure (EO-EO-EO-PO-PO-PO). In this illustrative example, there are an equal number of different alkoxy groups (here, three EO and three PO), but there may also be different numbers of each alkoxy group (eg, five EO and one PO). Furthermore, when the polyether amine comprises alkoxy groups in a block structure, the polyether amine may comprise two blocks as shown in the illustrative example (where the three EO groups form one block and the three PO groups form another). block), or the polyether amine may comprise more than two blocks.
[0027] In some respects, the sum of x+y+z is in the range from about 3 to about 100, or from about 3 to about 30, or from about 3 to about 10, or from about from 5 to about 10.
[0028] Typically, the polyether amines of the present invention have a weight average molecular weight of about 150, or about 200, or about 350, or from about 500 grams/mol, to about 1,000, or to about 1000. about 900, or about 800 grams/mol. The molecular weight of a polymer differs from typical molecules in that polymerization reactions produce a molecular weight distribution, which is summarized by the weight average molecular weight. The polyether amine polymers of the invention are then distributed over a range of molecular weights. Differences in molecular weights are primarily attributable to differences in the number of monomer units that sequence together during synthesis. With respect to the polyether amine polymers of the invention, the monomer units are the alkylene oxides which react with the triols of formula (II) to form alkoxylated triols, which are then aminated to form the resulting polyether amine polymers. The resulting polyether amine polymers are characterized by the sequence of alkylene oxide units. The alkoxylation reaction results in a distribution of alkylene oxide sequences and therefore a distribution of molecular weights. The alkoxylation reaction also produces unreacted alkylene oxide monomer ("unreacted monomers") that do not react during the reaction and remain in the composition.
[0029] In some aspects, in the polyether amine of formula (I), R is an ethyl group, each of k1, k2, and k3 is 1, and the molecular weight of the polyether amine is from about 500 to about 1,000 grams/mol. In some aspects, in the polyether amine of formula (I), R is an ethyl group, each of k1, k2, and k3 is 1, and at least one of A1, A2, A3, A4, A5, or A6 is ethylene , butylene or a mixture thereof, typically butylene.
[0030] In some aspects, the composition comprises a polyether amine with the following structure:
wherein average n is from about 0.5 to about 5, or from about 1 to about 3, or from about 1 to about 2.5.
[0031] In some aspects, the composition comprises a polyether amine selected from the group consisting of formula A, formula B, formula C and mixtures thereof:
where n average is from about 0.5 to about 5.
[0032] The polyether amines of the present invention, for example the polyether amine of formula (I), can be obtained by a process comprising the following steps: a) reacting a low molecular weight organic triol, such as glycerin and/or 1,1,1-trimethylolpropane, with C2-C18 alkylene oxide, to form an alkoxylated triol, where the molar ratio of the low molecular weight organic triol to the alkylene oxide is in the range of about 1:3 to about of 1:10, and b) amine the alkoxylated triol with ammonia.
[0033] This process is described in more detail below. alkoxylation
[0034] The polyether amines according to formula (I) can be obtained by reductive amination of an alkoxylated triol. The alkoxylated triols according to the present disclosure can be obtained by reacting low molecular weight organic triols, such as glycerin and/or 1,1,1-trimethylolpropane, with alkylene oxides according to known general alkoxylation procedures. in the technique.
[0035] By "low molecular weight," it is meant that the triol has a molecular weight of from about 64 to about 500, or from about 64 to about 300, or from about 78 to about 200, or from about 92 to about 135 g/mol. The triol may be soluble in water.
[0036] In some respects, low molecular weight organic triol (or simply "low molecular weight triol," as used here) has the structure of formula (II):
wherein R is selected from H or a C1-C6 alkyl group and where each is independently selected from 0, 1, 2, 3, 4, 5, or 6. In some aspects, R is H or a C1 alkyl group -C6 selected from a methyl, ethyl or propyl group. In some respects, R is H or ethyl. In some respects, each of k1, k2, and k3 is selected independently of 0, 1, or 2. Each of k1, k2, and k3 can be selected independently of 0 or 1. In some respects, at least two of k1 , k2, and k3 are 1. In some respects, each of k1, k2, and k3 is 1.
[0037] In some aspects, the low molecular weight triol is selected from glycerin, 1,1,1-trimethylolpropane, or mixtures thereof.

[0038] The alkoxylated triol, such as alkoxylated glycerin or alkoxylated 1,1,1-trimethylolpropane, can be prepared in a known manner by reacting the low molecular weight triol with an alkylene oxide. Suitable alkylene oxides are linear or branched C2-C18 alkylene oxides, typically C2-C10 alkylene oxides, more typically C2-C6 alkylene oxides or C2-C4 alkylene oxides. Suitable alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, pentene oxide, hexene oxide, decene oxide and dodecene oxide. In some aspects the C2 -C18 alkylene oxide is selected from ethylene oxide, propylene oxide, butylene oxide or a mixture thereof. In some aspects the C2 -C18 alkylene oxide is butylene oxide, optionally in combination with other C2 -C18 alkylene oxides.
[0039] Low molecular weight triols such as glycerin or 1,1,1-trimethylolpropane can be reacted with a single type of alkylene oxide or combinations of two or more different types of alkylene oxides, e.g. ethylene and propylene oxide. If two or more different types of alkylene oxides are used, the resulting alkoxylate may have a block structure or a random structure.
[0040] Typically, the molar ratio between the low molecular weight triol and the C2-C18 alkylene oxide in which the alkoxylation reaction is carried out is in the range of about 1:3 to about 1:10, plus typically about 1:3 to about 1:6, more typically about 1:4 to about 1:6. In some aspects, the molar ratio of the low molecular weight triol to the C2-C18 alkylene oxide in which the alkoxylation reaction is carried out is in the range of about 1:5 to about 1:10.
[0041] In some aspects, the low molecular weight triol is 1,1,1-trimethylolpropane and the resulting polyether amine has a weight average molecular weight of from about 500 to about 1,000, or up to about 900, or up to about of 800 grams/mol.
[0042] The reaction is generally performed in the presence of a catalyst in an aqueous solution at a reaction temperature of about 70°C to about 200°C, and typically, from about 80°C to about 160°C . The reaction can take place at a pressure of up to about 1 MPa (10 bar), or up to about 0.8 MPa (8 bar).
[0043] Examples of suitable catalysts include basic catalysts such as alkali metal and alkaline earth metal hydroxides, for example sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal alkoxides, in particular C1-C4 alkoxides of sodium and potassium, e.g. sodium methoxide, sodium ethoxide and potassium tert-butoxide, alkali metal and alkaline earth metal hydrides such as sodium hydride and calcium hydride, and alkali metal carbonates such as sodium carbonate and potassium carbonate. In some aspects, the catalyst is an alkali metal hydroxide, typically potassium hydroxide or sodium hydroxide. Typical use amounts for the catalyst are from about 0.05 to about 10% by weight in particular from about 0.1 to about 2% by weight based on the total amount of the low molecular weight triol and of alkylene oxide. During the alkoxylation reaction, certain impurities - unintended constituents of the polymer - can be formed, such as catalyst residues. Amination
[0044] Polyether amines according to formula (I) can be obtained by reductive amination of an alkoxylated triol such as those described above, for example alkoxylated glycerin or alkoxylated 1,1,1-trimethylolpropane, with ammonia in the presence of hydrogen and a catalyst, such as a nickel-containing catalyst. Suitable catalysts are described in WO 2011/067199 A1, in WO2011/067200 A1, and in EP0696572 B1.
[0045] The amination can be performed in the presence of catalyst containing copper, nickel or cobalt. Preferred catalysts are supported copper, nickel and cobalt containing catalysts, wherein the catalytically active material of the catalyst, prior to reduction thereof with hydrogen, comprises oxygenated compounds of aluminum, copper, nickel and cobalt, and in the range of about 0 .2% to about 5.0% by weight of tin oxygenates, calculated as SnO. Other suitable catalysts are supported catalysts containing copper, nickel and cobalt, where the catalytically active material of the catalyst, prior to its reduction with hydrogen, comprises oxygenated compounds of aluminum, copper, nickel, cobalt, tin, and, in the range of about from 0.2 to about 5.0% by weight of oxygenated compounds of yttrium, lanthanum, cerium and/or hafnium, each calculated as Y2O3, La2O3, Ce2O3 and Hf2O3, respectively. Another suitable catalyst is a zirconium, copper and nickel catalyst, wherein the catalytically active composition comprises from about 20 to about 85% by weight of oxygen-containing zirconium compounds, calculated as ZrO2, from about 1 to about 30% by weight of oxygen-containing copper compounds, calculated as CuO, from about 30 to about 70% by weight of nickel oxygen-containing compounds, calculated as NiO, from about 0.1 to about 5% by weight of compounds containing aluminum and/or manganese oxygen, calculated as Al2O3 and MnO2, respectively.
[0046] For the reductive amination step, a supported as well as an unsupported catalyst can be used. The supported catalyst may be obtained by deposition of the metallic components of the catalyst compositions on support materials known to those skilled in the art, using techniques that are well known in the art, including, but not limited to, known forms of alumina, silica , charcoal, carbon, graphite, clays, mordenites; Molecular sieves can also be used to provide supported catalysts. When the catalyst is supported, the catalyst support particles can have any geometric shape, for example, the shape of spheres, tablets, or cylinders in a regular or irregular version.
[0047] The process can be performed in a continuous or batch mode, for example in an autoclave, a tubular reactor or a fixed bed reactor. Various reactor designs can be used. For example, the feed to it can be upflow or downflow and design features in the reactor that optimize the piston flow in the reactor can be employed.
[0048] The degree of amination can be from about 67% to about 100%, or from about 85% to about 100%. The degree of amination is calculated from the total value of amine (AZ) divided by the sum of the total value of acetylates (AC) and by the value of tertiary amine (AZ tert.) multiplied by 100 (total AZ / ((AC+ AZ tert. )x100)).
[0049] The total value of amine (AZ) is determined according to DIN 16945.
[0050] The total value of acetylables (AC) is determined according to DIN 53240.
[0051] Secondary and tertiary amines are determined in accordance with ASTM D2074-07.
[0052] The hydroxyl value is calculated from (total value of acetylables + value of tertiary amine) - total value of amine.
[0053] The polyether amines of the invention are effective for removing stains, particularly grease/grease, from soiled material. Cleaning compositions containing the polyether amines of the invention also do not exhibit the negative cleaning aspects seen with conventional amine-containing cleaning compositions on hydrophilic bleachable stains such as coffee, tea, wine or particulates. Additionally, unlike conventional amine-containing cleaning compositions, the polyether amine-containing cleaning compositions of the invention do not contribute to the negative aspects of whiteness in white fabrics.
[0054] The polyether amines of the invention can be used in the form of a water-based, water-containing or water-free solution, emulsion, gel or paste of the polyether amine together with an acid such as citric acid, lactic acid, sulfuric acid, methanesulfonic acid, hydrogen chloride, eg aqueous hydrogen chloride, phosphoric acid or mixtures thereof. Alternatively, the acid may be represented by a surfactant, such as, alkylbenzene sulfonic acid, alkyl sulfonic acid, monoalkyl esters of sulfuric acid, mono alkyl ethoxy esters of sulfuric acid, fatty acids, alkyl ethoxy carboxylic acids, and the like, or mixtures thereof. Where applicable or measurable, the preferred pH of the solution or emulsion is in the range of pH 3 to pH 11, or pH 6 to pH 9.5, most preferably pH 7 to pH 8.5.
[0055] An additional advantage of cleaning compositions containing the polyether amines of the invention is their ability to remove grease/greasy stains in cold water, for example, as a detergent in the wash water or through pre-treatment of a grease/greasy stain. greasy followed by washing in cold water. Without being bound by theory, it is believed that cold water washing solutions have the effect of hardening or solidifying the greases/fats, making them more resistant to removal, specifically on fabrics. Cleaning compositions containing the polyether amines of the invention are surprisingly effective when used as part of a pretreatment regimen followed by a cold water wash. surfactant system
[0056] Cleaning compositions comprise a surfactant system in an amount sufficient to provide the desired cleaning properties. In some embodiments, the cleaning composition comprises, by weight of the composition, from about 1% to about 70% of a surfactant system. In other embodiments, the liquid cleaning composition comprises, by weight of the composition, from about 2% to about 60% of the surfactant system. In additional embodiments, the cleaning composition comprises, by weight of the composition, from about 5% to about 30% of the surfactant system. The surfactant system may comprise a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof. Those skilled in the art will understand that a detersive surfactant encompasses any surfactant or mixture of surfactants that provides cleaning, stain removal or other laundry benefit to soiled material. anionic surfactants
[0057] In some examples, the surfactant system of the cleaning composition may comprise from about 1% to about 70% by weight of the surfactant system, of one or more anionic surfactants. In other examples, the surfactant system of the cleaning composition may comprise from about 2% to about 60% by weight of the surfactant system, one or more anionic surfactants. In further examples, the surfactant system of the cleaning composition may comprise from about 5% to about 30% by weight of the surfactant system, one or more anionic surfactants. In further examples, the surfactant system may consist essentially of, or even consist of, one or more anionic surfactants.
[0058] Specific non-limiting examples of suitable anionic surfactants include any conventional anionic surfactant. This may include a sulfate detersive surfactant, for example, alkoxylated and/or non-alkoxylated alkyl sulfate materials and/or sulfonic detersive surfactants, for example, alkylbenzenesulfonates.
[0059] Alkoxylated alkyl sulfate materials comprise surfactants based on ethoxylated alkyl sulfate, also known as alkyl ether sulfates or alkyl polyethoxylate sulfates. Examples of ethoxylated alkyl sulfates include water-soluble salts, particularly the alkali metal, ammonium and alkylol ammonium salts of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 30 carbon atoms. and a sulfonic acid and its salts. (Included in the term "alkyl" is the alkyl portion of acyl groups. In some examples, the alkyl group contains from about 15 carbon atoms to about 30 carbon atoms. In other examples, the alkyl ether sulfate surfactant may be a mixture of alkyl ether sulfates, said mixture having an average carbon chain length (arithmetic average) within the range of about 12 to 30 carbon atoms, and in some examples, an average carbon chain length of about 25 carbon atoms of carbon, and an average degree (arithmetic average) of ethoxylation of about 1 mol to 4 mol of ethylene oxide, and in some examples, an average degree (arithmetic average) of ethoxylation of 1.8 mol of ethylene oxide. In further examples, the alkyl ether sulfate surfactant may have a carbon chain length of from about 10 carbon atoms to about 18 carbon atoms, and a degree of ethoxylation of from about 1 to about 6 mol. of ethylene oxide. In still further examples, the tens The alkyl ether sulfate active may contain a peak ethoxylate distribution.
[0060] Non-alkoxylated alkyl sulfates can also be added to the disclosed cleaning compositions and used as an anionic surfactant component. Examples of non-alkoxylated, eg non-ethoxylated, alkyl sulfate-based surfactants include those produced by the sulfation of higher C8-C20 fatty alcohols. In some examples, primary alkyl sulfate-based surfactants have the general formula: ROSO3-M+, where R is typically a linear C8-C20 hydrocarbyl group, which may be straight-chain or branched, and M is a cation of water solubilization. In some examples, R is a C10-C15 alkyl and M is an alkali metal. In other examples, R is a C12-C14 alkyl and M is a sodium.
[0061] Other useful anionic surfactants may include the alkali metal salts of alkylbenzenesulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, in a straight-chain (linear) or branched-chain configuration, for example, those of the type described in US Patent Nos. 2,220,099 and 2,477,383. In some examples, the alkyl group is linear. These linear alkyl benzene sulfonates are known as "LAS". In other examples, the linear alkyl benzene sulfonate may have an average number of carbon atoms in the alkyl group of about 11 to 14. In one specific example, straight chain linear alkylbenzene sulfonates may have an average number of carbon atoms in the alkyl group. alkyl group of about 11.8 carbon atoms, which may be abbreviated as C11.8 LAS. Such surfactants and their preparation are described, for example, in US Patent Nos. 2,220,099 and 2,477,383.
[0062] Suitable alkyl benzene sulfonate (LAS) can be obtained by sulfonating commercially available linear alkyl benzene (LAB), suitable LAB including 2-lower phenyl LAB such as those supplied by Sasol under the trade name Isochem® or those supplied by Petresa under the tradename Petrelab®, and other suitable LABs include high 2-phenyl LABs, such as those supplied by Sasol under the tradename Hyblene®. A suitable anionic detersive surfactant is alkyl benzene sulfonate which is obtained by the DETAL catalyzed process, although other synthesis routes such as HF may also be suitable. In one aspect, a magnesium salt of LAS is used.
[0063] The detersive surfactant may be a branched medium chain detersive surfactant, in one aspect a branched medium chain anionic detersive surfactant, in one aspect a branched medium chain alkyl sulfate and/or a branched medium chain alkylbenzene sulfonate , for example, a branched-medium chain alkyl sulfate. In one aspect, the medium chain branches are C1-4 alkyl groups, typically methyl and/or ethyl groups.
[0064] Other anionic surfactants useful in the present invention are the water-soluble salts of: paraffin sulfonates and secondary alkane sulfonates which contain about 8 to about 24 (in some examples about 12 to 18) carbon atoms, sulfonates glyceryl alkyl ether, especially ethers of C8-18 alcohols (eg those derived from tallow and coconut oil). Mixtures of the alkylbenzenesulfonates with the above-described paraffin sulfonates, secondary alkane sulfonates and alkyl glyceryl ether sulfonates are also useful. Additional suitable anionic surfactants further include methyl ester sulfonates and alkyl ether carboxylates. Additional suitable anionic surfactants useful in the present invention are found in US Patent No. 4,285,841, issued to Barrat et al. on August 25, 1981, and in US Patent No. 3,919,678, issued to Laughlin, et al. on December 30, 1975, both of which are incorporated herein by reference.
[0065] Anionic surfactants can exist in an acid form and the acid form can be neutralized to form a surfactant salt. Typical agents for neutralization include metal counterion bases such as hydroxides, eg NaOH or KOH. Additional suitable agents for neutralizing anionic surfactants to their acidic forms include ammonia, amines or alkanolamines. Non-limiting examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine and other linear or branched alkanolamines known in the art, suitable alkanolamines include 2-amino-1-propanol, 1-aminopropanol, monoisopropanolamine or 1-amino-3-propanol. Amine neutralization can be done to a full or partial extent, for example, part of the anionic surfactant mixture can be neutralized with sodium or potassium and part of the anionic surfactant mixture can be neutralized with amines or alkanolamines. non-ionic surfactants
[0066] The surfactant system of the cleaning composition may comprise a non-ionic surfactant. In some examples, the surfactant system comprises up to about 25% by weight of the surfactant system, of one or more non-ionic surfactants, eg as a co-surfactant. In some examples, the cleaning compositions comprise from about 0.1% to about 15% by weight of the surfactant system, one or more nonionic surfactants. In further examples, the cleaning compositions comprise from about 0.3% to about 10% by weight of the surfactant system, one or more non-ionic surfactants.
[0067] Suitable nonionic surfactants useful in the present invention may comprise any conventional nonionic surfactant. These may include, for example, alkoxylated fatty alcohols and amine oxide surfactants. In some examples, the cleaning compositions may contain an ethoxylated nonionic surfactant. These materials are described in US Patent No. 4,285,841, to Barrat et al., issued August 25, 1981. The nonionic surfactant can be selected from ethoxylated alcohols and ethoxylated alkylphenols with the following formula R(OC2H4)nOH , wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkylphenyl radicals, wherein the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15. These surfactants are described more fully in US Patent No. 4,284,532, Leikhim et al., issued August 18, 1981. In one example, the nonionic surfactant is selected from ethoxylated alcohols which have an average of about 24 carbon atoms in the alcohol and an average degree of ethoxylation of about 9 moles of ethylene oxide per mole of alcohol.
[0068] Other non-limiting examples of non-ionic surfactants usable here include: C8-C18 alkyl ethoxylates, such as the NEODOL® nonionic surfactants available from Shell; C6 -C12 alkyl phenol alkoxylates, wherein the alkoxylate units may be ethyleneoxy units, propyleneoxy units or a mixture thereof; C12-C18 alkyl alcohols and C6-C12 alkyl phenol condensed with ethylene oxide/propylene oxide block polymers such as Pluronic® available from BASF; C14C22 medium chain branched alcohols, BA, as discussed in US 6,150,322; C14-C22 medium chain branched alkyl alkoxylates, BAEx, where x is from 1 to 30, as discussed in US 6,153,577, US 6,020,303 and US 6,093,856; alkyl polysaccharides as discussed in US 4,565,647 to Llenado, issued January 26, 1986; specifically, alkyl polyglycosides as discussed in US 4,483,780 and US 4,483,779; polyhydroxy fatty acid amides as discussed in the U.S. 5,332,528 , WO 92/06162 , WO 93/19146 , WO 93/19038 , and WO 94/09099 ; and ether-terminated poly(oxyalkylated) alcohol surfactants as discussed in US 6,482,994 and WO 01/42408.
[0069] Suitable detersive nonionic surfactants also include alkyl polyglycoside and/or an alkoxylated alkyl alcohol. Suitable nonionic surfactants also include those sold under the tradename Lutensol® from BASF.
[0070] In some aspects, the nonionic surfactant is selected from alkoxylated alkyl alcohols, such as a C8-18 alkoxylated alkyl alcohol, for example an ethoxylated C8-18 alkyl alcohol. The alkyl alkoxylated alcohol may have an average degree of alkoxylation of from about 1 to about 50, or from about 1 to about 30, or from about 1 to about 20, or from about 1 to about of 10. In certain aspects, the alkyl alkoxylated alcohol is a C8-18 alkyl ethoxylated alcohol having an average degree of ethoxylation of from about 1 to about 10, or from about 1 to about 7, or from about 10. 1 to about 5, or from about 3 to about 7. The alkyl alkoxylated alcohol can be straight or branched, substituted or unsubstituted. Anionic/non-ionic combinations
[0071] The surfactant system may comprise combinations of anionic and non-ionic surfactant materials. In some examples, the ratio between the weight of the anionic surfactant and the weight of the nonionic surfactant is at least about 2:1. In other examples, the ratio of the weight of the anionic surfactant to the weight of the nonionic surfactant is at least about 5:1. In additional examples, the ratio of the weight of the anionic surfactant to the weight of the nonionic surfactant is at least about 10:1. cationic surfactants
[0072] The surfactant system may comprise a cationic surfactant. In some aspects, the surfactant system comprises from 0% to about 7%, or from about 0.1% to about 5%, or from about 1% to about 4% by weight of the surfactant system, of a cationic surfactant, eg a co-surfactant. In some aspects, the cleaning compositions of the invention are substantially free of cationic surfactants and surfactants that become cationic below a pH of 7, below a pH of 6.
[0073] Non-limiting examples of cationic surfactants include: quaternary ammonium surfactants, which can have up to 26 carbon atoms, including: alkoxylate-based quaternary ammonium (AQA) surfactants as discussed in US 6,136,769, dimethyl quaternary hydroxy ethyl ammonium as discussed in 6,004,922, dimethyl hydroxy ethyl lauryl ammonium chloride, cationic polyamine surfactants as discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005 and WO 98/ 35006, cationic ester surfactants as discussed in US Patent Nos. 4,228,042, 4,239,660 4,260,529 and US 6,022,844, and amino-based surfactants as discussed in US 6,221,825 and WO 00/47708, specifically amido propyldimethyl amine (APA).
[0074] Suitable cationic detersive surfactants also include alkyl pyridinium compounds, quaternary alkyl ammonium compounds, quaternary alkyl phosphonium compounds, ternary alkyl sulfonium compounds and mixtures thereof.
[0075] Suitable cationic detersive surfactants are quaternary ammonium compounds with the following general formula: (R)(R1)(R2)(R3)N+ X- wherein, R is a substituted or unsubstituted C6-18 alkenyl or alkyl moiety substituted, linear or branched, R1 and R2 are independently selected from methyl or ethyl moieties, R3 is a hydroxyl, hydroxymethyl or a hydroxyethyl moiety, X is an anion providing charge neutrality, suitable anions include: halides , as chloride; sulfate; and sulfonate. Suitable cationic detersive surfactants are C6-18 mono-alkyl monohydroxyethyl dimethyl quaternary ammonium chlorides. Highly suitable detersive cationic surfactants are C8-10 monoalkyl monohydroxyethyldimethyl quaternary ammonium chloride, C10-12 monoalkyl monohydroxyethyldimethyl quaternary ammonium chloride and C10 monoalkyl monohydroxyethyldimethyl quaternary ammonium chloride. zwitterionic surfactants
[0076] Examples of zwitterionic surfactants include: derivatives of secondary and tertiary amines, derivatives of secondary and tertiary heterocyclic amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See US Patent No. 3,929,678, column 19, line 38, through column 22, line 48, for examples of zwitterionic surfactants; betaines, including alkyldimethyl betaine and cocodimethyl amidopropyl betaine, C8 to C18 amine oxides (preferably C12 to C18 amine oxides), and sulfo and hydroxybetaines such as N-alkyl-N,N-dimethylamino-1-propanesulfonate, wherein the alkyl group may be C8 to C18, and in certain embodiments from C10 to C14. amphoteric surfactants
[0077] Examples of amphoteric surfactants include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight-chain or branched and where one of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one of the aliphatic substituents contains an anionic water-solubilizing group, e.g. carboxyl, sulfonate, sulfate. Examples of compounds that fit this definition are sodium 3-(dodecylamino)propionate, sodium 3-(dodecylamino)propane-1-sulfonate, sodium 2-(dodecylamino)ethyl sulfate, sodium 2-(dimethylamino)octadecanoate , sodium 3-(N-carboxymethyldodecylamino)propane 1-sulfonate, disodium octadecylaminodiacetate, sodium 1-carboxymethyl-2-undecylimidazole, and sodium N,N-bis(2-hydroxyethyl)-2-sulfate-3-dodekoxypropylamine. See US Patent No. 3,929,678, issued to Laughlin et al., December 30, 1975, at column 19, lines 18 through 35, for examples of amphoteric surfactants. Suitable amphoteric surfactants also include sarcosinates, glycinates, taurinates, and mixtures thereof.
[0078] In one aspect, the surfactant system comprises an anionic surfactant and, as a co-surfactant, a nonionic surfactant, for example an ethoxylated C12-C18 alkyl. In another aspect, the system comprises C10-C15 alkylbenzenesulfonates (LAS) and, as a co-surfactant, an anionic surfactant, for example, C10-C18 alkylalkoxy sulfates (AExS), wherein x is from 1 to 30. In another aspect , the surfactant system comprises an anionic surfactant and, as a co-surfactant, a cationic surfactant, for example dimethyl hydroxyethyl lauryl ammonium chloride. In other aspects, the additional surfactant comprises an anionic surfactant and an amphoteric surfactant, for example C12-C14 dimethylamine oxide. branched surfactants
[0079] Suitable branched detersive surfactants include branched anionic surfactants selected from branched or branched sulphate surfactants, e.g. branched alkyl sulfate, branched alkoxylated alkyl sulfate, and branched alkylbenzenesulfonates, comprising one or more random alkyl branches, e.g. C1 alkyl groups -4, typically methyl and/or ethyl groups.
[0080] In some respects, the detersive surfactant is a branched-medium-chain detersive surfactant, typically a branched-medium-chain anionic detersive surfactant, for example, a branched-medium-chain alkyl sulfate and/or an alkylbenzenesulfonate branched medium chain. In some aspects, the detersive surfactant is a branched medium chain alkyl sulfate. In some aspects, the medium chain branches are C1-4 alkyl groups, typically methyl and/or ethyl groups.
[0081] In some aspects, the branched surfactant comprises a medium-chain branched surfactant compound, with a longer alkyl chain, of the formula: Ab - X — B where: (a) Ab is a hydrophobic C9 to C22 (total carbons in the chemical moiety), typically from about C12 to about C18, with the branched mid-chain alkyl moiety having: (1) a longer linear carbon chain attached to the -X-B moiety in the range of 8 to 21 carbon atoms ; (2) one or more C1 - C3 alkyl moieties branching off from that longer linear carbon chain; (3) at least one of the branched alkyl moieties attached directly to a carbon of the longest straight carbon chain at a position that lies in the range of the 2-position carbon (counting from the 1-position carbon which is attached to the 2-position carbon moiety). - X - B, up to the carbon of position w - 2, (the terminal carbon minus 2 carbons); and (4) the surfactant composition has an average total number of carbon atoms in the Ab-X moiety in the above formula in the range from about greater than 14.5 to about 17.5 (typically from about 15 to about 17); (b) B is a hydrophilic moiety selected from sulfates, sulfonates, amine oxides, polyoxyalkylene (such as polyoxyethylene and poly - oxypropylene), alkoxylated sulfates, polyhydroxy moieties, phosphate ester, glycerol sulfonates, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosucaminates, polyalkoxylated carboxylates, glucamides, taurinates, sacsinates, glycinates, isethionates, dialkanolamides, monoalkanolamides , monoalcan olamide sulfates, diglycolamides, diglycolamide sulfates, glycerol esters, glycerol ester sulfates, glycerol ethers, glycerol ether sulfates, polyglycerol ethers, polyglycerol ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters , ammonialkanesulfonates, amidopropyl betaines, quaternary alkylates, queternary alkylated/polyhydroxyalkylated, quaternary alkylated/polyhydroxylated oxypropyl, imidazolines, 2-yl succinates, sulfonated alkyl esters and sulfonated fatty acids (it should be noted that more than one portion hydrophobic can be linked to B, for example, as in (Ab-X)zB to produce dimethyl quaternaries); and (c) X is selected from -CH2- and -C(O)-.
[0082] Generally, in the above formula, the Ab moiety does not have any substituted quaternary carbon atoms (i.e. 4 carbon atoms directly attached to a carbon atom). Depending on which hydrophilic moiety (B) is selected, the resulting surfactant can be anionic, nonionic, cationic, zwitterionic, amphoteric or ampholytic. In some respects, B is sulfate and the resulting surfactant is anionic.
[0083] In some aspects, the branched surfactant comprises a medium-chain branched, longer-chain alkyl surfactant compound of the above formula, wherein the Ab moiety is a branched primary alkyl moiety having the formula:
wherein the total number of carbon atoms in the branched primary alkyl portion of this formula (including the R, R1 and R2 branches) is from 13 to 19; R, R1, and R2 are each independently selected from hydrogen and C1-C3 alkyl (typically, methyl), provided that R, R1, and R2 are not all hydrogen, and that when z is 0, at least R or R1 is not is hydrogen; w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer from 0 to 13; and w + x + y + z is from 7 to 13.
[0084] In certain aspects, the branched surfactant comprises a medium-chain branched, longer-chain alkyl surfactant compound of the above formula, wherein the Ab moiety is a branched primary alkyl moiety having the formula selected from:
or mixtures thereof; where a, b, dee are integers, a+b is from 10 to 16, d+e is from 8 to 14 and where even when a+b=10, a is an integer from 2 to 9 and b is an integer from 1 to 8; when a+b=11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a+b=12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a+b=13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a+b=14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a+b=15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a+b=16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d+e=8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d+e=9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d+e=10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d+e=11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d+e=12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d+e=13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d+e=14, d is an integer from 2 to 13 and e is an integer from 1 to 12.
[0085] In the medium-branched chain surfactant compounds described above, certain branch points (e.g., the location along the chain of the R, R1, and/or R2 moieties in the above formula) are preferred over other branch points. along the surfactant main chain. The formula below illustrates the mid-chain branching range (i.e., where the branch points occur), the preferred mid-chain branching range, and the most preferred mid-chain branching range for Ab moieties of alkyl branched with monomethyl .

[0086] For monomethyl substituted surfactants, these bands exclude the two terminal carbon atoms of the chain, and the two carbon atoms immediately adjacent to the -X-B group.
[0087] The formula below illustrates the medium chain branching range, the preferred medium chain branching range and the most preferred medium chain branching range for Ab moieties of dimethyl substituted alkyl.

[0088] Additional adequate branched surfactants are revealed at US 6008181, US 6020303, US 6153577, US 6015781, US 6133222, US 6326348, US 6677289, US 6903059, US 6335312, and WO 9918929. Still other suitable branched surfactants include those described in WO9738956, WO9738957 and WO0102451.
[0089] In some aspects, the branched anionic surfactant comprises a branched-modified MLAS (alkyl benzenesulfonate) as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99 /05241, WO 99/07656, WO 00/23549 and WO 00/23548.
[0090] In some aspects, the branched anionic surfactant comprises a C12/C13 alcohol-based surfactant comprising a methyl branch randomly distributed along the hydrophobic chain, eg Safol®, Marlipal® available from Sasol.
[0091] Additional suitable branched anionic detersive surfactants include surfactants derived from branched alcohols in the 2-alkyl position, such as those sold under the trade names Isalchem®123, Isalchem®125, Isalchem®145, Isalchem®167, which are derived from the oxo process . Due to the oxo process, the branch is situated at the 2-alkyl position. These 2-alkyl branched alcohols are typically in the range of C11 to C14/C15 in length and comprise structural isomers that are all branched at the 2-alkyl position. These branched alcohols and surfactants are described in US20110033413.
[0092] Other suitable branched surfactants include those disclosed in S6037313 (P&G), WO9521233 (P&G), US3480556 (Atlantic Richfield), US6683224 (Cognis), US20030225304A1 (Kao), US2004236158A1 (R&H), US6818700 (04004) (1546) et al.), EP1280746 (Shell), EP1025839 (L'Oreal), US6765119 (BASF), EP1080084 (Dow), US6723867 (Cognis), EP1401792A1 (Shell), EP1401797A2 (Degussa AG), US2004048766 (Raths et al.) , US6596675 (L'Oreal), EP1136471 (Kao), EP961765 (Albemarle), US6580009 (BASF), US2003105352 (Dado et al.), US6573345 (Cryovac), DE10155520 (BASF), US6534691 (du Pont), US6407279 (ExxonMobil ), US5831134 (Peroxid-Chemie), US5811617 (Amoco), US5463143 (Shell), US5304675 (Mobil), US5227544 (BASF), US5446213A (MITSUBISHI KASEI CORPORATION), EP1230200A2 (BASF), EP1159237B1 (BASF), US200040 , EP1230200B1 (BASF), WO2004014826A1 (SHELL), US6703535B2 (CHEVRON), EP1140741B1 (BASF), WO2005037752A1 (SHELL), US6906230B1 (BASF), WO2005037747A2 (SHELL) OIL COMPANY.
[0093] Additional suitable branched detersive anionic surfactants include isoprenoid-based polybranched detergent alcohol surfactant derivatives as described in US 2010/0137649. Isoprenoid-based surfactants and isoprenoid derivatives are also described in the book entitled "Comprehensive Natural Products Chemistry: Isoprenoids Including Carotenoids and Steroids (Vol. II)", Barton and Nakanishi, © 1999, Elsevier Science Ltd and are included in structure E , and are incorporated herein by reference.
[0094] Additional suitable branched detersive anionic surfactants include those derived from anteiso and iso alcohols. Such surfactants are disclosed in WO2012009525.
[0095] Additional suitable branched anionic detersive surfactants include those described in US Patent Application Nos. 2011/0171155A1 and 2011/0166370A1.
[0096] Suitable branched anionic surfactants also include Guerbet's alcohol-based surfactants. Guerbet alcohols are non-functional, branched primary alcohols that have two linear carbon chains with the branch point always at the second carbon position. Guerbet alcohols are chemically described as 2-alkyl-1-alkanols. Guerbet alcohols generally have from 12 carbon atoms to 36 carbon atoms. Guerbet alcohols can be represented by the general formula: (R1)(R2)CHCH2OH, where R1 is a linear alkyl group, R2 is a linear alkyl group, the sum of carbon atoms in R1 and R2 is 10 to 34, and both R1 and R2 are present. Guerbet alcohols are commercially available from Sasol as Isofol® alcohols and from Cognis as Guerbetol.
[0097] The surfactant system disclosed herein may comprise any of the branched surfactants described above individually or the surfactant system may comprise a mixture of the branched surfactants described above. In addition, each of the branched surfactants described above may include a biobased content. In some aspects, the branched surfactant has a biobased content of at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 90% 95%, at least about 97% or about 100%. Auxiliary cleaning additives
[0098] The cleaning compositions of the invention may also contain auxiliary cleaning additives. Suitable cleaning auxiliary additives include builders (sequestering agents), builders or thickeners, clay soil removal agents/anti-redeposition agents, polymeric soil release agents, polymeric dispersing agents, polymeric grease, enzymes, enzyme stabilizing systems, bleach compounds, bleaching agents, bleach activators, bleach catalysts, bleaches, dyes, tinting agents, dye transfer inhibiting agents, chelating agents, foam suppressants, softeners and perfumes. enzymes
[0099] The cleaning compositions described herein may comprise one or more enzymes that provide cleaning and/or fabric care performance benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxydases, ligninases, pullulanases , tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase and amylases, or mixtures thereof. A typical combination is an enzyme cocktail which may comprise, for example, a protease and a lipase together with amylase. When present in a cleaning composition, the aforementioned additional enzymes can be present in levels ranging from about 0.00001% to about 2%, from about 0.0001% to about 1%, or even from about 0.0001% to about 1% 0.001% to about 0.5% enzyme protein by weight of the cleaning composition.
[0100] In one aspect, preferred enzymes would include a protease. Suitable proteases include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases such as subtilisins (EC 3.4.21.62). Suitable proteases include those of animal, plant or microbial origin. In one aspect, such a suitable protease may be of microbial origin. Suitable proteases include chemically or genetically modified mutants of the aforementioned suitable proteases. In one aspect, the suitable protease may be a serine protease, such as an alkaline microbial protease and/or a trypsin-like protease. Examples of suitable neutral or alkaline proteases include: (a) subtilisins (EC 3.4.21.62), including those derived from Bacillus, such as Bacillus lentus, Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii , described in US 6,312,936 B1 , US 5,679,630 , US 4,760,025 , US 7,262,042 and WO09/021867 . (b) trypsin-like or chymotrypsin-like proteases, such as trypsin (e.g. of porcine or bovine origin), including the Fusarium protease described in WO 89/06270 and the Cellumonas-derived chymotrypsin proteases described in WO 05/052161 and WO 05/052146. (c) metalloproteases, including those derived from Bacillus amyloliquefaciens described in WO 07/044993A2.
[0101] Preferred proteases include those derived from Bacillus gibsonii or Bacillus lentus.
[0102] Suitable commercially available protease enzymes include those sold under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®, Ovozyme® , Neutrase®, Everlase® and Esperase®, available from Novozymes A/S (Denmark), those sold under the trade name Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime® , Purafect Ox®, FN3®, FN4®, Excellase® and Purafect OXP®, available from Genencor International, those sold under the tradename Opticlean® and Optimase® by Solvay Enzymes, those available from Henkel/Kemira, namely, BLAP (sequence shown in Figure 29 of US 5,352,604 with the following mutations S99D + S101 R + S103A + V104I + G159S, later in this document called BLAP), BLAP R (BLAP with S3T + V4I + V199M + V205I + L217D), BLAP X (BLAP with S3T + V4I + V205I) and BLAP F49 (BLAP with S3T + V4I + A194P + V199M + V205I + L217D) - all available levels next to Henkel/Kemira; and KAP (Bacillus alkalophilus subtilisin with A230V + S256G + S259N mutations) from Kao.
[0103] Suitable alpha-amylases include those of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included. A preferred alkaline alpha amylase is derived from a bacillus strain, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus sp., such as Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 (USP 7,153,818) DSM 12368, DSMZ no. 12649, KSM AP1378 (WO 97/00324), KSM K36 or KSM K38 (EP 1,022,334). Preferred amylases include: (a) variants described in WO 94/02597, WO 94/18314, WO96/23874 and WO 97/43424, especially variants with substitutions at one or more of the following positions versus the enzyme mentioned as SEQ ID NO: 2 in WO 96/23874: 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391 , 408 and 444. (b) the variants described in USP 5,856,164 and WO99/23211, WO 96/23873, WO00/60060 and WO 06/002643, especially variants with one or more substitutions at the following positions versus the AA560 enzyme mentioned as SEQ ID NO: 12 in WO 06/002643: 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 203, 214, 231 I , 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484, preferably also containing the D183* and G184* deletions. (c) variants that show at least 90% identity to SEQ ID No. 4 in WO06/002643, the naturally occurring enzyme obtained from Bacillus SP722, especially the variants deleted at positions 183 and 184 and the variants described in WO 00/60060, which is incorporated herein by reference. (d) variants that show at least 95% identity with the naturally occurring enzyme obtained from Bacillus sp.707 (SEQ ID NO: 7 in US 6,093,562), especially those comprising one or more of the following M202 mutations, M208, S255, R172, and/or M261. Preferably, said amylase comprises one or more of M202L, M202V, M202S, M202T, M202I, M202Q, M202W, S255N and/or R172Q. Particularly preferred are those comprising the M202L or M202T mutations. (e) variants described in WO 09/149130, preferably those showing at least 90% identity with SEQ ID NO: 1 or SEQ ID NO: 2 in WO 09/149130, the wild type Geobacillus Stearophermophilus enzyme or a version truncated the same.
[0104] Suitable commercially available alpha-amylases include DURAMYL®, LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, FUNGAMYL® and BAN® (Novozymes A/S, Bagsvaerd, Denmark), KEMZYM® AT 9000 (Biozym Biotech Trading GmbH Wehlistrasse 27b A-1200, Vienna, Austria), RAPIDASE®, PURASTAR®, ENZYSIZE®, OPTISIZE HT PLUS®, POWERASE® and PURASTAR OXAM® (Genencor International Inc. , Palo Alto, California, USA) and KAM® (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku, 1038210, Tokyo, Japan). In one aspect, suitable amylases include NATALASE®, STAINZYME® and STAINZYME PLUS® and mixtures thereof.
[0105] In one aspect, such enzymes may be selected from the group consisting of: lipases, including "first cycle lipases" such as those described in US patent 6,939,702 B1 and US PA 2009/0217464 . In one aspect, the lipase is a first-wash lipase, preferably a wild-type lipase variant of Thermomyces lanuginosus comprising one or more of the T231R and N233R mutations. The naturally occurring sequence consists of the 269 amino acids (amino acids 23 to 291) of Swiss-Prot accession number O59952 (derived from Thermomyces lanuginosus (Humicola lanuginosa)). Preferred lipases would include those sold under the tradenames Lipex® and Lipolex®.
[0106] In one aspect, other preferred enzymes include microbe-derived endo-glycanases, endoglycanases that exhibit endo-beta-1,4-glucanase activity (EC 3.2.1.4), which includes a bacterial polypeptide endogenous to a member. of the genus Bacillus which has a sequence of at least 90%, 94%, 97% and even 99% identity to the amino acid sequence SEQ ID NO:2 in 7,141,403B2) and mixtures thereof. Suitable endoglucanases are sold under the tradenames Celluclean® and Whitezyme® (Novozymes A/S, Bagsvaerd, Denmark).
[0107] Other preferred enzymes include pectawash lyases sold under the tradenames Pectawash®, Pectaway®, Xpect® and mannanases sold under the tradenames Mannaway® (all available from Novozymes A/S, Bagsvaerd, Denmark) and Purabrite® (Genencor International Inc., Palo Alto, California, USA). Enzyme stabilizing system
[0108] The enzyme-containing compositions described herein may optionally comprise from about 0.001% to about 10%, in some examples from about 0.005% to about 8%, and in other examples from about 0. 01% to about 6% by weight of the composition of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system that is compatible with detersive enzymes. Such a system may be inherently provided by other active agents present in the formulation, or be added separately, for example, by the formulator or by a manufacturer of ready-to-use enzymes in detergents. Such stabilizing systems may, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, chlorine bleach sequestrants and mixtures thereof and are designed to deal with different stabilization problems. depending on the type and physical form of the cleaning composition. See US Patent No. 4,537,706 for a review of borate stabilizers. In the case of aqueous detergent compositions comprising protease, a reversible protease inhibitor, such as a boron compound that includes borate, 4-formylphenylboronic acid, phenylboronic acid and derivatives thereof, or compounds such as calcium formate, sodium formate and 1,2- propanediol may be added to further optimize stability. Builders (hijackers)
[0109] The cleaning compositions of the present invention may optionally comprise a builder. Detergents typically comprise about 1% by weight of builder, based on the total weight of the composition. Liquid cleaning compositions can comprise up to about 10% builder and in some examples up to 8% builder, based on the total weight of the composition. Granular cleaning compositions can comprise up to about 30% builder and in some examples up to 5% builder, based on the total weight of the composition.
[0110] Builders selected from aluminosilicates (e.g. zeolite-based builders such as zeolite A, zeolite P, and zeolite MAP) and silicates help control mineral hardness in wash water, specifically calcium and/or calcium. or magnesium, or to help remove particulate matter from surfaces. Suitable builders can be selected from the group consisting of phosphates, such as polyphosphates (eg sodium tri-polyphosphate), especially their sodium salts; carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate; organic mono, di, tri and tetracarboxylates, especially water-soluble non-surfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as water-soluble or oligomeric low molecular weight polymer carboxylates, including aliphatic and aromatic types; and phytic acid. These may be supplemented by borates, for example, for pH buffering purposes, or by sulfates, especially sodium sulfate, and any other fillers or other carriers that may be important for engineering stable cleaning compositions containing surfactants and/or or builders. Other suitable additional builders can be selected from citric acid, lactic acid, fatty acid, polycarboxylate based builders, for example acrylic acid copolymers, acrylic acid and maleic acid copolymers and acrylic acid and/or maleic acid copolymers and others suitable ethylenic monomers with various types of additional functionality. Also suitable for use as builders in the present invention are synthesized crystalline ion exchange materials or hydrates thereof, which have a chain structure and a composition represented by the following general anhydride form: x(M2O)^ySiO2^zM'O where M is Na and/or K, M' is Ca and/or Mg; y/x is 0.5 to 2.0; and z/x is 0.005 to 1.0 as taught in the U.S. patent. no. 5,427,711.
[0111] Alternatively, the composition may be substantially builder free. Structuring / Thickeners i. Dibenzylidene polyol acetal derivative
[0112] The fluid detergent composition may comprise from about 0.01% to about 1% by weight of a dibenzylidene polyol acetal (DBPA) derivative, or from about 0.05% to 0.8%, or from about 0.1% to about 0.6%, or even from about 0.3% to about 0.5%. Non-limiting examples of suitable DBPA molecules are disclosed in US 61/167604. In one embodiment, the DBPA derivative may comprise a dibenzylidene sorbitol acetal (DBS) derivative. Said DBS derivative may be selected from the group consisting of: 1,3:2,4-dibenzylidene sorbitol; 1,3:2,4-di(p-methyl benzylidene) sorbitol; 1,3:2,4-di(p-chlorobenzylidene) sorbitol; 1,3:2,4-di(2,4-dimethyldibenzylidene) sorbitol; 1,3:2,4-di(p-ethylbenzylidene) sorbitol; and 1,3:2,4-di(3,4-dimethyldibenzylidene) sorbitol or mixtures thereof. These and other suitable DBS derivatives are described in US 6,102,999, column 2, line 43 to column 3, line 65. ii. bacterial cellulose
[0113] The fluid detergent composition may also comprise from 0.005% to 1% by weight of a bacterial cellulose network. The term "bacterial cellulose" encompasses any type of cellulose produced by fermentation of a bacterium of the genus Acetobacter, such as CELLULON® by CPKelco U.S., and includes materials popularly called microfibrillated cellulose, cross-linked bacterial cellulose, and the like. Some examples of suitable bacterial cellulose can be found in US 6,967,027 , US 5,207,826 , US 4,487,634 , US 4,373,702 , US 4,863,565 , and US 2007/0027108 . In one aspect, said fibers have cross-sectional dimensions of 1.6 nm to 3.2 nm by 5.8 nm to 133 nm. Additionally, bacterial cellulose fibers have an average microfiber length of about at least 100 nm or from about 100 to about 1500 nm. In one aspect, bacterial cellulose microfibers have an aspect ratio, which means the average length of the microfiber divided by the greatest cross-sectional width of the microfiber, from about 100:1 to about 400:1, or even from about 200:1 to about 300:1. iii. Coated Bacterial Cellulose
[0114] In one aspect, the bacterial cellulose is at least partially coated with a polymeric thickener. Bacterial cellulose at least partially can be prepared according to the methods set out in US 2007/0027108 paragraphs 8 to 19. In one aspect, the at least partially coated bacterial cellulose comprises from 0.1% to 5%, or even from about 0.5% to about 3% by weight bacterial cellulose; and from about 10% to about 90% by weight of the polymeric thickener. Suitable bacterial cellulose may include the bacterial cellulose described above and suitable polymeric thickeners include: carboxymethyl cellulose, cationic hydroxy methyl cellulose and mixtures thereof. iv. Cellulose fibers not derived from bacterial cellulose
[0115] In one aspect, the composition may additionally comprise from about 0.01 to about 5% by weight of the composition of a cellulosic fiber. Said cellulosic fiber can be extracted from vegetables, fruits or wood. Commercially available examples are Avicel® from FMC, Citri-Fi from Fiberstar or Betafib from Cosun. v. Non-polymeric crystalline hydroxyl-functional materials
[0116] In one aspect, the composition may further comprise from about 0.01 to about 1% by weight of the composition of a crystalline, non-polymeric hydroxyl-functional structurant. Said crystalline non-polymeric hydroxy-functional builders may generally comprise a crystallisable glyceride which may be pre-emulsified in order to aid dispersion in the final fluid detergent composition. In one aspect, the crystallisable glycerides may include hydrogenated castor oil or "HCO" or derivatives thereof, so long as it is capable of crystallizing in the liquid detergent composition. saw. Polymer structuring agents
[0117] Fluid detergent compositions of the present invention may comprise from about 0.01% to about 5% by weight of a synthetic and/or naturally derived polymeric builder. Examples of naturally derived polymeric builders for use in the present invention include: hydroxy ethyl cellulose, hydrophobically modified hydroxy ethyl cellulose, carboxy methyl cellulose, polysaccharide derivatives and mixtures thereof. Suitable polysaccharide derivatives include: pectin, alginate, arabinogalactan (gum arabic), carrageenan, gellan gum, xanthan gum, guar gum and mixtures thereof. Examples of synthetic polymeric builders for use in the present invention include: polycarboxylates, polyacrylates, hydrophobically modified ethoxylated urethanes, hydrophobically modified nonionic polyols and mixtures thereof. In one aspect, said polycarboxylate polymer is a polyacrylate, polymethacrylate or mixtures thereof. In another aspect, the polyacrylate is a copolymer of a mono- or di-unsaturated carbonic acid and a C1-C30 alkyl ester of (meth)acrylic acid. Said copolymers are available from Noveon Inc. under the trade name Carbopol Aqua 30. vii. diamido gelling agents
[0118] In one aspect, the external structuring system may comprise a di-starch gelling agent having a molecular weight of from about 150 g/mol to about 1500 g/mol or even from about 500 g/mol to about 900 g /mol. Such dia-starch gelling agents may comprise at least two nitrogen atoms, at least two of said nitrogen atoms forming amidofunctional substitution groups. In one aspect, the amide groups are different. In another aspect, the amide-functional groups are the same. The diamido gelling agent has the following formula:
wherein: R1 and R2 are amino-functional end groups, or even amidofunctional end groups, in one aspect R1 and R2 may comprise a pH-adjustable group, wherein the pH-adjustable starch gelling agent may have a pKa of about 1 to about 30, or even from about 2 to about 10. In one aspect, the adjustable pH group may comprise a pyridine. In one aspect, R1 and R2 may be different. In another aspect, they may be the same. L is a linking moiety having a molecular weight of from 14 to 500 g/mol. In one aspect, L may comprise a carbon chain comprised between 2 and 20 carbon atoms. In another aspect, L may comprise an adjustable pH group. In one aspect, the adjustable pH group is a secondary amine.
[0119] In one aspect, at least one of R1, R2 or L may comprise an adjustable pH group.
[0120] Non-limiting examples of di-starch gelling agents are: N,N'-(2S,2'S)-1,1'-(dodecane-1,12-diylbis(azanediyl))bis(3-methyl-1-oxobutane) -2,1-diyl)diisonicotinamide
Dibenzyl (2S,2'S)-1,1'-(propane-1,3-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)dicarbamate
Dibenzyl (2S,2'S)-1,1'-(dodecane-1,12-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)dicarbamate
Polymeric dispersing agents
[0121] The cleaning composition may comprise one or more polymeric dispersing agents. Examples are carboxymethylcellulose, poly(vinylpyrrolidone), poly(ethylene glycol), poly(vinyl alcohol), poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates such as polyacrylates, maleic acid copolymers /acrylic and lauryl methacrylate/acrylic acid copolymers.
[0122] The cleaning composition may comprise one or more amphiphilic cleaning polymers such as the compound having the following general structure: bis((C2H5O)(C2H4O)n)(CH3)-N+-CxH2x-N+-(CH3)- bis((C2H5O)(C2H4O)n), where n = from 20 to 30, ex = from 3 to 8, or sulphated or sulfonated variants thereof.
[0123] The cleaning composition may comprise alkoxylated amphiphilic grease/grease cleaning polymers that have balanced hydrophilic and hydrophobic properties so that they can remove grease/grease particles from fabrics and surfaces. Specific embodiments of the alkoxylated amphiphilic grease/grease cleaning polymers of the present invention comprise a core structure and a plurality of alkoxylate groups attached to the core structure. These may comprise alkoxylated polyalkyleneimines, for example, having an inner block of poly(ethylene oxide) and an outer block of poly(propylene oxide).
[0124] Carboxylate Polymer - The cleaning composition of the present invention may also include one or more carboxylate polymers such as a random maleate/acrylate copolymer or polyacrylate homopolymer. In one aspect, the carboxylate polymer is a polyacrylate homopolymer having a molecular weight of from 4000 Da to 9000 Da, or from 6000 Da to 9000 Da. Polymer for dirt release
[0125] The cleaning compositions described herein may include from about 0.01% to about 10.0%, typically from about 0.1% to about 5%, in some aspects from about 0.2 % to about 3.0% by weight of the composition of a soil release polymer (also known as polymeric soil release agents or "SRA").
[0126] The soil release polymers typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments to deposit on hydrophobic fibers and remain adhered to them until the end of the washing cycles and rinse, thus serving as an anchor for the hydrophilic segments. This can make stains that occur after treatment with the dirt removal agent to be cleaned more easily in later washing procedures.
[0127] Soil release agents can include a variety of charged monomer units, e.g., anionic or cationic (see e.g. US Patent No. 4,956,447), as well as uncharged. The dirt release agent structure can be linear, branched or even star-shaped. The soil release polymer may include a capping portion, which is especially effective for controlling the molecular weight of the polymer or altering the physical or surface active properties of the polymer. The structure and load distribution of the soil release polymer can be adjusted for application to different types of fibers or textiles and for formulation into different detergent products or detergent additives. Suitable soil release polyester polymers have a structure as defined by one of the following structures (III), (IV) or (V):
where: a, b and c are from 1 to 200; d, e and f are from 1 to 50, Ar is a 1,4-substituted phenylene, sAr is 1,3-phenylene substituted at the 5-position with SO 3 Me; Me is H, Na, Li, K, Mg+2, Ca+2, Al+3, ammonium, mono, di, tri or tetra-alkylammonium, the alkyl groups being C1C18 alkyl or C2-C10 hydroxyalkyl, or any other mixing thereof; R1 , R2 , R3 , R4 , R5 and R6 are independently selected from H or C1 -C18 n- or isoalkyl; and R7 is a linear or branched C1C18 alkyl, or a linear or branched C2-C30 alkenyl or a cycloalkyl group having 5 to 9 carbon atoms, or a C6-C30 aryl group or a C6-C30 arylalkyl group.
[0128] Suitable polyester soil release polymers are terephthalate polymers with structure (III) or (IV) above. Other suitable soil release polymers may include, for example, sulfonated or non-sulfonated PET/POET polymers, either end-blocked or end-blocked. Examples of suitable polyester soil release polymers are the REPEL-O-TEX® polymer range supplied by Rhodia, including REPEL-O-TEX® SRP6 and REPEL-O-TEX® SF-2. Other suitable soil release polymers include TexCare® polymers, including TexCare® SRA-100, TexCare® SRA-300, TexCare® SRN-100, TexCare® SRN-170, TexCare® SRN-240, TexCare® SRN-300, and TexCare® SRN-325, all provided by Clariant. Especially useful soil release polymers are the sulfonated chain-blocked terminalless polyesters described in WO 95/32997A (Rhodia Chimie). Other suitable soil release polymers are Marloquest® polymers such as Marloquest® SL supplied by Sasol. Examples of SRAs are described in US Patent Nos. 4,968,451; 4,711,730; 4,721,580; 4,702,857; 4,877,896; 3,959,230; 3,893,929; 4,000,093; 5,415,807; 4,201,824; 4,240,918; 4,525,524; 4,201,824; 4,579,681; and 4,787,989; European patent application 0 219 048; 279,134 A; 457,205 A; and DE 2,335,044; and WO201419792; WO2012104156/57/58. WO201419658; WO20141965; WO201429479. Cellulosic Polymer
[0129] The cleaning compositions described herein may include from about 0.1% to about 10%, from about 0.5% to about 7%, or in some aspects, from about 3% to about 5% by weight of a cellulosic polymer composition.
[0130] Suitable cellulosic polymers include alkyl cellulose, alkyl alkoxyalkylcellulose, carboxyalkylcellulose, and alkyl carboxyalkylcellulose. In some aspects, the cellulosic polymer is selected from carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose, methylcarboxymethylcellulose, or mixtures thereof. In certain aspects, the cellulosic polymer is a carboxymethyl cellulose having a degree of carboxy methyl substitution of about 0.5 to about 0.9 and a molecular weight of about 100,000 Da to about 300,000 Da. Carboxymethylcellulose polymers include Finnfix® GDA (sold by CP Kelko), a hydrophobically modified carboxymethylcellulose, for example, the alkyl ketene dimer derivative of carboxymethylcellulose sold under the tradename Finnfix® SH1 (CP Kelko), or carboxymethylcellulose in blocks sold under the trade name Finnfix®V (sold by CP Kelko). additional amines
[0131] Additional amines may be used in the cleaning compositions described herein for additional removal of grease/grease and particulates from soiled materials. Cleaning compositions described herein may comprise from about 0.1% to about 10%, in some examples from about 0.1% to about 4%, and in other examples from about 0.1% to about 2% by weight of the cleaning composition, of additional amines. Non-limiting examples of additional amines may include, but are not limited to, polyamines, oligoamines, triamines, diamines, pentamines, tetraamines, or combinations thereof. Specific examples of suitable additional amines include tetraethylene pentamine, triethylene tetraamine, diethylene triamine, or a mixture thereof.
[0132] For example, alkoxylated polyamines can be used for grease/fat and particulate removal. These compounds may include, but are not limited to, ethoxylated polyethylene imine, ethoxylated hexamethylene diamine, and sulfated versions thereof. Polypropoxylated derivatives may also be included. A wide variety of amines and polyalkylene imines can be alkoxylated to varying degrees. A useful example is 600 g/mol of ethoxylated polyethyleneimine core for 20 EO groups per NH and is available from BASF. The cleaning compositions described herein may comprise from about 0.1% to about 10%, and in some examples, from about 0.1% to about 8%, and in other examples, from about 0.1 % to about 6% by weight of the cleaning composition of alkoxylated polyamines.
[0133] Alkoxylated polycarboxylates can also be used in the cleaning compositions of the present invention to provide grease/grease removal. Such materials are described in WO 91/08281 and PCT 90/01815. Chemically, these materials comprise polyacrylates that have one ethoxy side chain for every 7 to 8 acrylate units. The side chains are of the following Formula - (CH2CH2O)m (CH2)nCH3 where m is 2 to 3 and n is 6 to 12. The side chains are ester linked to the polyacrylate "backbone" to provide a polymer-like structure "in comb". Molecular weight can vary but can be in the range of around 2000 to around 50,000. The cleaning compositions described herein may comprise from about 0.1% to about 10%, and in some examples, from about 0.25% to about 5%, and in other examples, from about 0.3 % to about 2% by weight of the cleaning composition of alkoxylated polycarboxylates. Bleach Compounds, Bleach Agents, Bleach Activators and Bleach Catalysts
[0134] The cleaning compositions described herein may contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. Bleaching agents may be present at levels from about 1% to about 30%, and in some examples from about 5% to about 20%, based on the total weight of the composition. If present, the amount of bleach activator can be from about 0.1% to about 60%, and in some examples from about 0.5% to about 40%, of the bleach composition that comprises the bleaching agent plus the bleach activator.
[0135] Examples of bleaching agents include oxygen-based bleaching agent, perborate-based bleaching agent, percarboxylic acid-based bleaching agent and its salts, peroxygen-based bleaching agent, persulfate-based bleaching agent, persulfate-based bleaching agent, percarbonate base, and mixtures thereof. Examples of bleaching agents are found in U.S. Patent No. 4,483,781, U.S. Patent Application. Serial No. 740,446, European Patent Application 0,133,354, U.S. Patent No. 4,412,934 and U.S. Patent no. 4,634,551.
[0136] Examples of bleach activators (eg, acyl lactam activators) are shown in patent nos. 4,915,854; 4,412,934; 4,634,551; 4,634,551 and 4,966,723.
[0137] In some examples, the cleaning compositions may also include a transition metal-based bleach catalyst. In other examples, the transition metal-based bleach catalyst may be encapsulated. The transition metal-based bleach catalyst may comprise a transition metal ion, which may be selected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe( II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu( II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo( IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III) and Ru(IV). The transition metal-based bleach catalyst comprises a linker, for example, a macropolycyclic linker, or a cross-bridged macropolycyclic linker. The transition metal ion can be coordinated with the ligand. The linker may comprise at least four donor atoms, at least two of which are bridgehead donor atoms. Suitable transition metal-based bleach catalysts are described in the U.S. 5,580,485, U.S. 4,430,243; U.S. 4,728,455; U.S. 5,246,621; U.S. 5,244,594; U.S. 5,284,944; U.S. 5,194,416; U.S. 5,246,612; U.S. 5,256,779; U.S. 5,280,117; U.S. 5,274,147; U.S. 5,153,161; U.S.5,227,084; U.S. 5,114,606; U.S. 5,114,611, EP 549,271 A1; EP 544,490 A1; EP 549,272 A1; and EP 544,440 A2. Another suitable transition metal bleaching catalyst is a manganese-based catalyst such as disclosed in US 5,576,282. Suitable cobalt bleach catalysts are described, for example, in US Patent Nos. 5,597,936 and US 5,595,967. Such cobalt-based catalysts are readily prepared by known procedures, as taught, for example, in US Document No. 5,597,936 and US Document No. 5,595,967. A suitable transition metal bleach catalyst is a ligand transition metal complex, such as bispidones, described in WO 05/042532 A1 incorporated herein by reference.
[0138] Bleaching agents in addition to oxygen-based bleaching agents are also known in the art and can be used in cleaning compositions. They include, for example, photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines described in US Patent No. 4,033,718, or preformed organic peracids, such as peroxycarboxylic acid or a salt thereof, or a peroxy sulfonic acid or salt thereof. A suitable organic peracid is phthaloylimido peroxycaproic acid. If used, the cleaning compositions described herein will typically contain from about 0.025% to about 1.25% by weight of the composition of such bleaching agents, and in some examples, zinc phthalocyanine sulfonate. brightening agents
[0139] Optical brighteners or other brightening or whitening agents can be incorporated at levels of from about 0.01% to about 1.2% by weight of the composition in the cleaning compositions described herein. Commercial brighteners that can be used in the present invention can be classified into subgroups, which include, but are not necessarily limited to, stilbene derivatives, pyrazoline, coumarin, benzoxazoles, carboxylic acid, methinocyanines, dibenzothiophene-5,5 -dioxide, azoles, heterocycles with 5- and 6-membered rings and other miscellaneous agents. Examples of these brighteners are given in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, published by John Wiley & Sons, New York (1982). Specific non-limiting examples of optical brighteners that may be useful in the present compositions are those identified in US Patent No. 4,790,856 and US Patent No. 4,790,856. 3,646,015.
[0140] In some examples, the fluorescent brightener comprises a compound of formula (1):
wherein: X1, X2, X3, and X4 are -N(R1)R2, wherein R1 and R2 are independently selected from hydrogen, phenyl, hydroxyethyl, or unsubstituted or substituted C1-C8 alkyl, or - N(R1)R2 form a heterocyclic ring, preferably R1 and R2 are independently selected from a hydrogen or phenyl, or -N(R1)R2 form an unsubstituted or substituted morpholine ring; and M is a hydrogen or a cation, preferably M is sodium or potassium, more preferably M is sodium.
[0141] In some examples, the fluorescent brightener is selected from the group consisting of 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbene disodium disulfonate (brightener 15, available commercially under the trademark Tinopal AMS-GX by Ciba Geigy Corporation), 4,4'-bis{[4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine -2-yl]-amino}-2,2'-stilbene disodium disulfonate (available commercially under the tradename Tinopal UNPA-GX by Ciba-Geigy Corporation), 4,4'-bis{[4-anilino- Disodium 6-(N-2-hydroxy-ethyl-N-methylamino)-s-triazine-2-yl]-amino}-2,2'-stilbene disulfonate (available for sale under the trademark Tinopal 5BM-GX by Ciba -Geigy Corporation). More preferably, the fluorescent brightener is disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazino-2-yl]-amino}-2,2'-stilbenedisulfonate. Brighteners can be added in particulate form or as a premix with a suitable solvent, for example a non-ionic surfactant monoethanolamine or propane diol. Dyeing agents for fabrics
[0143] The compositions may comprise a coloring agent for fabrics (sometimes called toning, bluening or bleaching agents). Typically, the tinting agent imparts a blue or violet tint to the fabric. The tinting agents can be used alone or in combination to create a specific shade of hue and/or to tone different types of fabrics. This can be achieved, for example, by mixing red and blue-green dyes to produce a blue or violet hue. Tinting agents may be selected from any known chemical class of dye, including, but not limited to, acridine, anthraquinone (including polycyclic quinones), azine, azo (e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), including premetallized azo, benzodifuran and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicianine, diphenylmethane, formazan, hemicianin, indigoids, methane, naphthalimides, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenes and mixtures thereof.
[0144] Suitable fabric tinting agents include dyes, dye-clay conjugates, and organic and inorganic pigments. Suitable dyes include small molecule dyes and polymeric dyes. Suitable small molecule dyes include small molecule dyes selected from the group consisting of dyes falling within the color index (CI) classifications of direct, basic, reactive or reactive hydrolyzed, solvent or disperse, e.g. those that are classified as blue , violet, red, green or black, and which provide the desired hue, alone or in combination. In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of Direct Violet Color Index (Society of Dyers and Colourists, Bradford, UK) numbers such as 9, 35, 48, 51, 66, and 99, Direct Blue dyes like 1, 71, 80 and 279, and Acid Red dyes like 17, 73, 52, 88 and 150, Acid Violet dyes like 15, 17, 24, 43, 49 and 50, Blue dyes Acid like 15, 17, 25, 29, 40, 45, 75, 80, 83, 90 and 113, and Acid Black dyes like 1, Basic Violet dyes 1, 3, 4, 10 and 35, Basic Blue dyes like 3, 16, 22, 47, 66, 75 and 159, Disperse dyes or Solvents such as those described in EP1794275 or EP1794276, or dyes such as those disclosed in US 7208459 B2 and mixtures thereof. In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of Color Index numbers Acid Violet 17, Direct Blue 71, Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113 or mixtures thereof.
[0145] Suitable polymeric dyes include polymeric dyes selected from the group consisting of polymers containing covalently linked (sometimes called conjugated) chromogens (dye-polymer conjugates), e.g. polymers with copolymerized chromogens in the chain. polymer and mixtures thereof. Polymeric dyes include those described in WO2011/98355, WO2011/47987, US2012/090102, WO2010/145887, WO2006/055787 and WO2010/142503.
[0146] In another aspect, suitable polymeric dyes include those selected from the group consisting of fabric adherent dyes commercially available under the name Liquitint® (Milliken, Spartanburg, South Carolina, USA), dye-polymer conjugates formed from at least one reactive dye and a polymer selected from the group consisting of polymers comprising a portion selected from the group consisting of a hydroxyl moiety, a primary amine moiety, a secondary amine moiety, a thiol moiety and mixtures thereof. In yet another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of Liquitint® Violet CT, carboxymethylcellulose (CMC) covalently linked to a reactive blue, reactive violet or reactive red dye such as CMC conjugated to C.I. Reactive Blue 19, sold by Megazyme, Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product code S-ACMC, alkoxylated triphenylmethane polymeric colorants, alkoxylated thiophene polymeric colorants, and mixtures thereof.
[0147] Preferred toning dyes include the bleaching agents found in WO 08/87497 A1, WO2011/011799 and WO2012/054835. Preferred tinting agents for use in the present invention may be the preferred dyes disclosed in these references, including those selected from examples 1 to 42 in table 5 of WO2011/011799. Other preferred dyes are disclosed in US 8138222. Other preferred dyes are disclosed in WO2009/069077.
[0148] Suitable clay dye conjugates include those selected from the group consisting of at least a cationic/basic dye and a smectite clay, as well as mixtures thereof. In another aspect, suitable clay dye conjugates include clay dye conjugates selected from the group consisting of a cationic/basic dye selected from the group consisting of C.I. Basic Yellow 1 to 108, C.I. Orange Basic 1 to 69, C.I. Basic Red 1 to 118, C.I. Violet Basic 1 to 51, C.I. Basic Blue 1 to 164, C.I. Basic Green 1 to 14, C.I. Basic Brown 1 to 23, CI Black Basic 1 to 11, and a clay selected from the group consisting of Montmorillonite clay, hectorite clay, saponite clay, and mixtures thereof. In yet another aspect, suitable clay dye conjugates include clay dye conjugates selected from the group consisting of: Montmorillonite Basic Blue B7 I.C. 42595 Conjugate, Montmorillonite Basic Blue B9 I.C. 52015 Conjugate, Violet Basic Montmorillonite V3 I.C. 42555 Conjugate, Montmorillonite Basic Green G1 I.C. 42040 Conjugate, Montmorillonite Basic Red R1 I.C. 45160 conjugate, Montmorillonite C.I. Black Basic 2 Conjugate, Basic Blue Hectorita B7 C.I. 42595 conjugate, Hectorite Basic Blue B9 I.C. 52015 Conjugate, Hectorite Basic Violet V3 I.C. 42555 Conjugate, Hectorite Basic Green G1 I.C. 42040 Conjugate, Hectorite Basic Red R1 I.C. 45160 conjugate, Hectorita C.I. Basic Black 2 Conjugate, Basic Saponita Blue B7 C.I. 42595 conjugate, Basic Blue of saponite B9 I.C. 52015 Conjugate, Violet Saponite Basic V3 I.C. 42555 Conjugate, Saponite Basic Green G1 I.C. 42040 Conjugate, Saponite Basic Red R1 I.C. 45160 conjugate, Saponita C.I. Basic Black 2 conjugated and mixtures thereof.
[0149] Suitable pigments include those selected from the group consisting of flavanthrone, indanthrone, chlorinated indanthrone containing from 1 to 4 chlorine atoms, pyranthrone, dichloropyrantrone, monobromodichloropyrantrone, dibromodichloropyranthrone, tetrabromopyrantrone, perylene-3 acid diimide, 4,9,10-tetracarboxylic, wherein the imide groups may be unsubstituted or substituted with C1-C3 alkyl or a phenyl or heterocyclic radical, and wherein phenyl and heterocyclic radicals may additionally carry substituents other than confer solubility in water, anthrapyrimidinecarboxylic acid amides, violantrone, isoviolantrone, dioxazine-based pigments, copper phthalocyanine which may contain up to 2 chlorine atoms per molecule, polychloro-copper phthalocyanine or polybromochloro-phthalocyanine copper containing up to 14 bromine atoms per molecule, as well as mixtures thereof.
[0150] In another aspect, suitable pigments include those selected from the group consisting of Ultramarine Blue (C.I. Blue Pigment 29), Ultramarine Violet (C.I. Violet Pigment 15) and mixtures thereof.
[0151] The aforementioned fabric toning agents can be used in combination (any mixture of fabric toning agents can be used). Dye transfer inhibiting agents
[0152] The cleaning compositions may also include one or more materials effective to inhibit the transfer of dyes from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents may include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinyl pyrrolidone and N-vinyl imidazole, manganese phthalocyanine, peroxidases and mixtures thereof. If used, these agents may be used at a concentration of from about 0.0001% to about 10% by weight of the composition in some examples, from about 0.01% to about 5% by weight of the composition, and in others. examples, from about 0.05% to about 2% by weight of the composition. Chelating Agents
[0153] The cleaning compositions described herein may also optionally contain one or more metal ion chelating agents. Suitable molecules include copper, iron and/or manganese chelating agents, and combinations thereof. Such chelating agents may be selected from the group consisting of phosphonates, amino carboxylates, amino phosphonates, succinates, polyfunctionally substituted aromatic chelating agents, 2-pyridinol-N-oxide compounds, hydroxamic acids, carboxymethyl inulins, and mixtures thereof. The chelating agents may be present in acid or salt form including alkali metal, ammonium, and substituted ammonium salts thereof, and mixtures thereof.
[0154] The chelator may be present in the cleaning compositions presented herein at from about 0.005% to about 15% by weight from about 0.01% to about 5% by weight from about 0.1% to about 3 .0% by weight or from about 0.2% to about 0.7% by weight or from about 0.3% to about 0.6% by weight of the cleaning composition.
[0155] Aminocarboxylates useful as chelating agents include, but are not limited to, ethylenediaminetetraacetates (EDTA); N-(hydroxyethyl)ethylenediaminetriacetates (HEDTA); nitrilotriacetates (NTA); ethylenediamine tetrapropionates; triethylenetetraamine-hexacetates, diethylentriamine-pentaacetates (DTPA); methyl glycine diacetic acid (MGDA); glutamic acid diacetic acid (GLDA); ethanol diglycines; triethylene-tetraamine-hexacetic acid (TTHA); N-hydroxyethyl iminodiacetic acid (HEIDA); dihydroxy ethylglycine (DHEG); ethylene diamine tetrapropionic acid (EDTP) and derivatives thereof.
[0156] Phosphorus-containing chelators include, but are not limited to, diethylene triamine penta (methylene phosphonic acid) (DTPMP CAS 1582760-8); ethylenediamine tetra(methylene phosphonic acid) (EDTMP CAS 142950-1); 2-phosphonobutane 1,2,4-tricarboxylic acid (Bayhibit® AM); hexamethylene diamine tetra(methylene phosphonic acid) (CAS 56744-47-9); hydroxyethane diphosphonic acid (HEDP CAS 2809-21-4); hydroxyethane dimethylene phosphonic acid; 2-phosphono-1,2,4-butanetricarboxylic acid (CAS 37971-36-1); 2-hydroxy-2-phosphonoacetic acid (CAS 23783-26-8); amino-tri(methylene phosphonic acid) (ATMP CAS 6419-19-8); P,P'-(1,2-ethanediyl)bis-phosphonic acid (CAS 6145-31-9); P,P'-methylonebis-phosphonic acid (CAS 1984-15-2); triethylenediaminetetra(methylene phosphonic acid) (CAS 28444-52-2); P-(1-hydroxy-1-methylethyl)-phosphonic acid (CAS 4167-10-6); bis(hexamethylene triamine penta(methylene phosphonic acid)) (CAS 3469000-1); N2,N2,N6,N6-tetrakis(phosphonomethyl)-lysine (CAS 194933-56-7, CAS 172780-03-9), salts thereof, and mixtures thereof. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups of more than about 6 carbon atoms.
[0157] Polyfunctionally substituted aromatic chelating agents may also be useful in cleaning compositions. See US Patent No. 3,812,044, issued May 21, 1974 to Connor et al. Compounds of this type, in acidic form, are dihydroxy-disulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene, also known as Tiron. Other sulfonated catechols may also be used. In addition to disulfonic acid, the term "thyron" may also include mono- or disulfonate salts of the acid, such as the disodium sulfonate salt, which shares the same core molecular structure with disulfonic acid.
[0158] Other chelating agents suitable for use in the present invention are the commercial DEQUEST series and chelators from Monsanto, Akzo-Nobel, DuPont, Dow, the Trilon® series from BASF and Nalco.
[0159] A biodegradable chelator that can also be used of the present invention is ethylenediamine disuccinate ("EDDS"). In some examples, but clearly not limited to this specific example, the [S,S] isomer as described in US patent 4,704,233 may be used. In other examples, the trisodium salt of EDDA may be used, although other forms, such as magnesium salts, may also be useful. Polymeric chelators such as BASF's Trilon P® may also be useful. foam suppressors
[0160] Compounds for reducing or suppressing foaming can be incorporated into the cleaning compositions described herein. Foam suppression may be of particular importance in the so-called "high concentration cleaning process" as described in US Patent Nos. 4,489,455 and 4,489,574 and in front loading washing machines.
[0161] A wide variety of materials can be used as foam suppressors, and foam suppressors are well known to those skilled in the art. See, for example, "Kirk Othmer Encyclopedia of Chemical Technology", Third Edition, Volume 7, pages 430 to 447 (John Wiley & Sons, Inc., 1979). Examples of suds suppressants include monocarboxylic fatty acid and salts soluble therein, high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18C40 ketones ( for example, stearone), N-alkylated aminotriazines, waxy hydrocarbons, preferably having a melting point below about 100°C, silicone foam suppressants and secondary alcohols. Foam suppressants are described in US Patent Nos. 2,954,347; 4,265,779; 4,265,779; 3,455,839; 3,933,672; 4,652,392; 4,978,471; 4,983,316; 5,288,431; 4,639,489; 4,749,740; and 4,798,679; 4,075,118; European Patent Application No. 89307851.9; EP 150,872; and DOS 2,124,526.
[0162] Additional suitable defoamers are those derived from phenylpropylmethyl substituted polysiloxanes.
[0163] In certain examples, the cleaning composition comprises a suds suppressant selected from organic silicone polymers modified with aryl or alkyl aryl substituents combined with silicone resin and a primary filler, which is modified silica. Cleaning compositions can comprise from about 0.001% to about 4.0% by weight of this foam suppressant composition. In further examples, the cleaning composition comprises a suds suppressant selected from: a) mixtures of from about 80 to about 92% ethylmethyl, methyl(2-phenylpropyl) siloxane; from about 5 to about 14% MQ resin in octyl stearate; and from about 3 to about 7% modified silica; b) mixtures of about 78 to about 92% of ethyl methyl, methyl(2-phenylpropyl)siloxane; from about 3 to about 10% MQ resin in octyl stearate; from about 4 to about 12% modified silica; or c) mixtures thereof, where the percentages are expressed in weight of the defoamer.
[0164] The cleaning compositions of the present invention may comprise from about 0% to about 10% by weight of the foam suppressant composition. When used as suds suppressants, monocarboxylic fatty acids and their salts may be present in amounts of up to about 5% by weight of the cleaning composition, and in some examples, from about 0.5% to about 3% by weight. weight of the cleaning composition. Silicone foam suppressants can be used in amounts of up to about 2.0% by weight of the cleaning composition, although larger amounts can be used. Monostearyl phosphate foam suppressants can be used in amounts ranging from about 0.1% to about 2% by weight of the cleaning composition. The hydrocarbon foam suppressants can be used in amounts ranging from about 0.01% to about 5.0% by weight of the cleaning composition, although higher levels can be used. Alcohol foam suppressants can be used at a concentration in the range of from about 0.2% to about 3% by weight of the cleaning composition. foam boosters
[0165] If high foaming is desired, foam boosters such as C10-C16 alkanolamides can be incorporated into cleaning compositions at a concentration ranging from about 1% to about 10% by weight of the cleaning composition. Some examples include C10-C14 monoethanol and diethanolamides. If desired, water-soluble magnesium and/or calcium salts such as MgCl2 , MgSO4 , CaCl2 , CaSO4 and the like can be added in amounts of, for example, about 0.1% to about 2% by weight of the cleaning composition to provide additional foam and to improve degrease performance. fabric softeners
[0166] Various fabric softeners for use throughout the wash, including the impalpable smectite clays of US Patent No. 4,062,647 as well as other softening clays known in the art, can be used at levels from about 0.5% to about 10% by weight of the composition to provide fabric softening benefits simultaneously with fabric cleaning. Clay-based softeners can be used in combination with amine and cationic softeners as shown, for example, in U.S. Patent No. 4,375,416 and U.S. Patent No. 4,375,416. no. 4,291,071. Cationic softeners can also be used without clay-based softeners. encapsulated
[0167] The compositions may comprise an encapsulate. In one aspect, the encapsulate comprises a core, a wrapper having an inner surface and an outer surface, said wrapper encapsulating the core.
[0168] In certain aspects, the encapsulated comprises a core and a wrapper, where the core comprises a material selected from perfumes; rinse aids; dyes; insect repellents; silicones; waxes; flavorings; vitamins; fabric softening agents; agents for treating skin, for example paraffins; enzymes; antibacterial agents; bleaching agents; sensory elements; or mixtures thereof; and wherein the wrapper comprises a material selected from polyethylenes; polyamides; poly(vinyl alcohols), optionally containing other comonomers; polystyrenes; polyisoprenes; polycarbonates; polyesters; polyacrylates; polyolefins; polysaccharides, for example alginate and/or chitosan; gelatin; shellac; epoxy resins; vinyl polymers; water-insoluble inorganics; silicone; aminoplasts, or mixtures thereof. In some aspects, the wrapper comprises an aminoplastic, the aminoplastic comprises polyurea, polyurethane and/or polyureaurethane. The polyurea may comprise polyoxymethylene urea and/or melamine formaldehyde.
[0169] In some aspects, the encapsulate comprises a core, and the core comprises a perfume. In certain aspects, the encapsulate comprises a wrapper and the wrapper comprises melamine formaldehyde and/or cross-linked melamine formaldehyde. In some aspects, the encapsulate comprises a core comprising a perfume and a wrapper comprising melamine formaldehyde and/or cross-linked melamine formaldehyde.
[0170] Suitable encapsulates may comprise a core material and a wrapper, where the wrapper at least partially surrounds the core material. At least 75%, or at least 85%, or even at least 90% of the encapsulates may have a fracture strength of about 0.2 MPa to about 10 MPa, from about 0.4 MPa to about 5 MPa, from about 0.6 MPa to about 3.5 MPa, or even from about 0.7 MPa to about 3 MPa; and a benefit agent flow from 0% to about 30%, from 0% to about 20%, or even from 0% to about 5%.
[0171] In some aspects, at least 75%, 85% or even 90% of said encapsulates may have a particle size of from about 1 micrometer to about 80 micrometers, from about 5 micrometers to 60 micrometers, from about 5 micrometers to 60 micrometers. 10 micrometers to about 50 micrometers, or even from about 15 micrometers to about 40 micrometers.
[0172] In some aspects, at least 75%, 85% or even 90% of said encapsulates may have a particle wall thickness of from about 30 nm to about 250 nm, from about 80 nm to about 180 nm , or even from about 100 nm to about 160 nm.
[0173] In some aspects, the encapsulated core comprises a material selected from the group of a perfume raw material and/or optionally a material selected from vegetable oil, including pure and/or mixed vegetable oils including castor oil, coconut oil, cottonseed oil, grapeseed oil, rapeseed oil, soybean oil, corn oil, babassu oil, linseed oil, safflower oil, olive oil, peanut oil, coconut oil, palm kernel oil, castor oil, lemon oil and mixtures thereof; vegetable oil esters, esters, including dibutyl adipate, dibutyl phthalate, butyl benzyl adipate, benzyl octyl adipate, tricresyl phosphate, trioctyl phosphate and mixtures thereof; straight-chain or branched hydrocarbons, including those straight-chain or branched hydrocarbons that have a boiling point greater than about 80°C; partially hydrogenated terphenyls, dialkyl phthalates, alkyl biphenyls, including monoisopropyl biphenyl, alkylated naphthalene, including dipropyl naphthalene, petroleum distillates, including kerosene, mineral oil or mixtures thereof; aromatic solvents, including benzene, toluene or mixtures thereof; silicone oils; or mixtures thereof.
[0174] In some aspects, the wall of the encapsulate comprises a suitable resin, as the reaction product of an aldehyde and an amine. Suitable aldehydes include formaldehyde. Suitable amines include melamine, urea, benzoguanamine, glycoluril, or mixtures thereof. Suitable melamines include methylolmelamine, methylated methylolmelamine, imimonomelamine and mixtures thereof. Suitable ureas include dimethylolurea, methylated dimethylolurea, urea-resorcinol, or mixtures thereof.
[0175] In some aspects, suitable formaldehyde sequestrants may be used with the encapsulates, for example, in a slurry capsule and/or added to a composition before, during or after the encapsulates are added to such a composition.
[0176] Suitable capsules are described in USPA 2008/0305982 A1; and/or USPA 2009/0247449 A1. Alternatively, suitable capsules can be purchased from Appleton Papers Inc. of Appleton, Wisconsin, USA.
[0177] In addition, materials for producing the aforementioned encapsulates can be obtained from Solutia Inc. (St. Louis, Missouri USA), Cytec Industries (West Paterson, New Jersey, USA), sigma-Aldrich (St. Louis, Missouri USA), CP Kelco Corp. of San Diego, California, USA; BASF AG of Ludwigshafen, Germany; Rhodia Corp. from Cranbury, New Jersey, USA; Hercules Corp. from Wilmington, Delaware, USA; Agrium Inc. from Calgary, Alberta, Canada, ISP from New Jersey, USA, Akzo Nobel from Chicago, IL, USA; Stroever Shellac Bremen from Bremen, Germany; Dow Chemical Company of Midland, MI, USA; Bayer AG of Leverkusen, Germany; Sigma-Aldrich Corp., St. Louis, Missouri, USA. Perfumes
[0178] Perfumes and perfumery ingredients can be used in the cleaning compositions described herein. Non-limiting examples of perfume and perfumery ingredients include, but are not limited to, aldehydes, ketones, esters, and the like. Other examples include various natural extracts and essences which may comprise complex mixtures of ingredients such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedarwood and the like. Finished perfumes can comprise extremely complex mixtures of these ingredients. The finished perfumes can be used at a concentration in the range of from about 0.01% to about 2% by weight of the cleaning composition. Pearlizing agent The laundry detergent compositions of the invention may comprise a pearlizing agent. Use pearlizing agents include those described in USPN 2008/0234165A1. Non-limiting examples of pearlizing agents include: mica; mica coated with titanium dioxide; bismuth oxychloride; fish scales; alkylene glycol mono and diesters with the formula:
where: a. R1 is a straight or branched C12-C22 alkyl group; B. R is a straight or branched C2 -C4 alkylene group; ç. P is selected from H; C1-C4 alkyl; or -COR2; d. n = 1-3.
[0179] In some aspects, the pearlizing agent is ethylene glycol distearate (EGDS). Fillers and vehicles
[0180] Fillers and vehicles can be used in the cleaning compositions described herein. As used herein, the terms "filler" and "vehicle" have the same meaning and may be used interchangeably.
[0181] Liquid cleaning compositions and other forms of cleaning compositions that include a liquid component (such as liquid-containing unit dose cleaning compositions) may contain water and other solvents as fillers or carriers. Suitable solvents also include lipophilic fluids including siloxanes, other silicones, hydrocarbons, glycol ethers, glycerin derivatives such as glycerin ethers, perfluorinated amines, perfluorinated and hydrofluoroether-based solvents, low volatility non-fluorinated organic solvents, diol and mixtures thereof.
[0182] Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohols can be used in some examples to solubilize surfactants and polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxyl groups (e.g. 1,3-propanediol, ethylene glycol, glycerin and 1, 2-propanediol) can also be used. Amine-containing solvents such as monoethanolamine, diethanolamine and triethanolamine may also be used.
[0183] Cleaning compositions may contain from about 5% to about 90% and in some examples from about 10% to about 50% by weight of the composition of such carriers. For compact or super-compact heavy duty liquids or other forms of cleaning compositions, the use of water can be lower than about 40% by weight of the composition or lower than about 20% or lower than about 5% or less than about 4% free water or less than about 3% free water, or less than about 2% free water or substantially free of free water (i.e., anhydrous).
[0184] For powder or bar cleaning compositions, or forms that include a solid or powder component (such as powder-containing unit dose cleaning composition), suitable fillers may include, but are not limited to, sodium sulfate, sodium chloride, clay, or other inert solid ingredients. Loads can also include biomass or discolored biomass. Fillers in granular, bar, or other solid cleaning compositions can comprise less than about 80% by weight of the cleaning composition, and in some examples, less than about 50% by weight of the cleaning composition. Compact or supercompact powder or solid cleaning compositions may comprise less than about 40% filler by weight of the cleaning composition, or less than about 20%, or less than about 10%.
[0185] For compacted or super-compacted liquid or powder cleaning compositions or other forms, the liquid or solid fill level in the product can be reduced so that the same amount of active chemical is released to the washing liquid compared to uncompacted cleaning compositions or in some examples, the cleaning composition is more effective so that less active chemical is released into the wash liquid compared to the uncompacted compositions. For example, the washing liquid can be formed by contacting the cleaning composition with water in an amount such that the concentration of cleaning composition in the washing liquid is from more than 0 g/l to 6 g/l. In some examples, the concentration may be from about 0.5 g/l or about 5 g/l to about 3.0 g/l or about 2.5 g/l or about 2.0 g /l or at about 1.5 g/l or from about 0 g/l to about 1.0 g/l or from about 0 g/l to about 0.5 g/l. These dosages are not intended to limit, and other dosages may be used, which will be apparent to those skilled in the art. buffer system
[0186] The cleaning compositions described in the present invention can be formulated so that, during use in aqueous cleaning operations, the wash water will have a pH between about 7.0 and about 12, and in some examples, between about 7.0 and about 11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis or acids, and are well known to those skilled in the art. These include, but are not limited to, the use of sodium carbonate, citric acid or sodium citrate, lactic acid or lactate, monoethanolamine or other amines, boric acid or borates, and other pH-adjusting compounds well known in the art.
[0187] The cleaning compositions of the present invention may comprise dynamic wash pH profiles. Such cleaning compositions may use wax coated citric acid particles in conjunction with other pH control agents so that (i) about 3 minutes after contact with water, the pH of the washing liquid is greater than 10; (ii) about 10 minutes after contact with water, the pH of the washing liquid is less than 9.5; (iii) about 20 minutes after contact with water, the pH of the washing liquid is less than 9.0; and (iv) optionally, wherein the equilibrium pH of the wash liquid is in the range of about 7.0 to about 8.5. water soluble film
[0188] The compositions of the present invention may also be encapsulated within a water-soluble film. Preferred film materials are preferably polymeric materials. The film material, for example, can be obtained by casting, blow molding, extrusion or blow extrusion of the polymeric material, as is known in the art.
[0189] The preferred polymers, copolymers or derivatives thereof suitable for use as material for containment bags are selected from poly(vinyl alcohols), polyvinylpyrrolidone, poly(alkylene oxides), acrylamide, acrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, poly(vinyl acetates), poly(carboxylic acids) and poly(carboxylic salts), polyamino acids or peptides, polyamides, polyacrylamide, maleic/acrylic acid copolymers, polysaccharides including starch and gelatin, natural gums such as xanthan and carrageenan. The most preferred polymers are selected from water-soluble polyacrylates and acrylate copolymers, methyl cellulose, sodium carboxymethyl cellulose, dextrin, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, maltodextrin, polymethacrylates and, most preferably, are selected from poly(vinyl alcohols), copolymers of poly(vinyl alcohol) and hydroxypropylmethylcellulose (HPMC), and combinations thereof. Preferably, the polymer content in the containment bag material, for example a PVA polymer, is at least 60%. The polymer may have any weight average molecular weight, preferably from about 1,000 to 1,000,000, more preferably from about 10,000 to 300,000, most preferably from about 20,000 to 150,000. Polymer blends can also be used as the material for a containment bag.
[0190] Naturally, different film materials and/or films of different thickness can be used in the production of the compartments of the present invention. A benefit of selecting different films is that the resulting compartments may exhibit different solubility or release characteristics.
[0191] More preferred film materials are PVA films known under the tradename MonoSol M8630, M8900, H8779 (as described in Applicant's copending application ref Nos. 44528 and 11599) and those described in US 6,166. 117 and US 6,787,512 and PVA films of corresponding solubility and deformability characteristics.
[0192] The film material of the present invention may also comprise one or more additive ingredients. For example, it may be beneficial to add plasticizers, for example glycerol, ethylene glycol, diethylene glycol, propylene glycol, sorbitol and mixtures thereof. Other additives include functional detergent additives to be released into the wash water, e.g. organic polymeric dispersants, etc. Other auxiliary ingredients
[0193] A wide variety of other ingredients can be used in the cleaning compositions of the present invention, including other active ingredients, vehicles, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, and solid fillers or other liquid fillers. , erythrosine, colloidal silica, waxes, probiotics, surfactin, aminocellulose polymers, zinc ricinoleate, perfume microcapsules, rhamnolipids, sophorolipids, glycopeptides, methyl ester sulfonates, methyl ester ethoxylates, sulfonated stolides, cleavable surfactants, biopolymers , silicones, modified silicones, aminosilicones, deposition aids, locust bean gum, cationic hydroxyethyl cellulose polymers, cationic guar gum, hydrotropes (especially cumenesulfonate salts, toluenesulfonate salts, xylenesulfonate salts and naphthalene salts), antioxy - before, BHT, dyes or perfumes encapsulated in particulate PVA, pearlizing agents, effervescent agents, color changing systems, silicone polyurethanes, opacifiers, tablet disintegrators, biomass fillers, quick-drying silicones, glycol distearate, hydroxy ethyl cellulose polymers, hydroxy polymers ethyl cellulose or hydrophobically modified cellulose polymers, starch encapsulated perfume, emulsified oils, bisphenol antioxidants, microfibrous cellulose builders, pro-perfumes, styrene/acrylate polymers, triazines, soaps, superoxide dismutase, benzophenone protease inhibitors, Functionalized TiO2, Dibutyl Phosphate, Silica Perfume Capsules and Other Auxiliary Ingredients, Diethylenetriaminepentacetic Acid, Tiron (1,2-Dihydroxy-Benzene-3,5-Disulfonic Acid), Hydroxy-ethanedimethylenephosphonic Acid, Methyl Glycine Acid diacetic acid, choline oxidase, pectate lyase, triaryl methane blue and violet basic dyes, triaryl methane blue and violet basic dyes methine, basic dyes anthraquinone blue and violet, azo dyes Basic Blue 16, Basic Blue 65, Basic Blue 66 Basic Blue 67, Basic Blue 71, Basic Blue 159, Basic Violet 19, Basic Violet 35, Basic Violet 38, Basic Violet 48 , oxazine dyes, Basic Blue 3, Basic Blue 75, Basic Blue 95, Basic Blue 122, Basic Blue 124, Basic Blue 141, Nile Blue A and xanthene dye Basic Violet 10, alkoxylated triphenyl methane polymeric dye; an alkoxylated thiophene polymeric dye; thiazolium dye, mica, titanium dioxide coated mica, bismuth oxychloride, paraffin waxes, sucrose esters, aesthetic dyes, hydroxamate chelators and other actives.
[0194] The cleaning compositions described herein may also contain vitamins and amino acids such as: water-soluble vitamins and their derivatives, water-soluble amino acids and their salts and/or derivatives, viscosity modifiers of water-insoluble amino acids, dyes, non-volatile solvents or thinners (insoluble and soluble in water), pearlizing aids, foam boosters, additional nonionic surfactants or co-surfactants, pediculocytes, pH adjusting agents, perfumes, preservatives, chelators, proteins, skin active agents , sunscreens, UV absorbers, vitamins, niacinamide, caffeine and minoxidil.
[0195] The cleaning compositions of the present invention may also contain pigment materials such as nitroso, monoazo, disazo, carotenoid, triphenyl methane, triaryl methane, xanthene, quinoline, oxazine, azine, anthraquinone, indigoid, thionindigoid, quinacridone , phthalocyanine, botanical component, natural colors including: water soluble components such as those having CI names names. The cleaning compositions of the present invention may also contain antimicrobial agents. Preparation of cleaning compositions
[0196] The cleaning compositions of the present disclosure can be prepared according to conventional methods known to those skilled in the art, such as by a batch process or a continuous loop process. Usage methods
[0197] The present invention includes methods for cleaning a dirty material. As will be understood by those skilled in the art, the cleaning compositions of the present invention are suitable for use in laundry pretreatment applications, laundry cleaning applications and home care applications.
[0198] Such methods include, but are not limited to, the steps of bringing the cleaning compositions in their pure or diluted form in washing liquid, contacting at least a portion of a soiled material, and then optionally rinsing the material. dirty. Dirty material can be subjected to a washing step before the optional rinsing step.
[0199] For use in laundry pretreatment applications, the method may include placing the cleaning compositions described herein in contact with soiled fabric. After pre-treatment, the soiled fabric can be washed in a washing machine or otherwise rinsed.
[0200] Methods for machine washing clothes may comprise treating soiled laundry items with an aqueous wash solution in a washing machine in which an effective amount of a laundry cleaning composition has been dissolved or dispensed with. machine according to the invention. An "effective amount" of the cleaning composition means from about 20g to about 300g of the product dissolved or dispersed in a washing solution of volume from about 5L to about 65L. Water temperatures can range from about 5°C to about 100°C. The ratio of water to soiled material (eg fabric) can be from about 1:1 to about 30:1. The compositions can be employed at concentrations from about 500 ppm to about 15,000 ppm in solution. In the context of a fabric washing composition, "use contents" can also vary depending not only on the type and severity of soils and stains, but also on the temperature of the wash water, the volume of the wash water and the washing machine type (e.g. Japanese vertical axis type automatic washing machine, top loading, front loading, top loading).
[0201] The cleaning compositions of the present invention can be used for washing fabrics at reduced washing temperatures. These methods of washing fabrics comprise the steps of applying a laundry cleaning composition to water to form a washing liquid and adding a fabric to be washed to said washing liquid, wherein the washing liquid has a temperature of about 0°C to about 20°C, or from about 0°C to about 15°C, or from about 0°C to about 9°C. The fabric may be contacted with water before or after, or simultaneously with, contacting the laundry cleaning compositions with water.
[0202] Another method includes placing a non-woven substrate impregnated with an embodiment of the cleaning composition in contact with soiled material. For use in the present invention, the term "non-woven substrate" may comprise any conventionally produced non-woven sheet or batt having suitable characteristics of basis weight, gauge (thickness), absorbency and strength. Non-limiting examples of suitable commercially available non-woven substrates include those available under the tradenames SONTARA® from DuPont and POLYWEB® from James River Corp. Methods for Machine Washing Dishes
[0203] Manual/immersion washing methods and washing machines combining hand and semi-automatic washing are included. Methods for machine washing or hand washing of dirty dishes, tableware, silverware, or other kitchen utensils are also included. A method of machine dishwashing comprises treating soiled dishes, tableware, silverware, or other kitchen utensils with an aqueous liquid in which an effective amount of a machine dishwashing composition has been dissolved or dispensed. according to the invention. By an "effective amount" of the machine dishwashing composition is meant from about 8 g to about 60 g of the product dissolved or dispersed in a washing solution of volume from about 3 L to about 10 L.
[0204] A method for hand washing dishes comprises dissolving the cleaning composition in a receptacle containing water, followed by contacting the soiled dishes, tableware, silverware, or other kitchen utensils with the washing liquid and, then hand scrubbing, wiping, or rinsing soiled dishes, tableware, silverware, or other kitchen utensils. Another method for washing dishes by hand comprises applying the cleaning composition directly to the soiled dishes, tableware, silverware or other kitchen utensils and then manually scrubbing, drying, or rinsing the soiled dishes, tableware, silverware or other kitchen utensils. In some examples, an effective amount of the hand dishwashing cleaning composition is from about 0.5 ml to about 20 ml diluted with water. Packaging for the Compositions
[0205] The cleaning compositions described herein may be packaged in any suitable container, including those constructed of paper, cardstock, plastic materials, and any suitable laminates. An optional packaging type is described in European application no. 94921505.7. Composition in bag
[0206] The cleaning compositions described herein may also be packaged as a single-compartment or multi-compartment cleaning composition, for example, in unitized dosage form. For example, cleaning compositions can be encapsulated in a water-soluble containment bag. The water soluble containment bag may comprise poly(vinyl alcohol) (PVOH). The containment bag may have contents in at least two compartments, or at least three compartments. The contents in each compartment can be the same color, or they can be different or contrasting colors. The contents in each compartment can be liquids, solids, or mixtures thereof. Suitable containment bags and methods of forming such containment bags are described, for example, in US patent applications 2002/0169092 and 2009/0199877, incorporated herein by reference. Examples
[0207] In the Examples below, the individual ingredients within the cleaning compositions are expressed as percentages by weight of the cleaning compositions unless otherwise noted. Also, in the Examples below, the following abbreviations are used: BuO = butylene oxide PO = propylene oxide Synthesis example 1: 1 mol of glycerin + 3 mol of BuO + 3 mol of PO, amines a) 1 mol of glycerin + 3 mol of BuO + 3 mol of PO
[0208] In a 3.5 L autoclave, 95.0 g of glycerin and 1.0 g of potassium tert-butylate are mixed. The autoclave is purged three times with nitrogen and heated to 140°C. 223.0 g of butylene oxide is added within 90 minutes. The mixture is left to post-react for 5 hours at 140°C. Then, 179.7 g of propylene oxide is added in portions within 1 hour. To complete the reaction, the mixture is allowed to post-react for an additional 3 hours at 140°C. The reaction mixture is stripped with nitrogen and the volatile compounds are removed in vacuo at 80°C. The catalyst is removed by adding 4.9 g of synthetic magnesium silicate (Macrosorb MP5plus, Ineos Silicas Ltd.), stirring at 100°C for 2 hours, and filtering.
[0209] A yellowish oil is obtained (490.0 g, hydroxy value: 314.5 mgKOH/g). b) 1 mol of glycerin + 3 mol of BuO + 3 mol of PO, amines
[0210] In a 9 L autoclave, 350 mL of the triol mixture resulting from example 1-a, 1,200 mL of THF and 1,500 g of ammonia are mixed in the presence of 200 mL of a solid catalyst, as described in EP0696572B1. The catalyst containing nickel, cobalt, copper, molybdenum and zirconium is in the form of 3x3 mm tablets. The autoclave is purged with hydrogen and the reaction is started by heating the autoclave. The reaction mixture is stirred for 15 h at 205°C; the total pressure is maintained at 28 MPa (280 bar) by hydrogen purge throughout the reductive amination step. After autoclave cooling, the final product is collected, filtered, flushed of excess ammonia and stripped on a rotary evaporator to remove light amines and water. A total of 350 to 400 grams of a low color etheramine mixture is recovered. The analytical results of the same are shown in Table 1.Table 1. Analytical results of etheramine of example 1
Synthesis example 2: 1 mol of glycerin + 3 mol of PO + 3 mol of BuO, amines a) 1 mol of glycerin + 3 mol of PO + 3 mol of BuO
[0211] In a 3.5 L autoclave, 88.1 g of glycerin and 0.9 g of potassium tert-butylate are mixed. The autoclave is purged three times with nitrogen and heated to 140°C. 166.6 g of propylene oxide are added within 1 hour. The mixture is allowed to post-react for 3 hours at 140°C. Then, 206.8 g of butylene oxide is added in portions within 1 hour. To complete the reaction, the mixture is allowed to post-react for an additional 3 hours at 140°C. The reaction mixture is stripped with nitrogen and the volatile compounds are removed in vacuo at 80°C. The catalyst is removed by adding 4.4 g of Macrosorb MP5plus, stirring at 100°C for 2 hours, and filtering.
[0212] A yellowish oil is obtained (410.0 g, hydroxy value: 336.5 mgKOH/g). b) 1 mol of glycerin + 3 mol of PO + 3 mol of BuO, amines
[0213] In a 9 L autoclave, 350 mL of the triol mixture resulting from example 2-a, 1,200 mL of THF and 1,500 g of ammonia are mixed in the presence of 200 mL of a solid catalyst, as described in EP0696572B1. The catalyst containing nickel, cobalt, copper, molybdenum and zirconium is in the form of 3x3 mm tablets. The autoclave is purged with hydrogen and the reaction is started by heating the autoclave. The reaction mixture is stirred for 15 h at 205°C; the total pressure is maintained at 28 MPa (280 bar) by hydrogen purge throughout the reductive amination step. After autoclave cooling, the final product is collected, filtered, flushed of excess ammonia and stripped on a rotary evaporator to remove light amines and water. A total of 300 to 350 grams of a low color etheramine mixture is recovered. The analytical results of the same are shown in Table 2.Table 2. Analytical results of etheramine of example 2
Synthesis example 3: 1 mol of glycerin + 6 mol of BuO, amines a) 1 mol of glycerin + 6 mol of BuO
[0214] In a 3.5 L autoclave, 103.4 g of glycerin and 1.2 g of potassium tert-butylate are mixed. The autoclave is purged three times with nitrogen and heated to 140°C. 485.5 g of propylene oxide are added within 2 hours. To complete the reaction, the mixture is allowed to post-react for an additional 7 hours at 140°C. The reaction mixture is stripped with nitrogen and the volatile compounds are removed in vacuo at 80°C. The catalyst is removed by adding 5.9 g of Macrosorb MP5plus, stirring at 100°C for 2 hours, and filtering.
[0215] A yellowish oil is obtained (589.0 g, hydroxy value: 285.0 mgKOH/g). b) 1 mol of glycerin + 6 mol of BuO, amines
[0216] In a 9 L autoclave, 500 g of the triol mixture resulting from example 3-a, 1,200 ml of THF and 1,500 g of ammonia are mixed in the presence of 200 ml of a solid catalyst, as described in EP0696572B1 . The catalyst containing nickel, cobalt, copper, molybdenum and zirconium is in the form of 3x3 mm tablets. The autoclave is purged with hydrogen and the reaction is started by heating the autoclave. The reaction mixture is stirred for 15 h at 205°C; the total pressure is maintained at 28 MPa (280 bar) by hydrogen purge throughout the reductive amination step. After autoclave cooling, the final product was collected, filtered, expelled of excess ammonia and stripped on a rotary evaporator to remove light amines and water. A total of 450 grams of a low-color etheramine blend is recovered. The analytical results of the same are shown in Table 3.Table 3. Analytical results of the etheramine of example 3.
Synthesis example 4: 1 mol of glycerin + 4.2 mol of PO + 1.8 mol of BuO, amines a) 1 mol of glycerin + 4.2 mol of PO + 1.8 mol of BuO
[0217] In a 3.5 L autoclave, 88.9 g of glycerin and 0.9 g of potassium tert-butylate are mixed. The autoclave is purged three times with nitrogen and heated to 140°C. 235.4 g of propylene oxide are added within 1.5 hours. The mixture is left to post-react for 3 hours at 140°C. Then, 125.2 g of butylene oxide is added in portions within 1 hour. To complete the reaction, the mixture is allowed to post-react for an additional 5 hours at 140°C. The reaction mixture is stripped with nitrogen and the volatile compounds are removed in vacuo at 80°C. The catalyst is removed by adding 4.7 g of Macrosorb MP5plus, stirring at 100°C for 2 hours, and filtering.
[0218] A yellowish oil is obtained (470.0 g, hydroxy value: 312.1 mgKOH/g). b) 1 mol of glycerin + 4.2 mol of PO + 1.8 mol of BuO, amines
[0219] In a 9 L autoclave, 350 mL of the triol mixture resulting from example 4-a, 1,200 mL of THF and 1,500 g of ammonia are mixed in the presence of 200 mL of a solid catalyst, as described in EP0696572B1. The catalyst containing nickel, cobalt, copper, molybdenum and zirconium is in the form of 3x3 mm tablets. The autoclave is purged with hydrogen and the reaction is started by heating the autoclave. The reaction mixture is stirred for 15 h at 205°C; the total pressure is maintained at 28 MPa (280 bar) by hydrogen purge throughout the reductive amination step. After autoclave cooling, the final product is collected, filtered, flushed of excess ammonia and stripped on a rotary evaporator to remove light amines and water. A total of 350 to 400 grams of a low color etheramine mixture is recovered. The analytical results of the same are shown in Table 4.Table 4. Analytical results of the etheramine of example 4.
Example 5: Comparative Grease/Grease Stain Removal of Laundry Detergent Compositions
[0220] The following laundry detergent compositions are prepared by traditional means known to those skilled in the art by mixing the aforementioned ingredients. Composition A is a conventional premium laundry detergent that uses Baxxodur EC301, an amine terminated linear polyalkylene glycol with the structure of formula D.

[0221] Liquid detergent composition B contains a polyether amine, prepared according to Synthesis Example 2 (see, for example, Formula A).


1. Polyethylene imine (MW = 600) with 20 ethoxylate groups per -NH. 2. Linear alkylbenzenesulfonate with an average aliphatic carbon chain length of C11-C12, available from Stepan, Northfield, Illinois, USA 3. AE9 is C12-13 alcohol ethoxylate, with an average degree of ethoxylation of 9, supplied by Huntsman, Salt Lake City, Utah, USA 4. Suitable chelators are, for example, diethylenetriaminepentaacetic acid (DTPA), supplied by Dow Chemical, Midland, Michigan, USA, or hydroxyethanediphosphonate (HEDP), supplied by Solutia, St Louis, USA. Missouri, USA Bagsvaerd, Denmark 5. Natalase®, Mannaway® are products of Novozymes, Bagsvaerd, Denmark. 6. Proteases can be supplied by Genencor International, Palo Alto, California, USA (eg, Purafect Prime®) or by Novozymes, Bagsvaerd, Denmark (eg, Liquanase®, Coronase®). 10. Suitable fluorescent whitening agents are, for example, Tinopal® AMS, Tinopal® CBS-X, sulfonated zinc phthalocyanine Ciba Specialty Chemicals, Basel, Switzerland. 11. Polyether amine prepared according to Synthesis Example 2.
[0222] CW120 cotton technical stain samples containing US clay, Frank® hot sauce, hamburger grease, and makeup are purchased from Empirical Manufacturing Co., Inc (Cincinnati). Samples are washed in a Whirlpool® front loading washing machine, using a water hardness of 6 grains per gallon and washed at 37.8 degrees Celsius (100 degrees Fahrenheit). The total amount of liquid detergent used in the test is 49 grams.
[0223] Image analysis is used to compare each stain to an unstained tissue control. The program converts the images taken into standard colorimetric values and compares them with the standards based on the commonly used Macbeth Color Rendition Chart, assigning each stain a colorimetric value (spot content). Eight replicates of each stain are prepared.
[0224] Stain removal from samples is measured as follows:

[0225] The stain removal index ratings for each stain are calculated and are mentioned in the table below (Table 5 data): Table 5 data

[0226] These results illustrate the surprising degreasing benefit of a polyether amine of the present disclosure (used in composition B) compared to a linear polyalkylene glycol diamine (composition A). Example 6: Comparative degreasing of laundry powder cleaning composition
[0227] The following laundry detergent powder compositions are prepared by traditional means known to those skilled in the art by mixing the aforementioned ingredients. Composition A is a laundry detergent using Baxxodur EC301, an amine terminated linear polyalkylene glycol (see structure of formula D above). Composition B is a detergent using a polyether amine, prepared according to Synthesis Example 2 (see, for example, Formula A above).

1. Linear alkylbenzenesulfonate with an average aliphatic carbon chain length of C11-C12, available from Stepan, Northfield, Illinois, USA 2. AE3S is C12-15 alkyl ethoxy sulfate (3), available from Stepan, Northfield, Illinois , USA 3. Zeolite A is supplied by Industrial Zeolite (UK) Ltd, Grays, Essex, UK 4. Silicate 1,6R is supplied by Koma, Nestemica, Czech Republic 5. Sodium carbonate is supplied by Solvay, Houston, Texas, USA 6. Soil release agent is Repel-o-tex® PF, available from Rhodia, Paris, France 7. Acrylic acid/maleic acid copolymer has a molecular weight of 70,000 and an acrylate:maleate ratio of 70: 30, is supplied by BASF, Ludwigshafen, Germany 8. Savinase®, Natalase®, Stainzyme®, Lipex®, Celluclean™, Mannaway® and Whitezyme® are all products from Novozymes, Bagsvaerd, Denmark. 9. Proteases can be supplied by Genencor International, Palo Alto, California, USA (eg, Purafect Prime®) or by Novozymes, Bagsvaerd, Denmark (eg, Liquanase®, Coronase®). 10. Polyether amine prepared according to Synthesis Example 2. 11. TAED is tetraacetylethylenediamine, available under the tradename Peractive® from Clariant GmbH, Sulzbach, Germany. 12. Sodium percarbonate is available from Solvay, Houston, Texas, USA 13. Ethylenediamine-N,N'-disuccinic acid, (S,S)-isomer (EDDS) sodium salt is available from Octel, Ellesmere Port, UK 14 Hydroxyethane Diphosphonate (HEDP) is available from Dow Chemical, Midland, Michigan, USA. 15. Agglomerate of foam suppressor, is supplied by Dow Corning, Midland, Michigan, USA 16. Fluorescent Brightener 1 is Tinopal® AMS, Fluorescent Brightener 2 is Tinopal® CBS-X, Sulfonated Zinc Phthalocyanine and Direct Violet 9 is Pergasol® Violet BN-Z, all supplied by Ciba Specialty Chemicals of Basel, Switzerland
[0228] CW120 cotton technical stain samples containing burnt butter, bacon fat, DMO, margarine, taco fat, hamburger fat, and Italian dressing are purchased from Empirical Manufacturing Co., Inc (Cincinnati). The stained samples are washed in conventional Western European washing machines (Meile®) using a hardness of 14 grains per gallon, cycle selection for cotton at 30°C, using 80 g of each of the respective detergent compositions. Image analysis is used to compare each stain to an unstained tissue control. The program converts the images taken into standard colorimetric values and compares them with the standards based on the commonly used Macbeth Color Rendition Chart, assigning each stain a colorimetric value (spot content). Eight replicates of each stain are prepared. The stain removal index is then calculated according to the formula shown above.
[0229] The main results are summarized in the following table (data from Table 6): Data from Table 6

[0230] These results illustrate the surprising degreasing benefit of a polyether amine of the present disclosure (used in composition B) compared to a linear polyalkylene glycol diamine (composition A). Example 7: Comparative grease/grease removal of liquid laundry compositions
[0231] The following liquid laundry detergent compositions are prepared by traditional means known to those skilled in the art by mixing the aforementioned ingredients. Composition A is a premium conventional laundry detergent that does not contain an amino terminated polyalkylene glycol compound. Composition B is a premium conventional laundry detergent that uses Baxxodur EC301, a linear amino-terminated polyalkylene glycol with the structure of formula D.

[0232] Composition C is a detergent containing a polyether amine prepared in accordance with Synthesis Example 3, comprising a polyether amine comprising three terminal primary amines (see, for example, formula B).


1. Polyethylene imine (MW = 600) with 20 ethoxylate groups per -NH. 2. Random graphitized copolymer is a copolymer of poly(ethylene oxide) grafted with poly(vinyl acetate) which has a poly(ethylene oxide) backbone and multiple poly(vinyl acetate) side chains. The molecular weight of the poly(ethylene oxide) backbone is about 6000 and the ratio of the weight of the poly(ethylene oxide) to the weight of the poly(vinyl acetate) is about 40 to 60 and not more than 1 graft point per 50 units of ethylene oxide. 3. Linear alkylbenzenesulfonate with an average aliphatic carbon chain length of C11-C12, available from Stepan, Northfield, Illinois, USA 4. AE3S is C12-15 alkyl ethoxy sulfate (3), available from Stepan, Northfield, Illinois , USA 5. AE7 is C12-15 alcohol ethoxylate, with an average degree of ethoxylation of 7, supplied by Huntsman, Salt Lake City, Utah, USA 6. AE9 is C12-13 alcohol ethoxylate, with an average degree of ethoxylation of 9, supplied by Huntsman, Salt Lake City, Utah, USA 7. Suitable chelators are, for example, diethylenetriaminepentaacetic acid (DTPA), supplied by Dow Chemical, Midland, Michigan, USA, or hydroxyethanediphosphonate (HEDP), supplied by Solutia, St Louis, Missouri, USA Bagsvaerd, Denmark 8. Savinase®, Natalase®, Stainzyme®, Lipex®, Celluclean™, Mannaway® and Whitezyme® are all products from Novozymes, Bagsvaerd, Denmark. 9. Proteases can be supplied by Genencor International, Palo Alto, California, USA (eg, Purafect Prime®) or by Novozymes, Bagsvaerd, Denmark (eg, Liquanase®, Coronase®). 10. Suitable fluorescent whitening agents are, for example, Tinopal® AMS, Tinopal® CBS-X, sulfonated zinc phthalocyanine Ciba Specialty Chemicals, Basel, Switzerland. 11. Polyether amine prepared according to Synthesis Example 3.
[0233] CW120 cotton technical stain samples containing dirty motor oil, margarine, bacon fat, burnt butter, hamburger fat, Taco fat, Italian sauce and US clay are purchased from Empirical Manufacturing Co., Inc (Cincinnati) . Stained samples are washed in conventional Western European washing machines (Miele®) using a hardness of 14 grains per gallon, cycle selection for cotton at 15°C, using 80 g of each of the respective detergent compositions. . Image analysis is used to compare each stain to an unstained tissue control. The program converts the images taken into standard colorimetric values and compares them to standards based on the commonly used Macbeth Color Rendition Chart, assigning each stain a colorimetric value (spot content). Eight replicates of each stain are prepared. The stain removal index is then calculated according to the formula shown above.
[0234] The results are summarized in the following table (data from Table 7): Data from Table 7


[0235] These results illustrate the surprising degreasing benefit of a polyether amine of the present disclosure (as used in composition C) compared to a conventional liquid detergent (nyl-polyether amine) (composition A) and compared to with a liquid detergent formulated with a linear polyalkylene glycol diamine (composition B), specifically on stains that are difficult to remove and highly frequent by the consumer such as hamburger grease and taco grease under stressed washing conditions in cold water. Example 8: Comparative degreasing of laundry cleaning composition
[0236] The following laundry detergent compositions are prepared by traditional means known to those skilled in the art by mixing the aforementioned ingredients. Compositions A, B and C comprise polyether amines having the general structure of formula C.

[0237] Composition A uses a polyether amine according to formula C with an average n = 1.0. Composition B uses a polyether amine according to formula C with an average n = 2.0. Composition C uses a polyether amine according to formula C with an average n = 2.5. Composition D does not contain polyether amine.

1. Polyethylene imine (MW = 600) with 20 ethoxylate groups per -NH. 2. Linear alkylbenzenesulfonate with an average aliphatic carbon chain length of C11-C12, available from Stepan, Northfield, Illinois, USA 3. AE9 is C12-13 alcohol ethoxylate, with an average degree of ethoxylation of 9, supplied by Huntsman, Salt Lake City, Utah, USA 4. Suitable chelators are, for example, diethylenetriaminepentaacetic acid (DTPA), supplied by Dow Chemical, Midland, Michigan, USA, or hydroxyethanediphosphonate (HEDP), supplied by Solutia, St Louis, USA. Missouri, USA Bagsvaerd, Denmark 5. Natalase®, Mannaway® are products of Novozymes, Bagsvaerd, Denmark. 6. Proteases can be supplied by Genencor International, Palo Alto, California, USA (eg, Purafect Prime®) or by Novozymes, Bagsvaerd, Denmark (eg, Liquanase®, Coronase®). 10. Suitable fluorescent whitening agents are, for example, Tinopal® AMS, Tinopal® CBS-X, sulfonated zinc phthalocyanine Ciba Specialty Chemicals, Basel, Switzerland. 11. A polyether amine according to formula C above with an average n = 1 (composition A), an average n =2.0 (B composition), or an average n = 2.5 (composition C).
[0238] CW120 cotton technical stain samples containing hamburger fat, taco fat, margarine and burnt butter are purchased from Empirical Manufacturing Co., Inc (Cincinnati). Samples are washed in a Whirlpool® front loading washing machine, using a water hardness of 6 grains per gallon and washed at 37.8 degrees Celsius (100 degrees Fahrenheit). The total amount of liquid detergent used in the test is 49 grams.
[0239] Image analysis is used to compare each stain to an unstained tissue control. The program converts the images taken into standard colorimetric values and compares them with the standards based on the commonly used Macbeth Color Rendition Chart, assigning each stain a colorimetric value (spot content). Eight replicates of each stain are prepared.
[0240] Stain removal from samples is measured as follows:

[0241] The stain removal index ratings for each stain are calculated and are mentioned in the table below (data from table 8). Data from Table 8

[0242] These results illustrate the surprising degreasing benefit of a detergent comprising a polyether amine of the present disclosure (used in compositions A, B and C), compared to a conventional detergent that does not contain polyether amine (composition D). ).
[0243] The dimensions and values disclosed in the present invention are not to be understood as being strictly limited to the exact numerical values mentioned. Instead, unless otherwise specified, each of these dimensions is intended to mean both the mentioned value and a range of functionally equivalent values around that value. For example, a revealed dimension as "40mm" is intended to mean "about 40mm".
[0244] Each document cited in the present invention, including any cross-referenced or related patent or patent application, and any patent application or patent in which the present application claims priority or benefit, is hereby fully incorporated into this invention by reference, except where expressly excluded or otherwise limited. Mention of any document is not an admission that it constitutes prior art in relation to any invention disclosed or claimed in the present invention, nor that alone or in any combination with any other reference or references, teaches, suggests or describes such invention. . In addition, if there is a conflict between any meaning or definition of a term mentioned in this document and any meaning or definition of the same term in a document incorporated by reference, the meaning or definition given to said term in this document will take precedence.
[0245] While specific embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the art that various other changes and modifications may be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that fall within the scope of the present invention.

权利要求:
Claims (16)
[0001]
1. Cleaning composition, characterized in that it comprises: from 1% to 70% by weight of the composition of a surfactant system; and from 0.1% to 10% by weight of the composition of a polyether amine of Formula (I):
[0002]
2. Cleaning composition according to claim 1, characterized in that in said polyether amine of formula (I), R is H or a C1-C6 alkyl group selected from methyl, ethyl or propyl.
[0003]
3. Cleaning composition according to claim 1, characterized in that in said polyether amine of formula (I), each of k1, k2, and k3 is independently selected from 0, 1 or 2.
[0004]
4. Cleaning composition according to claim 1, characterized in that at least two of k1, k2, and k3 are 1.
[0005]
5. Cleaning composition according to claim 1, characterized in that in said polyether amine of formula (I), each one of A1, A2, A3, A4, A5, and A6 is independently selected from a linear or branched alkylene group having from 2 to 10 carbon atoms.
[0006]
6. Cleaning composition, according to claim 1, characterized in that in said polyether amine of formula (I), the sum of x+y+ z is in the range of 3 to 30.
[0007]
7. Cleaning composition, according to claim 1, characterized in that said polyether amine of formula (I) has a weight average molecular weight of 350 to 800 grams/mol.
[0008]
8. Cleaning composition, according to claim 1, characterized in that said cleaning composition comprises from 0.2% to 5% by weight of the polyether amine composition of formula (I).
[0009]
9. Cleaning composition, according to claim 1, characterized in that it additionally comprises from 0.001% to 1% by weight of an enzyme.
[0010]
10. Cleaning composition, according to claim 9, characterized in that said enzyme is selected from lipase, amylase, protease, mannanase or combinations thereof.
[0011]
11. Cleaning composition, according to claim 1, characterized in that said surfactant system comprises one or more surfactants selected from anionic surfactants, cationic surfactants, non-ionic surfactants, amphoteric surfactants.
[0012]
Cleaning composition according to claim 1, characterized in that it additionally comprises from 0.1% to 10% by weight of an additional amine selected from oligoamines, triamines, diamines, or a combination thereof, preferably selected from tetraethylenepentamine, triethylenetetraamine, diethylenetriamine, or a mixture thereof.
[0013]
Cleaning composition according to any one of claims 1 to 12, characterized in that it comprises: from 1% to 70% by weight of a surfactant system; and from 0.1% to 10% by weight of a polyether amine selected from among
[0014]
Cleaning composition according to any one of claims 1 to 12, characterized in that it comprises: from 1% to 70% by weight of a surfactant system; and from 0.1% to 10% by weight of a polyether amine obtainable by: a) reacting a low molecular weight triol with C2-C18 alkylene oxide to form an alkoxylated triol, wherein the molar ratio of the low triol molecular weight and the alkylene oxide is in the range of 1:3 to 1:10, and b) amine said alkoxylated triol with ammonia.
[0015]
15. Cleaning composition according to claim 14, characterized in that the low molecular weight triol is selected from the group consisting of glycerin, 1,1,1-trimethylolpropane and mixtures thereof.
[0016]
16. Cleaning composition according to claim 14, characterized in that the low molecular weight triol is 1,1,1-trimethylolpropane and the resulting polyether amine has a weight average molecular weight of 500 to 1,000.

类似技术:

---

公开号 | 公开日 | 专利标题

---

EP3039112B1|2019-03-20|Cleaning compositions containing a polyetheramine

---

CA2958655C|2018-09-18|Cleaning compositions containing a polyetheramine

---

US9771547B2|2017-09-26|Cleaning compositions containing a polyetheramine

---

JP6081658B2|2017-02-15|Cleaning composition containing polyetheramine, soil release polymer, and carboxymethylcellulose

---

JP6275864B2|2018-02-07|Cleaning composition containing polyetheramine

---

EP3212753B1|2019-07-31|Detergent compositions containing salts of polyetheramines and polymeric acid

---

EP3197993B1|2018-08-29|Detergent compositions containing a polyetheramine and an anionic soil release polymer

---

US9388368B2|2016-07-12|Cleaning compositions containing a polyetheramine

---

BR112015023827B1|2021-10-05|CLEANING COMPOSITIONS CONTAINING A POLYETHER AMINE AND METHOD OF PRE-TREATMENT OR TREATMENT OF A DIRTY TISSUE

---

BR112016003384B1|2021-12-07|COMPOSITIONS COMPRISING ALCOXYLATED POLYAMINES WITH LOW MELTING POINTS

同族专利:

---

公开号 | 公开日

---

BR112016002081A2|2017-08-01|

---

EP3039112A1|2016-07-06|

---

CN105492587B|2018-04-10|

---

CA2918838A1|2015-03-05|

---

JP6178011B2|2017-08-09|

---

CN105492587A|2016-04-13|

---

WO2015031071A1|2015-03-05|

---

MX2016002496A|2016-05-31|

---

US9550965B2|2017-01-24|

---

EP3039112B1|2019-03-20|

---

CA2918838C|2018-07-24|

---

JP2016534205A|2016-11-04|

---

ES2728011T3|2019-10-21|

---

US20150057212A1|2015-02-26|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US2295623A|1941-07-10|1942-09-15|William H Armstrong|Nonmetallic piping|

---

GB1185239A|1966-12-16|1970-03-25|Jefferson Chem Co Inc|Polyoxyalkylene Polyamines|

---

US3654370A|1970-08-28|1972-04-04|Jefferson Chem Co Inc|Process for preparing polyoxyalkylene polyamines|

---

US4450091A|1983-03-31|1984-05-22|Basf Wyandotte Corporation|High foaming liquid shampoo composition|

---

US4537705A|1984-04-25|1985-08-27|Economics Laboratory, Inc.|Aqueous alkaline polyamine paint stripping compositions|

---

US4556509A|1984-10-09|1985-12-03|Colgate-Palmolive Company|Light duty detergents containing an organic diamine diacid salt|

---

US4619775A|1985-05-16|1986-10-28|Colgate-Palmolive Company|Antistatic agents which are multiamides of trialkylacetic acids and multiamines|

---

US4764291A|1985-05-16|1988-08-16|Colgate-Palmolive Company|Process for treating laundry with multiamide antistatic agents|

---

US4609683A|1985-06-21|1986-09-02|Texaco Inc.|Quasi-prepolymers from isatoic anhydride derivatives of polyoxyalkylene polyamines and rim products made therefrom|

---

US4820436A|1985-06-22|1989-04-11|Henkel Kommanditgesellschaft Auf Aktien|Detergents for low laundering temperatures|

---

DE3832589A1|1988-09-24|1990-03-29|Henkel Kgaa|DETERGENT FOR LOW TEMPERATURES|

---

GB8916906D0|1989-07-24|1989-09-06|Precision Proc Textiles Ltd|New prepolymers and their use in a method for the treatment of wool|

---

WO1997030103A2|1996-02-15|1997-08-21|The Dow Chemical Company|Preparation of polyetheramines and polyetheramine derivatives|

---

WO1998028392A1|1996-12-20|1998-07-02|The Procter & Gamble Company|Dishwashing detergent compositions containing alkanolamine|

---

US6069122A|1997-06-16|2000-05-30|The Procter & Gamble Company|Dishwashing detergent compositions containing organic diamines for improved grease cleaning, sudsing, low temperature stability and dissolution|

---

DE69824743T2|1997-07-29|2005-07-07|The Procter & Gamble Company, Cincinnati|AQUEOUS, YELLOW DETERGENT COMPOSITIONS FOR WASHING|

---

US5863886A|1997-09-03|1999-01-26|Rhodia Inc.|Nonionic gemini surfactants having multiple hydrophobic and hydrophilic sugar groups|

---

WO1999014297A1|1997-09-15|1999-03-25|The Procter & Gamble Company|Laundry detergent compositions with linear amine based polymers to provide appearance and integrity benefits to fabrics laundered therewith|

---

US6191099B1|1997-12-04|2001-02-20|Tomah Products, Inc.|Method for cleaning hydrocarbon-containing soils from surfaces|

---

US6146427A|1997-12-04|2000-11-14|Crutcher; Terry|Method for cleaning hydrocarbon-containing greases and oils from fabric in laundry washing applications|

---

CZ20004477A3|1998-06-02|2002-01-16|The Procter & Gamble Company|Dishwashing detergent compositions containing organic diamines|

---

US6710023B1|1999-04-19|2004-03-23|Procter & Gamble Company|Dishwashing detergent compositions containing organic polyamines|

---

AR018715A1|1999-04-19|2001-11-28|Procter & Gamble|DETERGENT COMPOSITIONS CONTAINING POLYAMINS FOR DISHWASHING|

---

JP2001014840A|1999-06-24|2001-01-19|Nec Corp|Plural line buffer type memory lsi|

---

WO2001005872A1|1999-07-16|2001-01-25|Basf Aktiengesellschaft|Zwitterionic polyetherpolyamines and a process for their production|

---

US6703523B1|1999-07-16|2004-03-09|Basf Aktiengesellschaft|Zwitterionic polyetherpolyamines and process for their production|

---

GB9923921D0|1999-10-08|1999-12-08|Unilever Plc|Fabric care composition|

---

US6857485B2|2000-02-11|2005-02-22|M-I Llc|Shale hydration inhibition agent and method of use|

---

AU5317901A|2000-04-06|2001-10-23|Huntsman Spec Chem Corp|Defoamer compositions and uses therefor|

---

US6437055B1|2000-04-07|2002-08-20|Ppg Industries Ohio, Inc.|Electrodepositable coating from gelled epoxy-polyester and amine|

---

US6172024B1|2000-04-17|2001-01-09|Colgate-Palmolive Co.|High foaming grease cutting light duty liquid detergent comprising a poly diamine|

---

JPWO2002033072A1|2000-10-20|2004-02-26|中外製薬株式会社|Small molecule TPO agonist antibody|

---

US6306805B1|2000-09-15|2001-10-23|Stepan Company|Shampoo and body wash composition comprising ternary surfactant blends of cationic, anionic, and bridging surfactants and methods of preparing same|

---

US20020147368A1|2000-12-18|2002-10-10|Wei Li|Branched reaction products of alcohols and aldehydes|

---

US20030134772A1|2001-10-19|2003-07-17|Dykstra Robert Richard|Benefit agent delivery systems|

---

US6652667B2|2002-01-23|2003-11-25|Chevron Oronite Company Llc|Method for removing engine deposits in a gasoline internal combustion engine|

---

CA2496480C|2002-08-30|2011-02-08|Huntsman Petrochemical Corporation|Polyether polyamine agents and mixtures therefor|

---

US6951710B2|2003-05-23|2005-10-04|Air Products And Chemicals, Inc.|Compositions suitable for removing photoresist, photoresist byproducts and etching residue, and use thereof|

---

JP2005048086A|2003-07-30|2005-02-24|Kao Corp|Method for manufacturing polyoxyalkylene triamine|

---

US7037883B2|2003-09-17|2006-05-02|Unilever Home & Personal Care Usa Division Of Conopco, Inc.|Process of making a liquid laundry detergent with polyanionic ammonium surfactant|

---

DE602004004289T2|2003-09-17|2007-04-19|Unilever N.V.|LIQUID DETERGENT WITH POLYANIONIC AMMONIUM TENSID|

---

JP4444610B2|2003-09-26|2010-03-31|ライオン株式会社|Liquid detergent in bag-like containers|

---

US20060074004A1|2004-10-04|2006-04-06|Johnson Andress K|Light duty liquid detergent composition|

---

US7387992B2|2005-03-15|2008-06-17|Unilever Home & Personal Care Usa Division Of Conopco, Inc.|Laundry detergent with polyamine mono-anionic surfactant|

---

EP2125920B1|2007-03-15|2014-12-31|Huntsman Petrochemical LLC|High functionality amine compounds and uses therefor|

---

WO2009045408A1|2007-10-01|2009-04-09|Ethox Chemicals, Llc|Alkoxylated polyamines and polyetherpolyamine polyol compositions for foam control|

---

BRPI0818891A2|2007-11-09|2015-05-05|Procter & Gamble|Alkoxylated polyalkanolamine cleaning compositions|

---

WO2009061980A1|2007-11-09|2009-05-14|The Procter & Gamble Company|Cleaning compositions comprising a multi-polymer system comprising at least one alkoxylated grease cleaning polymer|

---

DE102007056525A1|2007-11-22|2009-10-08|Henkel Ag & Co. Kgaa|Polyoxyalkylenamine for improved perfume yield|

---

AU2009223566B2|2008-03-10|2013-12-12|Huntsman Petrochemical Llc|Cyclohexanedimethanamine by direct amination of cyclohexanedimethanol|

---

GB0810881D0|2008-06-16|2008-07-23|Unilever Plc|Improvements relating to fabric cleaning|

---

US8597668B2|2009-02-09|2013-12-03|L'oreal|Clear carrier compositions for lipophilic compounds, and method of treating keratinous substrates using such compositions|

---

EP2264138B1|2009-06-19|2013-03-13|The Procter & Gamble Company|Liquid hand dishwashing detergent composition|

---

JP5340821B2|2009-06-22|2013-11-13|三洋化成工業株式会社|Kitchen cleaner composition|

---

MX341950B|2009-12-02|2016-09-08|Huntsman Petrochemical Llc|Preparation and use of poymeric dispersant compositions.|

---

CN106632994B|2009-12-22|2019-05-14|亨斯迈石油化学有限责任公司|Ether amines and its in Macroscopic single crystal as the purposes of intermediate|

---

WO2012126665A1|2011-03-21|2012-09-27|Unilever Plc|Dye polymer|

---

CN105026539A|2013-03-05|2015-11-04|宝洁公司|Mixed sugar compositions|

---

EP2978831B1|2013-03-28|2020-12-02|The Procter and Gamble Company|Cleaning compositions containing a polyetheramine, a soil release polymer, and a carboxymethylcellulose|EP2978831B1|2013-03-28|2020-12-02|The Procter and Gamble Company|Cleaning compositions containing a polyetheramine, a soil release polymer, and a carboxymethylcellulose|

---

WO2015028191A1|2013-08-26|2015-03-05|Basf Se|Alkoxylated polyethyleneimine with a low melting point|

---

EP2842936A1|2013-08-26|2015-03-04|Basf Se|Etheramines based on alkoxylated glycerine or trimethylolpropane.|

---

CN106062078B|2014-02-26|2020-05-08|信越化学工业株式会社|Defoaming agent composition|

---

US9771547B2|2014-03-27|2017-09-26|The Procter & Gamble Company|Cleaning compositions containing a polyetheramine|

---

EP3122849B1|2014-03-27|2021-07-21|The Procter & Gamble Company|Cleaning compositions containing a polyetheramine|

---

WO2015144436A1|2014-03-27|2015-10-01|Basf Se|Etheramines based on dialcohols|

---

EP2940117B1|2014-04-30|2020-08-19|The Procter and Gamble Company|Cleaning composition containing a polyetheramine|

---

EP2940116B1|2014-04-30|2018-10-17|The Procter and Gamble Company|Detergent|

---

BR112016028904A8|2014-06-09|2021-05-04|Stepan Co|laundry detergent, liquid, powder, paste, granule, tablet, molded solid, water soluble sheet, water soluble sachet, capsule, or water soluble cocoon and method|

---

US9617502B2|2014-09-15|2017-04-11|The Procter & Gamble Company|Detergent compositions containing salts of polyetheramines and polymeric acid|

---

WO2016041697A1|2014-09-15|2016-03-24|Basf Se|Salts of etheramines and polymeric acid|

---

JP6430632B2|2014-09-25|2018-11-28|ザ プロクター アンド ギャンブル カンパニー|Fabric care composition containing polyetheramine|

---

US9631163B2|2014-09-25|2017-04-25|The Procter & Gamble Company|Liquid laundry detergent composition|

---

CA2958655C|2014-09-25|2018-09-18|The Procter & Gamble Company|Cleaning compositions containing a polyetheramine|

---

US9752101B2|2014-09-25|2017-09-05|The Procter & Gamble Company|Liquid laundry detergent composition|

---

US9388368B2|2014-09-26|2016-07-12|The Procter & Gamble Company|Cleaning compositions containing a polyetheramine|

---

EP3034592A1|2014-12-17|2016-06-22|The Procter and Gamble Company|Method of automatic dishwashing|

---

EP3034597A1|2014-12-17|2016-06-22|The Procter and Gamble Company|Detergent composition|

---

EP3034588B1|2014-12-17|2019-04-24|The Procter and Gamble Company|Detergent composition|

---

EP3298115B1|2015-05-22|2019-03-20|The Procter and Gamble Company|Method of making surfactant compositions and detergent compositions comprising alkoxylated glycerine as a solvent|

---

WO2016191237A1|2015-05-22|2016-12-01|The Procter & Gamble Company|Surfactant and detergent compositions containing ethoxylated glycerine|

---

EP3162880A1|2015-10-29|2017-05-03|The Procter and Gamble Company|Liquid detergent composition|

---

EP3170886B1|2015-11-20|2019-01-02|The Procter and Gamble Company|Cleaning product|

---

CN105694529B|2015-11-30|2017-06-23|南京工业大学|The active cationic dye of one class containing polyetheramine segment and preparation method thereof|

---

WO2017120354A1|2016-01-05|2017-07-13|Saudi Arabian Oil Company|Removal of barite weighted mud|

---

US20170275565A1|2016-03-24|2017-09-28|The Procter & Gamble Company|Compositions containing an etheramine|

---

US10457900B2|2016-05-20|2019-10-29|The Proctor & Gamble Company|Detergent composition comprising an alkyl ether sulfate-rich surfactant system and coated encapsulates|

---

EP3458567A1|2016-05-20|2019-03-27|Stepan Company|Polyetheramine compositions for laundry detergents|

---

EP3458563B1|2016-05-20|2020-10-14|The Procter and Gamble Company|Detergent composition comprising encapsulates and deposition aid|

---

US10494592B2|2016-05-20|2019-12-03|The Procter & Gamble Company|Detergent composition comprising anionic/nonionic/cationic surfactant system and encapsulates|

---

US20170355930A1|2016-06-09|2017-12-14|The Procter & Gamble Company|Cleaning compositions including nuclease enzyme and amines|

---

WO2018048364A1|2016-09-08|2018-03-15|Hayat Kimya San. A. Ş.|Laundering of fabrics woven from polyester fibres|

---

BR112019015865A2|2017-02-06|2020-04-14|Procter & Gamble|laundry detergent sheet with printed graphic patterns|

---

CN108949394B|2018-08-14|2020-09-11|广州立白企业集团有限公司|Concentrated liquid detergent composition substantially free of solubilizer|

---

WO2020070209A1|2018-10-02|2020-04-09|Novozymes A/S|Cleaning composition|

法律状态:
2018-11-27| B25A| Requested transfer of rights approved|Owner name: BASF SE (DE) |

---

2019-11-12| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2021-09-08| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

---

2021-11-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

---

2022-01-25| 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 15/08/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

---

申请号 | 申请日 | 专利标题

---

US201361869848P| true| 2013-08-26|2013-08-26|

---

US61/869,848|2013-08-26|

---

PCT/US2014/051165|WO2015031071A1|2013-08-26|2014-08-15|Cleaning compositions containing a polyetheramine|

---