ITACONIC ACID POLYMERS

专利摘要:
itaconic acid polymers the disclosed technology refers to poly-itaconic acid homopolymers and copolymers free of the less reactive tri-substituted vinyl monomers (e.g. citraconic acid or mesaconic acid) that can be used, for example, as builders in detergent applications, such as in the personal care and home care market.
公开号:BR112015023790B1
申请号:R112015023790-8
申请日:2014-03-14
公开日:2021-09-14
发明作者:Krishnan Tamareselvy；Feng-Lung Gordon Hsu；Smita Brijmohan；Francine I. Shuster；John Ta-Yuan Lai；Guarave Mago
申请人:Lubrizol Advanced Materials, Inc；
IPC主号:

专利说明:

BACKGROUND OF THE INVENTION
[0001] The disclosed technology refers to poly-itaconic acid homopolymers and copolymers free of the less reactive tri-substituted vinyl monomers (for example, citraconic acid or mesaconic acid) that can be used, for example, as builders in applications detergent, such as in the home and personal care market.
[0002] Builders (herein used interchangeably with "chelants") are used in detergent cleaners, typically surfactant containing systems, to enhance and improve the cleaning properties of the detergent cleaner. The builder's role is to remove calcium and other unwanted metal ions from wash solutions by precipitation or sequestration. Additionally, builders can chelate hardness ions, and provide a pH buffering function and some anti-redeposition functionality that can improve cleaning performance. Inorganic Sodium Tripolyphosphate (STPP) is a conventional builder that has historically been used in detergent cleaning products. However, environmental problems associated with STPP are not perceived and its use has been reduced or eliminated from many detergent products, such as, for example, dishwashing detergents. The loss of STPP as a builder created immediate product performance issues in the dishwashing detergent market, particularly in relation to inefficiencies of cleaning and film formation due to a failure to remove metal ion residues.
[0003] Due to the lack of performance in current phosphate free detergent systems, there is an unmet need in the market for an improved functional builder. A sustainable or "green" product solution with better performance is highly desirable.
[0004] There are several patents of prior art processes that provide processes for the production of homopolymer of itaconic acid (AI). A common thread in the prior art is the use of neutralization in the process. For example, Pat. No. 5,223,592 reports that the critical aspect in the preparation of itaconic acid is to provide the total neutralization of a monomer of the itaconic acid type, before carrying out the polymerization reaction. Complete neutralization is identified when it has two moles of base neutralizer for every mole of itaconic acid. Similarly, Pat. No. 5,336,744 discloses a process that utilizes between 5% and 50% neutralization along with a polyvalent metal ion and an initiator. Another US Patent No. 7,910,676 from the University of New Hampshire teaches a process that uses a degree of partial neutralization (25-75%) and an initiator to make a high molecular weight polymer. The itaconic acid polymerization process, which involves a neutralization step, as per the above references, leads to a rearrangement of di-substituted itaconic acid-derived monomers to less reactive tri-substituted vinylic monomers (eg derivative monomers of citraconic acid or mesaconic acid, as represented in Formula I below). Such isomerization to the tri-substituted monomers results in polymers with unreacted residues and subsequently causes reduced chelation efficiency. Formula I

[0005] In contrast, the polymerization of itaconic acid in acidic medium does not favor the rearrangement of itaconic acid to less reactive citraconic acid. The polymerization of itaconic acid in an acidic medium has been reported in "Polymerization of itaconic acid and some of its derivatives" Marvel et al, Journal of Organic Chemistry, (1959), 24, 599, and in "Polymerization of Itaconic Acid In Aqueous Solution : Structure Of The Polymer And Polymerization Kinetics At 25°C Studied By Carbon-13 NMR, " Grespos et al, Makromolekulare Chemie, Rapid Communications (1984), 5(9), 489-494. However, these methods have disadvantages such as poor conversion with long polymerization times and corrosiveness issues. Likewise, the document WO 2001/21677 describes a polymerization of itaconic acid, which comprises a free radical generator (persulfate) and a reducing agent containing phosphorus, which generates a product with undesirable phosphorous components.
[0006] US 4,485,223 teaches an "essentially homogeneous" (meth)acrylic/itaconic acid copolymer. The process taught in the '223 patent teaches a post-neutralization step, and process temperatures ranging from 80 to 120°C, as well as a 5 to 20 mol% initiator amount. The level of initiator required in the polymerization step of the ‘223 process results in a corrosive copolymer solution (pH <1), which poses significant safety issues from a standpoint that would make scale-up manipulation difficult. Furthermore, the high level of initiator used in the polymerization taught in the "223 patent generates a dark colored copolymer with a strong unpleasant sulfur odor that would not be suitable for use in the personal care and home market. The high temperatures used in the process '223 cause the initiator to decompose rapidly, resulting in oxidized and/or sulfurized impurities of the itaconic acid, and resulting in an inferior product.
[0007] Itaconic acid polymers and copolymers that have improved purity, and that are free of tri-substituted vinyl monomer impurities that provide improved chelating, anti-redeposition, drag reduction, and chlorine stabilization capabilities, along with chlorine preparation methods. themselves, would be desirable. SUMMARY OF THE INVENTION
[0008] The disclosed technology therefore solves the problem of inefficient binding capacity of ions by providing polymers, copolymers and/or terpolymers that are derived from substantially pure itaconic acid and that are free of impurities from vinyl tri-monomers replaced and therefore suitable for personal and home care applications.
[0009] Furthermore, it has also been observed that polymers and copolymers of partially esterified itaconic acid and/or impurity-free terpolymers of tri-substituted vinyl monomer provide better dispersibility of hydrophobic particles, for example, in detergent applications , such as laundry and dish detergents.
[0010] In one embodiment, a polymer composition comprising monomeric units derived from itaconic acid is provided. Preferably, the polymer is free of tri-substituted vinyl monomers, such as citraconic acid and/or mesaconic acid isomers.
[0011] The polymer composition may further comprise comonomer units. Suitable comonomer units may be those derived, for example, from acrylic acid, methacrylic acid, and its salts, esters and/or anhydrides, 2-acrylamide-2-methylpropane sulfonic acid (AMPS™ a registered trademark of Lubrizol Corporation) and its salts, and/or combinations thereof. Preferably, the monomeric units derived from itaconic acid are present in more than 25% or 50% molar, for example between 60% and 70% or 80% molar, and the comonomer units are present in less than 50% or 75% mole, such as from 10% or between 20% and 30% or 40% mole or between 50% and 70% mole. In one embodiment, the polymeric composition can include monomer units derived from itaconic acid and (meth)acrylic from about 90% to about 99.9 mol% and monomer units derived from AMPS from about 0.1% to about 10% molar.
[0012] The polymer or copolymer, or terpolymer, can be from about 0.1% to about 60% esterified.
[0013] The polymer composition preferably has a number average molecular weight (Mn) of between about 500 and 100,000 and is included in an aqueous polymer solution comprising the polymer composition and water. In some embodiments, the polymer composition can have an Mn between about 100 or 150 and 500. When in polymer solution, the solution preferably has a pH greater than 1.8 and is transparent or substantially transparent.
[0014] In a further aspect, the disclosed technology provides a solution of polymer, polymer or copolymer, or terpolymer of itaconic acid. The polymer solution may contain less than 0.5% w/w of unreacted monomer based on the total weight of polymer present in the solution, and preferably, may be characterized by a pH greater than 1.8.
[0015] In another aspect, the technology disclosed provides a process for the preparation of the polymer or copolymers, or terpolymers of itaconic acid. The process may include in the preparation steps in an aqueous medium, a solution of itaconic acid monomer greater than about 25% or 50% molar itaconic acid monomer, with less than about 50% or 75% molar a comonomer composition comprising acrylic acid, methacrylic acid, and AMPS, or a mixture thereof, wherein said comonomer composition is added to said itaconic acid monomer, over a period of about 2 at 12, or 14, or 16 hours, at a polymerization temperature of more than 50 or 60°C in the presence of from about 0.01 to about 5 mol% polymerization initiator, based on the total amount of said monomers. The comonomer composition and at least half of said initiator can be added separately and continuously, essentially during the entire period, to the itaconic acid monomer, in solution in said medium.
[0016] In one embodiment, the itaconic acid monomer and about 0.5 to about 10% by weight, or from about 2 to about 25% by weight of the initiator are dissolved in the medium, and the remainder of the initiator is introduced over the period.
[0017] In one embodiment, the initiator is a redox system. In a preferred embodiment, the redox system contains a sodium persulfate oxidant and a reductant comprising a mixture of a disodium salt of 2-hydroxy-2-sulfinateacetic acid and sodium sulfite. In other embodiments, the redox system comprises a sodium persulfate, a tert-butyl perpivalate, or a tert-butyl perbenzoate oxidant, and a reductant comprising a mixture of a disodium salt of 2-hydroxy-2-sulfinateacetic acid and sodium sulfite.
[0018] In some embodiments, the process may include the additional step of pre-neutralizing the monomer solution with less than 5% mole of a neutralizer per total acid group of all monomers present in the monomer solution. In some embodiments, the neutralizer is a base that has less than 25 mol% carboxylic acid functionality.
[0019] The process may further include a step of post-neutralizing the resulting polymer solution with up to 120 mol% of a neutralizer per total acid group in the polymer solution.
[0020] In another embodiment, the process may include the additional step of converting the polymer solution into a powder by (i) granulating the polymer with inorganic bases, (ii) spray drying the pre-neutralized polymer solution, or (iii) granulating the spray dried powders with binders.
[0021] A further aspect of the disclosed technology is a dishwashing detergent comprising the polymer or copolymer, or itaconic acid terpolymer, or polymer solution containing the polymer or copolymer, or itaconic acid terpolymer. Likewise, the disclosed technology provides a laundry detergent and hard surface cleaner comprising the polymer or copolymer, or terpolymer of itaconic acid, or polymer solution containing the polymer or copolymer, or terpolymer of itaconic acid.
[0022] The dishwashing detergent may be in the form of a gel, liquid, powder, bars, paste, hard or soft single layer tablet, hard or soft multi-layer tablet, single-dose and single-phase detergent, dose single multiphase, or unit dose. The laundry detergent may be in the form of a gel, liquid, powder, bars, paste, hard or soft single layer tablet, hard or soft multi layer tablet, single dose and single phase detergent, multiphase single dose, or dose unitary.
[0023] In one embodiment, the polymer can be used in a cosmetically acceptable formulation, for example, a body cleansing formulation or shampoo.
[0024] In one embodiment, the polymeric composition and/or polymeric solution can be used in an ion chelation process, providing the polymer composition or polymer formulation to a pharmaceutically, cosmetically, or industrially acceptable composition.
[0025] In another embodiment, the technology provides a method of providing industrial water treatment and/or industrial water purification that comprises the addition of a deposit control agent, comprising an itaconic acid polymer as described above, for a water solution in need of industrial water treatment and/or industrial water purification. In such an embodiment, the method may include mixing the itaconic acid polymer with other known scale inhibitors and/or dispersing agents comprising phosphonates, homo- or copolymers of polymaleic and/or polyacrylic acid; and/or corrosion inhibitors comprising tolyltriazole, polyphosphates, phosphonates, and molybdate.
[0026] In yet another embodiment, the technology provides a method that provides for the modification of rheology in drilling operations and/or mud transport applications, which comprises adding an acid polymer to a drilling mud or paste. itaconic, and operating a drill with the drilling mud or paste. In such an embodiment, the method may include mixing the itaconic acid polymer with other known scale inhibitors and/or dispersing agents comprising phosphonates, homo- or copolymers of polymaleic and/or polyacrylic acid; and/or corrosion inhibitors comprising tolyltriazole, polyphosphates, phosphonates, and molybdate. BRIEF DESCRIPTION OF THE DRAWINGS
[0027] Figure 1: 1H NMR of Comparative Sample I
[0028] Figure 2: 1H NMR of Comparative Sample II
[0029] Figure 3: 1H NMR of Sample 5 DETAILED DESCRIPTION OF THE INVENTION
[0030] Various preferred aspects and embodiments will be described below, by way of non-limiting illustration.
[0031] A first aspect of the invention is a homogeneous or substantially homogeneous polymer. As used herein, the term polymer can include any type of polymer, such as, for example, random or block copolymers, terpolymers and other polymers that contain more than two monomers ("improved polymers"). The improved polymer can provide greater builder efficiency for personal care, home care, healthcare, and industrial and institutional (I&I) applications. The improved polymers may consist of monomers derived from itaconic acid, or consist of, consist essentially of, or comprise monomers derived from itaconic acid and an acrylic acid, methacrylic acid or co-monomers derived from 2-acrylamide-2-methylpropane sulfonic acid ( AMPS) or other carboxylic acid containing comonomers such as maleic acid and fumaric acid.
[0032] As used herein, (meth)acrylic acid refers to both acrylic acid and methacrylic acid. Furthermore, when discussing itaconic acid, (meth)acrylic, and AMPS, in relation to a polymer, copolymer and/or terpolymer, it is to be understood that reference to the acid form encompasses the monomer unit derived therefrom. Thus, for example, a polymer of itaconic acid and acrylic acid is to be understood as comprising monomeric units derived from itaconic acid and monomeric units derived from acrylic acid.
[0033] Itaconic acid is an organic compound that is non-toxic and can be derived from renewable resources. Itaconic acid can be obtained by distilling citric acid or by fermenting carbohydrates such as glucose using Aspergillus terreus. Itaconic acid may be referred to as methylenesuccinic acid or 2-methylidenebutanedioic acid. Itaconic acid can be represented by the formula C5H6O4 or by the formula CH2=C(COOH)CH2COOH.
[0034] The improved polymer can be a homopolymer, wherein the main part of the polymer comprises structural units derived from itaconic acid, or an anhydride, ester or salt (collectively referred to as itaconic acid). The improved polymer can also be a copolymer or terpolymer in which the main part of the polymer comprises structural units derived from itaconic acid, or an anhydride, ester or salt thereof, and at least one of (meth)acrylic acid, and its anhydrides , esters and salts, AMPS and its salts (collectively referred to as (meth)acrylic acid and AMPS).
[0035] Salts of (meth)acrylic acid and AMPS may be the same as salts of itaconic acid, namely sodium salts, potassium or ammonia salts, and alkylated ammonium salts, such as triethylammonium salt, and alkylated hydroxylammonium salts such as triethanol ammonium salt, and the like.
[0036] The improved polymer may contain monomer units derived from itaconic acid. Preferably, the improved polymer may contain greater than about 25 mol%, 50 mol%, 60 mol%, or greater than 70 mol%, monomer units derived from itaconic acid. In some embodiments, the improved polymer may contain from about 35 mol% to about 60 mol%, or 35, 50 or 60 mol% to about 70 or 80 mol%, monomeric units derived from itaconic acid. In certain cases, the monomeric units derived from itaconic acid can be from about 1 to about 99 mol%, or about 5 to about 95 mol%, or even about 10 to about 90 mol%, and in some cases from about 20 to about 80% molar. In certain cases, about 0.1 to about 15 or 20 mol%, or about 0.5 or 1.0 to about 2.5 or 5 or 10 mol% of monomer units derived from itaconic acid may be replaced by monomer units derived from AMPS.
[0037] The improved polymer may optionally contain comonomer units derived from (meth)acrylic acid or carboxylic acid containing other comonomer such as maleic acid and fumaric acid. The amount of comonomer units derived from (meth)acrylic acid or other carboxylic acids that contain comonomers such as maleic acid and fumaric acid can be up to about 75 mol%, 50 mol% of the copolymer and/ or terpolymer, or up to about 30 or 40 mol%. In certain embodiments, (meth)acrylic acid-derived comonomer units can be from about 15 or 20 or 25 mol% to about 30 or 40 or 50 mol% of the copolymer or terpolymer composition. In certain cases about 0.1 to about 15 or 20 mol%, or about 0.5 or 1.0 to about 2.5, or 5 or 10 mol% of comonomer units derived from (meth)acrylic acid may be replaced by units of AMPS-derived comonomers.
[0038] The improved polymer may optionally contain AMPS-derived comonomer units. The amount of AMPS-derived comonomer units can be up to about 75 mol%, 50 mol% of the copolymer and/or terpolymer, or up to about 30 or 40 mol%. In certain instances, the AMPS-derived comonomer units can be from about 15 or 20 or 25 mol%, to about 30 or 40 or 50 mol% of the copolymer or terpolymer composition. In some cases, AMPS comonomer units may replace a portion of the itaconic acid monomers, (meth)acrylic acid monomers, or a combination thereof. AMPS-derived monomers can replace about 0.1 to about 20% mole, or about 0.5 to about 10% or 15% mole, or about 1 to about 2.5 or 5% mole of itaconic acid monomers, of (meth)acrylic acid monomers, or a combination thereof, in which case the other comonomers will be in a range of about 80% or 85% to about 99.9 mol%, or about 90% or 95% to about 99.5% molar, or about 97.5% to about 99% of the copolymer and/or terpolymer.
[0039] The improved polymers are free, or substantially free from moieties of tri-substituted vinyl monomer isomers of itaconic acid, such as citraconic acid and mesaconic acid. By "substantially free of tri-substituted vinyl monomer isomer moieties", it is meant that there is an insufficient amount of the isomer moieties present in the improved polymer to effect the effectiveness of the improved polymer, such as, for example, less than 0.5 mole %, or 0.1 mole %, or less than 0.05 mole %, or less than 0.01 mole %, based on the number of monomer units in the improved polymer.
[0040] In addition, the improved polymer solution will include less than 0.5% w/w of unreacted monomer and comonomer, based on the total weight of polymer present in the solution, or less than 0.25% w/w , or free or substantially free of unreacted monomer and comonomer. Here again, by "substantially free of unreacted monomer" is meant that there is an insufficient amount of unreacted monomer present in the improved polymer solution to affect the effectiveness of the solution, such as, for example, less than than 0.5% molar, or 0.1% w / w, or less than 0.05% w / w, or less than 0.01% w / w, or less than 0.001% w / w, based on the weight of the improved polymer in the solution , or less than 2.5 or 2.0% by weight, or 1% by weight, or less than 0.5% by weight, or less than 0.1% by weight.
The improved polymers can have a number average molecular weight (Mn) of from about 500 to 100,000, preferably from about 1000 to 50,000, more preferably from about 2500 to about 25,000. The polymer can also have a Mn of from about 3000 to about 20,000. In some embodiments, the Mn of the improved polymers can be from about 500 to about 10,000 or about 1000 to 5000. In some embodiments, the polymer composition can have a Mn of about 100 or between 150 and 500. Accordingly, the improved polymer may have a polydispersity of from about 1 to 20, more preferably from 1 to 10, or from 1 to 5 or 8.
[0042] Improved polymers can be prepared by polymerizing itaconic acid alone, or with a large amount of itaconic acid monomer with at least one (meth)acrylic acid comonomer, AMPS comonomer, or its combinations. The polymerization process can provide homogeneous, substantially homogeneous, random or block polymers and copolymers.
[0043] Block copolymers are defined by the art as polymers derived from two or more different monomers, in which multiple sequences, or blocks, of the same monomer alternate in series with the different monomer blocks. Block copolymers can contain two blocks (diblock), three blocks (triblock), or more than three blocks (multiblock). Block copolymers can be alternated with copolymers of two or more different monomers along the main portion of the polymer at regularly alternating intervals. There are also periodic copolymers in which the two or more monomers are arranged in a sequence that repeats regularly, and statistical copolymers, in which the sequence of the two or more different monomers is repeated based on the statistical rule. Preferably, the block copolymer created in accordance with the process of the invention is a multi-alternate block copolymer.
[0044] In one aspect of the invention, the best polymers of the invention can be synthesized by free radical polymerization of the monomer mixture described above. Polymers can be prepared by means of solution, dispersion, precipitation, bulk or bulk, emulsion (or inverse emulsion) polymerization techniques that are well known in the polymer art.
[0045] In one aspect, the present polymers are prepared by solution polymerization in an aqueous medium. By aqueous medium is meant water, mixtures of water and other solvents such as alcohols, as well as the alcohols themselves.
[0046] The polymerization can be carried out in a variety of solvents, such as alcohols, ethers, esters, aromatic solvents, glycols, glycol ethers, and glycol esters, all of which are herein considered to be aqueous media. Preferred solvents include ethyl alcohol, isopropyl alcohol, t-butyl alcohol, ethyl acetate, methyl acetate, butyl acetate, benzene, toluene, methyl ethyl ketone, and methylene chloride. These solvents can also be used in combination with hydrocarbon solvents such as hexane, cyclohexane, mineral spirits and the like. A preferred aqueous medium is water. Another preferred solvent is a mixture of isopropyl alcohol and water. Isopropyl alcohol is another preferred aqueous medium.
[0047] The polymerization process is carried out in an aqueous medium in the presence of a polymerization initiator and under lower temperatures taught in the prior art. In general, (meth)acrylic acid, AMPS, their combinations and the initiator are added separately from itaconic acid, but they can also be added simultaneously with itaconic acid. Acrylic acid, methacrylic acid and AMPS copolymerize essentially the same way with itaconic acid, and can therefore be interchanged or mixed in the process to generate products with essentially the same molecular weight, and improved metal ion binding characteristics for a copolymer of a molar ratio of AMPS or (meth)acrylic acid / itaconic acid given.
[0048] The process may include a pre-neutralization step in which the pH of the polymerization solution is neutralized with a neutralizer, (i.e., a source of sodium, potassium or ammonia, and alkylated ammonia, such as triethyl ammonia, and alkylated hydroxylammonia such as triethanol ammonia, and the like) at a pH greater than about 1.8, or greater than about 2 or 3. The closer to neutral the pH, (ie, 7) the less corrosive the polymer solution will be. . However, the greater the amount of neutralization, the more likely it is that itaconic acid will isomerize. Thus, the neutralizer is added in an adequate amount to reach a pH greater than 1.8 but less than the critical threshold at which it will isomerize the itaconic acid. Generally, the neutralizer can be added during the pre-neutralization step in a dosage to neutralize no more than 20 mol% of the carboxylic acid groups from the itaconic acid monomers. Preferably, the neutralizer can be added during the pre-neutralization step at a dosage to neutralize, of no more than 20 mol%, 15 mol%, or 10 mol% of the total carboxylic acid groups of all monomers, more preferably not more than 5 mole % (which is referred to in terms of degree of neutralization, based on mole % acid). In some embodiments, the neutralizer can be added during the pre-neutralization step at a dosage to neutralize from about 0.01 to about 20 mol% of the carboxylic acid groups from all monomers, more preferably, from about 0.1 to about 15% mole, or from about 0.5 to about 10% mole, or even from 1 to about 5% mole of the carboxylic acid groups of all monomers.
[0049] The process can also include a post-neutralization step in which the pH of the final product is neutralized with a neutralizer. Post-neutralization can make the polymer more alkaline so that it can be used in high pH applications. An amount of up to about 120 mol% of the amount of neutralizer needed to completely neutralize the polymer can be added during post-neutralization, or up to about 100 mol%. In another embodiment, a neutralizer can be added from about 60% to about 100% mole, or about 65% or 70%, or 75% to about 85%, or 90% or 95% mole.
[0050] The neutralizer can be an alkali metal base, ammonia, and/or amine base. Alkali metal bases suitable for neutralization include sodium hydroxide, potassium hydroxide and lithium hydroxide, while suitable ammonia and amine bases include ammonia, ammonium hydroxide, mono-, di- and trialkylamines which have from 1 to 5 carbon atoms in each alkyl, pyridine, morpholine and lutidine group. The neutralizer may also be a base having a carboxylic acid functionality, although it is preferred that said neutralizer has a carboxylic acid functionality of less than 25 mol%. Examples of carboxylic acid functional neutralizers include, but are not limited to, amino acids, peptides, polypeptides and derivatives thereof. The amino acid can be chosen from, for example, alanine, arginine, asparagine, aspartic acid, cysteine, glutamine, glutamic acid, glycine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, and valine.
[0051] Any water-soluble free radical initiator can be used as the polymerization initiator of the present process. Suitable initiators include persulfates, such as sodium and potassium persulfate, as well as redox systems.
[0052] Other initiators include peroxy- and/or azo-type initiators, such as hydrogen peroxide, benzoyl peroxide, acetyl peroxide, and lauryl peroxide, t-butyl peroxypivalate, cumyl t-butyl peroxide and/ or cumene hydroperoxide, di-t-butyl peroxide and/or t-butyl hydroperoxide, ethyl hexyl peroxydicarbonate, diisopropyl peroxy-dicarbonate, 4-(t-butylperoxylperoxycarbonyl)-3- hexyl-6-7-(t-butylperoxycarbonyl)hepti 1 cyclohexene (4-TBPCH), t-butyl peroxyneodecanoate and other organic peroxides sold by Elf Atochem North America, Inc., Philadelphia, Pennsylvania, under the names commercials for Lupersol, Luperco, Lucidol and Luperox; organic peracids such as peracetic acid; and petroleum and water soluble free radical producing agents such as azobis-dimethylvaleronitrile, 2,2'-azobisisobutyranitrile, azobis-methylbutyranitrile and others sold by DuPont, Wilmington, Del. under the trademark VAZO and Wako Pure Chemical Industries , Richmond, Va. under the trade name V-40 for V501; and the like, and mixtures thereof can also be used in combination with the water-soluble initiators. Preferred oil-soluble initiators are t-butyl peroxybenzoate, di-T-butyl peroxide, cumyl T-butyl peroxide, t-butyl peroxypivalate, lauryl peroxide, cumene hydroperoxide, ethyl hexyl peroxydicarbonate, peroxy -diisopropyldicarbonate, 4-(t-butylperoxylperoxycarbonyl)-3-hexyl-6-7-(t-butylperoxycarbonyl)heptylcyclohexene, cumene hydroperoxide and t-butylperoxyneodecanoate, hydroperoxide t-butyl, benzoyl peroxide, and combinations thereof.
Suitable reductants for the redox system include sulfur compounds such as, for example, the sodium salt of hydroxymethanesulfinic acid, a mixture of a disodium salt of 2-hydroxy-2-sulfinatoacetic acid and sodium sulfite, Briiggolit™ FF6 and FF7, sodium sulfite, sodium bisulfite, sodium thiosulfate, and acetone bisulfite adduct (registered trademarks of Brüggemann). A typical redox system may include, consist essentially of, or consist of, for example, sodium persulfate type oxidizers with sodium bisulfite type reductants such as Brüggolit™ FF6. In one embodiment, the reaction mixture is free of metal activators such as copper and the like.
[0054] The polymerization initiator should be present in an amount of less than about 5% mole based on the total amount of the monomers, such as from about 0.001 to about 5% mole, or 0.01 or 0.25 to about 4.95% mole, and up to about 0.1 to about 4.9% mole based on the total amount of the monomers. All or at least half of the initiator can be added separately from the itaconic acid monomer. In one embodiment, the initiator can be added continuously, essentially throughout the polymerization period. Initiator can also be added in discrete amounts at various times during the polymerization period. Preferably, from about 0.5 to about 25 or 50% by weight of the initiator charge is dissolved together with the itaconic acid in the aqueous medium and the remainder (i.e. 50% or 75% to 99.5% by weight ) of the initiator is then introduced, preferably as an aqueous solution, throughout the polymerization period or with (meth)acrylic acid and/or AMPS monomers. The concentration of initiator in the aqueous addition solution is usually about 0.5% to 10% by weight.
[0055] A bleaching agent can be used to improve the color of the polymer blend. Bleaching agents can include, for example, hydrogen peroxide, its derivatives, and addition products that release hydrogen peroxide.
[0056] The polymerization process may also include a peroxide cleaning agent to reduce and/or remove hydrogen peroxide residues from any bleaching agent that may have been used. Examples of peroxide cleaning agents may include peroxide cleaning enzymes and/or chemical reducing agents and/or heat processes that remove hydrogen peroxide. Peroxide cleaning enzymes refer to enzymes that can catalyze the conversion of hydrogen peroxide to water and oxygen, such as catalase (EC 1.11.1.6). Exemplary catalases include those derived from bacteria such as Bacillus, Pseudomonas strain or Streptomyces; yeasts such as Candida, Kluyveromyces, Pichia, Saccharomyces, Schizosaccharomyces or Yarrowia; fungi such as Acremonium, Aureobasidium, Aspergillus, Bjerkandera, Ceriporiopsis, Coprinus, Coriolus, Cryptococcus, Filibasidium, Fusarium, Humicola, Magnaporthe, Mucor, Myceliphthora, Neocallimastix, Neurospora, Paecilomyces, Penicillephyllium, Phoellium Talaromyces, Thermoascus, Thielavia, Tolypocladium, Trametes or Trichoderma strains; or from animals such as pork and beef liver. Non-limiting examples of suitable catalases are described in WO 92/17571, CN 1563373, US 2003100112-Al, EP-A 1336659, US 2003/074697, Pat. US No. 62011671 Pat. No. 6022721, EP 931831-A, JP 11046760-A, WO 93/17721, WO 93/09219, JP 1086879-A and/or JP 63003788-A. Non-limiting examples are T 100; Terminox™ Ultra 200L (Novazyme); Oxy-Gone 400 (GOD; Fermcolase 1000 (Mitsubishi Gas Chemical) or Thermocatalase CTL 200 or JH CT 1800 (Mitsubishi Gas Chemical) Depending on the catalase activity and the pH of the liquor used to apply the catalase, preferably the amount of catalase is used from 0.001 to 1 g / 1, especially about 5 g / 1 of liquor used to apply the catalase. Chemical reducing system refers to any chemical reducing agent(s) to remove the hydrogen peroxide by catalyzing the conversion of hydrogen peroxide to water and oxygen Examples of reducing agents include, for example, sodium thiosulfate, sodium bisulfite, sodium hydrosulfite and sodium hyposulfate, and the like.
[0057] Optionally, other polymerization additives and processing aids that are well known in the solution polymerization art, such as, chain transfer agents, solvents, emulsifiers, processing aids, antifoam agents, buffering agents, chelating agents , inorganic electrolytes, polymeric stabilizers, biocides, and pH adjusting agents can be included in the polymerization system.
[0058] Polymerization can be carried out in a variety of solvents such as alcohols, ethers, esters, aromatic solvents, glycols, glycerol, glycol ethers, and glycol esters. Preferred solvents include ethyl alcohol, isopropyl alcohol, t-butyl alcohol, ethyl acetate, methyl acetate, butyl acetate, benzene, toluene, and methylene chloride. These solvents can also be used in combination with hydrocarbon solvents such as hexane, cyclohexane, mineral spirits and the like. A preferred solvent is a mixture of isopropyl alcohol and water, or isopropyl alcohol, or water.
[0059] The polymerization temperature and duration of polymerization are influential in determining the nature of the resulting copolymer. Polymerization, therefore, can be limited to low temperatures of less than 80°C or 95°C, for example, from about 50°C to about 95°C, or from about 55°C to about 90°C. C, or from about 60°C to about 85°C, or even from about 60°C to about 80°C. This low temperature polymerization can be completed in an aqueous medium of water, alcohol, or a combination thereof.
[0060] In one embodiment, polymerization is carried out in water at a temperature greater than about 60°C. In another embodiment, the polymerization is carried out in a mixed solvent of water/alcohol (such as, for example, isopropyl alcohol) at a temperature greater than about 40°C, or 50°C or 60°C. In another embodiment, polymerization is carried out in water at a polymerization temperature of 99°C, or 95°C, or 90°C or less. In another embodiment, the polymerization is carried out in an alcohol solvent (such as, for example, isopropyl alcohol) at a temperature greater than 50°C or 55°C.
[0061] The presence of alcohol solvent can result in partial esterification of the acid groups so that the resulting copolymer comprises ester functionality. The percentage of acid groups in the copolymer that become esterified may depend, in part, on the temperature and pressure at which the polymerization is maintained. The resulting polymer or copolymer can be from about 0.1% to about 60% molar esterified, that is, from about 0.1% to about 60% of the total acid groups of all monomers in the polymer/copolymer are esterified. . The polymer or copolymer can also be from about 0.5%, or 1% to about 50% esterified, or from 1.5%, or 5%, or 10% to about 40% esterified. In some embodiments, the polymer or copolymer can be from about 0.1% to about 10% or 15% esterified. In some embodiments, the polymer/copolymer is essentially free or completely free of esterified acid groups.
[0062] The polymerization period can be maintained from about 2 to about 8 hours. The final polymerization solution is generally held at the polymerization temperature until the reaction is complete, after the completion of the initiator addition period and (meth)acrylic acid and/or AMPS comonomers.
[0063] By selecting the reaction parameters mentioned above within the specified ranges, homogeneous or substantially homogeneous polymers, or random or block copolymers and/or terpolymers, of itaconic acid, (meth)acrylic acid and/or AMPS, can be prepared with number average molecular weights (Mn) from about 500 to 100,000, preferably from about 1000 to 50,000, more preferably 1,000 to 10,000. In some embodiments, the polymer composition can have an Mn between about 100 or 150 and 500.
[0064] It is important to note, that improved polymers, e.g. homopolymers, copolymers and/or terpolymers, and the like, produced in accordance with the above-described process will be free or substantially free of tri-substituted vinyl monomeric isomer parts of itaconic acid, such as citraconic acid and mesaconic acid. In addition, the resulting polymer solution will include less than 0.5% w/w of unreacted monomer, based on the total weight of polymer present in the solution, or less than 0.25% w/w, or free or substantially free of monomer who did not react.
[0065] Furthermore, the polymer solution will be transparent or substantially transparent. The transparency of a solution can be measured in terms of the solution's turbidity; which is the cloudiness or turbidity of the solution. Turbidity is measured on a nephelometer in nephelometric turbidity unit ("NTU"). By transparent, it is understood that the solution has a turbidity of less than 5 NTUs. Substantially clear means that the polymer solution has a turbidity of between about 5 and 100 NTUs, or more preferably between 5 and 50 NTUs, 5 to 25 NTUs, or 5 to 15 NTUs.
[0066] Preferred embodiments of the present process include those in which from about 30% to 40% mole of acrylic acid is copolymerized with itaconic acid of about 60% to 70% mole. In a particularly preferred process, about 30 to 40 mol% acrylic acid, 1 to 2 mol% sodium persulfate and 1 to 2 mol% Brüggolit™ FF6 are added separately over a period of about 3 to 5 hours to an aqueous solution of about 60% to 70% molar itaconic acid at a temperature of between about 60°C to 80°C, and the polymerization solution is held at that temperature for a period additional 4 hours after addition.
[0067] Improved polymers may consist essentially of about 30 to 40 mol% of units derived from (meth)acrylic acid or AMPS, of about 60 to 70 mol% of units derived from itaconic acid, or may consist essentially of units derived from itaconic acid. in about 25% to 35% mole of (meth)acrylic acid, 5% to 15% mole of units derived from AMPS, and from about 50% to 60% mole of units derived from itaconic acid, and having a number of average molecular weight from about 500 to 100,000, preferably from about 1000 to 50,000, more preferably 1,000 to 10,000. The copolymer will normally be added to aqueous systems. The final polymerization solution, such as diluted or concentrated as desired, will generally be used without isolating the copolymer product.
[0068] Liquid polymers can also be dried using various drying techniques as known in the prior art [Handbook of Industrial Drying, by Arun S. Mujumdar, Third Edition, 2007]. Some polymer dryers used are rotary dryer, flash dryer, spray dryer, fluid bed dryer, fluid bed dryer, vibrating fluid bed dryer, contact fluid bed dryer, paddle dryer, plate dryer, plate dryer, spray granulation and spiral DRT dryer.
[0069] Evaluation of these improved polymers has shown them to be superior to prior art itaconic acid polymers.
[0070] The improved polymers, therefore, can be used in a process of chelation of hardness ions (eg chelating or sequestering metal ions, and the like) from a solution. The method may comprise adding a solution containing hardness ions, or something containing hardness ions, to the improved polymers or their solutions. Many applications in the personal care and home care industry are subject to liquids that contain hardness ions, eg hard water.
[0071] Hard water is water that has a high mineral content or "hardness ions" (in contrast to "soft water"). The most prevalent hardness ions are generally calcium and magnesium, but other hardness ions can include, for example, iron, aluminum, and manganese, and the like. The level of "hardness" can be measured, for example, using the sum of the total molar concentrations of hardness ions in the system, such as Ca2+ and Mg2+, in units of mol / L or mmol / L. Hardness can also be be measured in other units such as, for example ppm, where ppm can be defined in terms of the mineral content in water, such as, for example, 1 mg/L of CaCO3.
[0072] Thus, polymers or improved solutions thereof can be used as performance enhancing builders in detergents, for example, household cleaning products, water treatment products, automotive care, surface care, I&I care products and personal. Exemplary automotive care applications include, for example, car washes, car protectants, car cleaners, car shampoos, and the like.
[0073] The polymers of the present invention can be used in domestic, institutional and industrial ("I&I") care applications. Home care and R&I products that may contain polymers of the invention, include, but are not limited to, fabric care products, such as laundry detergents (powder, liquid, gel, and unit doses) and fabric softeners ( liquids or sheets), ironing sprays, dry cleaning aids, anti-wrinkle sprays, mark and stain removers, and the like; hard surface cleaners for kitchens and bathrooms, and utilities and appliances used or located therein, such as toilet gels, bath and shower cleaners, "hard water" deposit removers, floor and tile cleaners, wall cleaners, chrome and floor fixing polishes, vinyl floor cleaners, ceramic and marble cleaners, air freshening gels, liquid cleaners, gels, powders or unit doses (eg packaging) for dishes (automatically and manually), and the like; disinfectant cleaners such as toilet and bidet cleaners, disinfectant hand soaps, room deodorants, heavy duty hand cleaning soaps, cleaners and disinfectants, car cleaners, and the like.
[0074] In a preferred embodiment, the polymers or improved solutions thereof are used in detergents for automatic dishwashing. These detergents can be of different forms such as, for example, liquid, powder, gels, tablets and unit dose packs, bar, paste, hard or soft single layer tablet, hard or soft multi layer tablet, dose detergent single and single phase, multiphase single dose, comprising, for example, any combination of powders, granules, liquids and gel phases. In another embodiment, the improved polymers can be used in laundry detergents, either in liquid, powder, gel, tablets, and unit dose packs, bars, paste, hard or soft single layer tablet, layered tablet multiple hard or soft, single-dose and single-phase detergent, multi-phase single-dose comprising, for example, any combination of powder, granular, liquid and gel phases.
[0075] Illustrative water treatment applications include, for example, water purification processes for potable and industrial uses, cooling water treatment, heating water treatment, desalination (eg reverse osmosis, distillation), water treatment. wastewater (eg municipal and industrial), and the like. In a preferred embodiment, the improved polymers are used in water treatment applications as scale inhibitors and/or dispersants.
[0076] Exemplary deposit control applications, dispersion of suspended solids and scale, as applied to water treatment including fresh process water, and saline, include, for example, cooling water treatment, heating water treatment , reverse osmosis (RO) and thermal desalination, municipal and industrial wastewater exploration, geothermal exploration, oil and gas exploration and production, pulp and paper manufacturing, sugar refining, as well as mining processes. Examples of scale include calcium carbonate; calcium phosphates and phosphonates; calcium, barium, and strontium sulfates; magnesium hydroxide; calcium fluoride; calcium oxalates; silica; and silicates. In some cases, the improved polymers can be used as scale removal agents, rheology modifiers in drilling operations, as well as for slurry transport of suspended solids in water.
[0077] Examples of personal care cleansers include, but are not limited to, shampoos (eg, 2-in-1 shampoos, conditioners, "bodifying"-type shampoos; moisturizing shampoos, temporary coloring shampoos, 3-in-1 shampoos, dandruff shampoos, hair color maintenance shampoos, acid (neutralizing) shampoos, salicylic acid shampoos, medicinal shampoos, baby shampoos, and similar items), and skin and body care and cleansing shampoos (eg, liquid soaps moisturizers, antibacterial liquid soaps; shower gels, liquid hand soaps, bar soaps, body scrubs, soaps for bubble baths, facial scrubs, foot scrubs, and the like). Likewise, the improved polymer can be used in general animal care and pet care applications. Examples of general animal care and pet care products include, but are not limited to, shampoos, medicated shampoos, conditioners (eg, to ease detangling, antistatic, grooming), foaming shampoos.
[0078] There is no limitation on the type of product to which the improved polymers can be incorporated, as long as the purpose for which the product is used is achieved. For example, healthcare and personal care products containing the improved polymer can be applied to the skin, hair, scalp and nails in the form of, but not limited to, gels, sprays (liquid or foam), emulsions. (creams, lotions, pastes), liquids (creams, shampoos), bars, ointments, suppositories, impregnated plasters, adhesives, and the like. Likewise, while the improved polymers can be used alone, said improved polymers can be used in compositions with additional optional ingredients.
[0079] It is known that compositions formulated for personal care and topical, dermatological health care, which are applied to the skin and mucous membranes, for cleansing or soothing, are composed of many of the same, or similar, physiologically tolerable ingredients and formulated in the same or similar product forms, differing principally in the degree of purity of the selected ingredient, the presence of pharmaceutically acceptable drugs or compounds, and the controlled conditions under which the products may be manufactured. Likewise, many of the ingredients used in home care and R&I products are the same or similar to the preceding ones, differing mainly in the quantities and grades of material used. It is also known that the selection and permitted amount of ingredients may also be subject to government regulations at the national, regional, local and international levels. Thus, the present discussion of several useful ingredients listed below can be applied to personal care, healthcare products, household products and I & I products and industrial applications.
The choice and amount of ingredients in formulated compositions containing an improved polymer as described herein will vary depending on the product and its function, as is well known to those skilled in the art of formulation. Ingredient formulations typically may include, but are not limited to, natural and synthetic soaps, solvents, surfactants (such as cleaning agents, emulsifying agents, foam activators, hydrotropes, solubilizing agents, and suspending agents), non-suspending agents. surfactants, anti-redeposition aids, brighteners, fillers (eg, sodium carbonate, sodium sulfate, sodium silicate and the like), deflocculating agents, enzymes and enzyme stabilizers, radical scavenging agents, corrosion inhibitors, salts, emulsifiers , conditioning agents (emollients, humectants, moisturizers and the like), fixatives, film formers, protectants, pastes, builders, chelating agents, chelators, co-chelants, antimicrobial agents, antifungal agents, antidandruff agents, abrasives, transfer inhibitors of dyes, adhesives, absorbents, dyes, deodorizing agents, antiperspirants, fluorescence agents, opacifying and nacreating agents, antioxidants, preservatives, propellants, dispersing aids, dirt release agents, sunscreen agents, sunless skin tanning accelerators, ultraviolet light absorbers, pH adjusting agents, originating of plants, hair dyes, oxidizing agents, reducing agents, bleaching agents, pigments, physiologically active agents, ceramic and glass corrosion inhibitors, plastic care ingredients, anti-inflammatory agents, topical anesthetics, bactericides, fragrances and solubilizers of fragrances, and the like, in addition to previously discussed ingredients that may not appear here. An extensive list of substances and their conventional functions and product categories appears in the INCI dictionary generally and in Vol. 2, sections 4 and 5 of the seventh edition in particular, incorporated herein by reference.
[0081] Any cleaning ingredient, other than the builders, can be used as part of the detergent product of the invention. Levels are given in percent by weight and refer to the total composition (excluding the surrounding water-soluble material in the case of unit dose forms with a shell or surrounding material). The detergent composition can contain a phosphate filler or be free of phosphate builder and comprise one or more active detergent components that can be selected from bleaches, bleach activators, bleach catalysts, alkalinity sources, polymer, color aids , anti-corrosion agents (eg sodium silicate) and care agents. Particularly suitable cleaning components for use in the present invention include a builder compound, a bleach, a source of alkalinity, a surfactant, an antifouling polymer, for example a polymer, an enzyme and an additional bleaching agent. Surfactant
[0082] Surfactants are generally used as cleaning agents, emulsifying agents, foam activators, hydrotropes and rheology modification systems. The polymers of the present invention can be used in formulations that contain surfactant agents of all classes, that is, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants. The term "amphoteric surfactant" as used herein includes zwitterionic surfactants. In addition to the above references, discussions of surfactant classes are in Cosmetics & Toiletries™ C&T Ingredient Resource Series, "Surfactant Encyclopedia", 2nd Edition, Rieger (ed), Allured Publishing Corporation (1996); Schwartz, et al. , Surface Active Agents, Their Chemistry and Technology, published 1949; and Surface Active Agents and Detergents, Volume II, published 1958, Interscience Publishers; each incorporated herein by reference. Anionic Surfactant Detergents
[0083] Anionic surface agents that can be used in the present invention are surfactant compounds that contain a long-chain hydrocarbon hydrophobic group in their molecular structure, and a hydrophilic group, i.e., water solubilization group, such as a group carboxylate, sulfonate or sulfate group or its corresponding acid form. Anionic surfactants include alkali metal (eg sodium and potassium) and nitrogen based bases (eg monoamines and polyamines), water soluble higher alkyl aryl sulfonate salts, alkyl sulfonates, alkyl sulfates, and the polyether alkyl sulfates. They can also include fatty acid or fatty acid soaps. One of the preferred groups of monoanionic surfactants are alkali metal, ammonia or alkanolamine salts of higher alkylaryl sulfonates, and alkali metal, ammonia or alkanolamine salts of higher alkyl sulfates or the monoanionic polyamine salts. Preferred higher alkyl sulfates are those in which the alkyl groups contain from 8 to 26 carbon atoms, preferably 12 to 22 carbon atoms and more preferably 14 to 18 carbon atoms. The alkyl group in the alkylaryl sulfonate preferably contains 8 to 16 carbon atoms and more preferably 10 to 15 carbon atoms. A particularly preferred alkylaryl sulfonate is sodium, potassium or C10 to C16 ethanolamine benzene sulfonate, for example linear sodium dodecyl benzene sulfonate. Primary and secondary alkyl sulfates can be made by reacting long-chain olefins with bisulfites or sulfites, eg sodium bisulfite. Alkyl sulfonates can also be made by reacting normal long-chain paraffin hydrocarbons with sulfur dioxide and oxygen as described in U.S. Patent Nos. 2,503,280, 2,507,088, 3,372, 188, and 3,260,741 to obtain normal or secondary higher alkyl sulfates suitable for use as surfactant detergents.
[0084] The alkyl substituent is preferably linear, i.e. normal alkyl, however branched chain alkyl sulfonates can be used, although they are not as good with respect to biodegradability. The alkane, i.e. substituent alkyl, can be sulfonated or can be terminally attached, for example, to the 2-carbon atom of the chain, i.e. it can be a secondary sulfonate. It is understood in the art that the substituent can be attached to any carbon in the alkyl chain. Higher alkyl sulfonates can be used as the alkali metal salts such as sodium and potassium. Preferred salts are sodium salts. Preferred alkyl sulfonates are C10 to C18 primary normal alkyl sodium and potassium sulfonates with the C10 to C15 normal primary alkyl sulfonate salt being more preferred.
Mixtures of higher alkylbenzene sulphonates and higher alkyl sulphates can be used, as well as mixtures of higher alkylbenzene sulphonates and higher alkyl polyether sulphates.
[0086] The alkali metal or ethanolamine sulphate can be used in admixture with the alkylbenzene sulphonate in an amount of 0 to 70%, preferably 5 to 50% by weight.
The alkyl polyethoxy sulfates used in accordance with the present invention may be straight or branched chain alkyl, and contain lower alkoxy groups which may contain two or three carbon atoms. Normal higher alkyl polyether sulfates are preferred in that they have a greater degree of biodegradability than branched chain alkyl groups and the lower polyalkoxy groups are preferably ethoxy groups.
The preferred higher alkyl polyethoxy sulfates used in accordance with the present invention are represented by the formula: R1-O(CH2CH2O)p-SO3M, Wherein R1 is C8 to C20 alkyl, preferably C10 to C18 and most preferably C12 to C15; p is 1 to 8, preferably 2 to 6, and more preferably 2 to 4; and M is an alkali metal such as sodium and potassium, an ammonia cation or polyamine. Sodium and potassium salts, and polyamines are preferred.
A preferred alkyl polyethoxylated sulfate is the sodium salt of a C12 to C15 triethoxy alcohol sulfate having the formula: C12-15-O-(CH2CH2O)3-SO3Na
[0090] Examples of suitable alkyl ethoxy sulfates which can be used in accordance with the present invention are primary or normal C12 -C15 triethoxyalkyl sulfate, sodium salt; n-decyl dietoxy sulfate, sodium salt; primary diethoxyalkyl sulfate, ammonium salt; C12 primary triethoxyalkyl sulfate, sodium salt; C15 primary alkyl tetraethoxy sulfate, sodium salt; C14-15 normal primary alkyl mixed tetra- and triethoxy sulfate, sodium salt; stearyl pentaethoxy sulfate, sodium salt; and C10-18 normal primary triethoxyalkyl sulfate, potassium salt.
Normal alkyl ethoxy sulfates are readily biodegradable and are preferred. The lower alkyl polyalkoxy sulfates can be used in mixtures with one another and/or in mixtures with the higher alkylbenzenes, sulfonates, or alkyl sulfates discussed above.
The alkali metal higher alkyl polyethoxy sulfate can be used with the alkylbenzene sulfonate and/or with an alkyl sulfate, in an amount of 0 to 70%, preferably 5 to 50% and more preferably 5 to 20% by weight of the entire composition. Non-Ionic Surfactant
[0093] Nonionic surfactants that can be used with the invention, alone or in combination with other surfactants are described below.
[0094] As is well known, nonionic surfactants are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an aliphatic organic compound or hydrophobic alkyl aromatic compound with ethylene oxide (hydrophilic in nature ). Typical suitable nonionic surfactants are those disclosed in U.S. Patents 4,316,812 and 3,630,929.
[0095] Typically, nonionic surfactants are lipophilic polyalkoxylated, in which the desired hydrophilic-lipophilic balance is obtained from the addition of a hydrophilic polyalkoxy group to a lipophilic moiety. A preferred class of nonionic detergent are alkoxylated alkanols where the alkanol is from 9 to 20 carbon atoms, and where the number of moles of alkylene oxide (from 2 or 3 carbon atoms) is from 3 to 20. Of such materials, it is preferred to use those in which the alkanol is a fatty alcohol of 9 to 11 or 12 to 15 carbon atoms, and which contain 5 to 9 or 5 to 12 alkoxy groups per mol. Also preferred is paraffin-based alcohol (eg non-ionic from Huntsman or Sassol).
[0096] Examples of such compounds are those in which the alkanol is 10 to 15 carbon atoms and which contain about 5 to 12 ethylene oxide groups per mol, eg Neodol® 25-9 and Neodol® 23- 6.5, wherein the products are made by Shell Chemical Company, Inc. The first is a condensation product of a mixture of higher fatty alcohols having an average of about 12 to 15 carbon atoms, with about 9 moles of carbon oxide. ethylene and the latter is a corresponding mixture in which the carbon atom content of the higher fatty alcohol is 12 to 13, and the number of ethylene oxide groups present averages about 6.5. Higher alcohols are primary alkanols.
[0097] Another subclass of alkoxylated surfactants that can be used contain a more precise alkyl chain length than a distribution of the above-described alkoxylated surfactants. Typically these are referred to as narrow range alkoxylates. Examples of these include Neodol-1(R) series of surfactants manufactured by Shell Chemical Company.
[0098] Other useful nonionics are represented by the commercially well-known class of nonionics sold under the trademark Plu-rafacs® by BASF. Plurafacs® are the reaction products of a superior linear alcohol and a mixture of ethylene oxide and propylene, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples include C13-C15 fatty alcohol condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide, in C13-C15 fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide, C13-C15 fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide or mixtures of any of the above.
[0099] Another group of liquid nonionics are commercially available from Shell Chemical Company, Inc. under the trademark Neodol® or Dobanol®: Dobanol® 91-5 is a C9-C11 ethoxylated fatty alcohol with an average of 5 moles of Ethylene Oxide and Dobanol ® 25-7 is an ethoxylated C12-C15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
[00100] In the compositions of the present invention, preferred nonionic surfactants include the C12-C15 primary fatty alcohols with relatively narrow ethylene oxide content in the range of from about 6 to 9 moles, and the C9 to C11 ethoxylated fatty alcohols with about 5 to 6 moles of ethylene oxide.
[00101] Another class of nonionic surfactants that can be used in accordance with this invention are glycoside surfactants. Suitable secondary glycoside surfactants for use in accordance with the present invention include those of the formula: RO-(R2O)y-(Z)x wherein R is a monovalent organic radical containing from about 6 to about 30 (preferably from about from 8 to about 18) carbon atoms; R2 is a divalent hydrocarbon radical containing from about 2 to 4 carbon atoms; O is an oxygen atom; y is a number that can have an average value of from 0 to about 12, but is more preferably zero; Z is a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms; and x is a number with an average value of from 1 to about 10 (preferably, between about 1 1/2 to about 10).
[0100] A particularly preferred group of glycoside surfactants for use in the practice of the present invention include those of the above formula wherein R is a monovalent organic radical (linear or branched) containing from about 6 to about 18 (especially from about 8 to about 18) carbon atoms; y is zero; Z is a glucose moiety or derivatives thereof; x is a number with an average value of from 1 to about 4 (preferably from about 1 1/2 to 4). Nonionic surfactants that can be used include polyhydroxy amides, as discussed in US Patent No. 5,312,954 to Letton et al. and aldobionamides such as those described in U.S. Patent No. 5,389,279 to Au et al.
[0101] Generally speaking, nonionics comprising 0% to 75% by weight, preferably 5% to 50%, more preferably 5% to 25% by weight of the composition. Mixtures of two or more of the nonionic surfactants can be used.
[0102] Surfactants suitable for use in the present invention include non-ionic surfactants. Traditionally, non-ionic surfactants have been used in detergent compositions for surface modification purposes, in particular, to avoid skin and stains, and to improve gloss. It was found that non-ionic surfactants can also help to prevent dirt redeposition.
[0103] In one aspect, the detergent product of the present invention comprises a nonionic surfactant agent or a nonionic surfactant system, in one aspect the nonionic surfactant agent or a nonionic surfactant system having an inversion temperature of phase, as measured at a concentration of 1% in distilled water, between 40°C and 70°C, preferably between 45°C and 65°C. A "nonionic surfactant system" means a mixture of two or more nonionic surfactants. Nonionic surfactant systems are often especially useful as they appear to have better cleaning and finishing properties, and better product stability, than nonionic surfactants alone.
[0104] The phase inversion temperature is the temperature below which a surfactant, or a mixture thereof, preferentially partitions into the aqueous phase as oil swollen micelles, and above which it partitions preferentially into the oil phase as micelles water-swollen inverted inverts. The phase inversion temperature can be determined visually by identifying at which temperature cloudiness occurs.
[0105] The phase inversion temperature of a nonionic surfactant, or system, can be determined as follows: a solution containing 1% of surfactants or corresponding mixture, by weight, of the solution in distilled water is prepared. The solution is gently shaken prior to phase inversion temperature analysis to ensure the process occurs in chemical equilibrium. The phase inversion temperature is measured in a thermostable bath by immersing the solutions in a sealed 75 mm glass test tube. To ensure that there are no leaks, the test tube is weighed before and after measuring the phase inversion temperature. The temperature is gradually increased at a rate of less than 1°C per minute, until the temperature reaches a few degrees below the pre-calculated phase inversion temperature. The phase inversion temperature is determined visually at the first sign of turbidity.
[0106] Suitable nonionic surfactants include: i) ethoxylated nonionic surfactants prepared by reacting a monohydroxy alkanol or alkylphenol having 6 to 20 carbon atoms, typically having at least 12 moles, at least 16 moles, or even at least at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol; ii) alkoxylated alcohol surfactants having 6 to 20 carbon atoms and at least one ethoxy and propoxy group. In one aspect, the surfactant mixtures of i) and ii) are particularly useful.
[0107] Another class of suitable nonionic surfactants are the epoxy-capped poly(oxyalkylated) alcohols represented by the formula: R>0|CH2CH(CH3)0]x|CH2CH20]y|CH2CH(OH)R2| (i) wherein R1 is a straight or branched chain aliphatic hydrocarbon radical having 4 to 18 carbon atoms; R2 is a straight or branched chain aliphatic hydrocarbon radical having 2 to 26 carbon atoms; x is an integer that has an average value of 0.5 to 1.5, or about 1; and y is an integer that has a value of at least 15, or at least 20. In one aspect, in the surfactant of formula I, at least about 10 carbon atoms in the 2-terminal epoxide unit [CH2CH(OH)R] . Suitable surfactants of formula I in accordance with the present invention include POLi-TERGENT® SLF-18B nonionic surfactants from Olin Corporation, as described, for example, in USP 5766371 and USP 5576281. Surfactants and/or non-system ionics suitable for use as the anti-redeposition agents herein may have a Draves wetting time of less than 360 seconds, less than 200 seconds, less than 100 seconds, or less than 60 seconds, as measured by the Draves wetting method (method standard ISO 8022 using the following conditions; 3-g hook, 5-g cotton skein, 0.1% by weight aqueous solution at a temperature of 25°C). Low foaming non-ionic surfactants
[0108] The detergent compositions of the present application comprise low foaming nonionic surfactants (LFNIs). LFNI can be present in amounts from about 0.1% to about 2%. LFNIs are most commonly used in detergents due to the improved “water-sheeting” action (especially in glass) that detergents give.
[0109] Preferred LFNIs include specially ethoxylated nonionic alkoxylated surfactants derived from primary alcohols, and mixtures thereof with more sophisticated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) reverse block polymers. PO / EO / PO polymer-type surfactants are well known to have foam suppressing or anti-foaming action, especially in relation to ingredients common in food soils such as eggs.
[0110] In a preferred embodiment, LFNI is an ethoxylated surfactant derived from the reaction of a monohydroxy alcohol or alkylphenol containing from about 8 to about 20 carbon atoms, excluding cyclic carbon atoms, with about 6 to about 15 moles of ethylene oxide per mole of alcohol or alkylphenol on an average basis.
[0111] The improved polymers of the present invention are particularly useful for water-based formulations, water-free formulations, powders, and formulations that contain water miscible auxiliary solvents, but are not limited thereto. Useful solvents typically used are typically liquids, such as water (deionized, distilled or purified), alcohols, polyols and the like, and mixtures thereof. Non-aqueous or hydrophobic auxiliary solvents are commonly used in substantially water-free products, such as propellant aerosol sprays, automotive and household surface cleaners, or for specific functions such as removing oily soils, tallow, stain, or dissolving dyes , fragrances, and the like, or are incorporated into the oil phase of an emulsion. Non-limiting examples of auxiliary solvents, other than water, include, linear and branched alcohols such as ethanol, propanol, isopropanol, hexanol, and the like; aromatic alcohols such as benzyl alcohol, cyclohexanol, and the like; C12-C30 saturated fatty alcohol, such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, and the like. Non-limiting examples of polyols include polyhydroxy alcohols such as glycerine, propylene glycol, butylene glycol, hexylene glycol, C2-C4 alkoxylated alcohols, and C2C4 alkoxylated polyols such as ethoxylated ethers, propoxylates, butoxylated alcohols with some alcohols, from 2 to about 30 carbon atoms and 1 to about 40 alkoxy units, polypropylene glycol, polybutylene glycol, and the like. Non-limiting examples of non-aqueous auxiliary solvents include silicones and silicone derivatives such as cyclomethicone and the like; ketones such as acetone and methyl ethyl ketone; natural and synthetic oils and waxes, such as vegetable oils, plant oils, animal oils, essential oils, mineral oils, C7-C40 isoparaffins, alkyl carboxylic esters, such as ethyl acetate, amyl acetate, ethyl lactate, and the likes, jojoba oil, shark liver oil and the like. Some of the above non-aqueous auxiliary solvents may also be diluents, solubilizers, emulsifiers and conditioners.
[0112] A particularly preferred LFNI is derived from a straight chain fatty alcohol containing from about 16 to about 20 carbon atoms (C16-C20 alcohol), preferably a C18 alcohol, condensed with an average of about 6 to about 15 moles, preferably from about 7 to about 12 moles, and more preferably from about 7 to about 9 moles of ethylene oxide per mole of alcohol. Preferably, the ethoxylated nonionic surfactant thus derived has a narrow ethoxylate distribution relative to the mean.
[0113] LFNI may optionally contain propylene oxide in an amount up to about 15% by weight. Some of the block polymer surfactant compounds designated PLURONIC® and TETRONIC® by BASF-Wyandotte Corp., Wyandotte, Mich., are suitable for the automatic gel detergents of the invention. Highly preferred automatic gel detergents present herein, wherein LFNI is present, make use of ethoxylated monohydroxy alcohol or alkylphenol, and additionally comprise a block polymeric compound of polyoxyethylene, polyoxypropylene; the ethoxylated monohydroxy alcohol or alkylphenol moiety of LFNI contains from about 20% to about 80%, preferably from about 30% to about 70%, of the total LFNI.
[0114] LFNIs that may also be used include a C18 polyethoxylated alcohol which has a degree of ethoxylation of about 8, SLF18 commercially available from Olin Corp.
[0115] The formulations may comprise low foaming nonionic surfactants. Paraffin oils and silicone oils can, where appropriate, be used as anti-foaming agents and to protect metal and plastic surfaces. Defoamers are generally used in proportions of from 0.001% by weight to 20% by weight, preferably from 0.1 to 15% by weight, and more preferably from 0.25 to 10% by weight. Cationic Surfactants
[0116] Many cationic surfactants are known in the art, and almost any cationic surfactant that has at least one long chain alkyl group of about 10 to 24 carbon atoms is suitable in the present invention. Such compounds are described in "Cationic Surfactants", Jungermann, 1970.
[0117] Specific cationic surfactants that can be used as the surfactants of the present invention are described in detail in US Patent No. 4,497,718.
[0118] As with nonionic and anionic surfactants, the compositions of the invention can use cationic surfactants alone or in combination with any of the other surfactants known in the art. Of course, the compositions may contain no cationic surfactants. Amphoteric Surfactants
[0119] Synthetic ampholytic surfactants can be broadly described as aliphatic derivatives or aliphatic derivatives of secondary and tertiary heterocyclic amines, in which the aliphatic radical can be straight-chain or branched, and in which one of the aliphatic substituents contains about 8 to 18 atoms of carbon and at least one contains a water-soluble anionic group, eg carboxylate, sulphonate, sulphate. Examples of compounds that fall within this definition are sodium 3-(dodecylamine) propionate, sodium 3-(dodecylamine) propane-1-sulfonate, sodium 2-(dodecylamine) ethyl sulfate, sodium 2-(dimethylamine) octadecanoate, Disodium 3-(N-carboxymethyldodecylamine) propane 1-sulfonate, disodium octadecyl-iminediacetate, sodium 1-carboxymethyl-2-undecylimidazole and sodium N,N-bis(2-hydroxyethyl)-2-sulfate-3-dodecoxypropylamine. Sodium 3-(dodecylamine)propane-1-sulfonate is preferred.
[0120] Zuiterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. The cationic atom in the quaternary compound may be part of a heterocyclic ring. In all of these compounds there is at least one aliphatic group, straight-chain or branched, containing from about 3 to 18 carbon atoms and at least one aliphatic substituent which contains a water-soluble anionic group, e.g., carboxy, sulfonate, sulfate , phosphate, or phosphonate.
[0121] Specific examples of zwitterionic surfactants that can be used are set forth in U.S. Patent No. 4,062,647.
[0122] The amount of additional surfactant used may range from 1% to 85% by weight, preferably 10% to 50% by weight.
[0123] As noted, the preferred surfactant systems of the invention are mixtures of anionic and nonionic surfactants.
[0124] Preferably, the nonionic should comprise, as a percentage of a nonionic/anionic system, at least 20%, more preferably, at least 25%, up to about 75% of the total surfactant system. Amine Oxide
[0125] Amine oxide surfactants are also useful in the present invention and include linear and branched compounds having the formula: O"I R3(OR4)x N+(R5)2 wherein R3 is selected from an alkyl group, hydroxyalkyl, acylamidepropyl and phenylalkyl, or mixtures thereof, containing from 8 to 26 carbon atoms, or between 8 and 18 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or 2 carbon atoms, or mixtures thereof; x is from 0 to 5, or from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group containing 1 to 3, or 1 to 2 carbon atoms, or a polyethylene oxide group containing 1 to 3 , or even 1, ethylene oxide group.The R5 groups may be linked together, for example, through an oxygen or nitrogen atom, to form a ring structure.
[0126] These amine oxide surfactants, in particular, include C18 dimethylalkylamine oxides and C8-C14 alkoxy ethyl dihydroxyethylamine oxides. Examples of such materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl) dodecylamine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dodecylamidepropyl dimethylamine oxide, dimethyl dimethylamine oxide, dimethyl stearyl oxide , tallow dimethylamine oxide, and dimethyl-2-hydroxyoctadecylamine oxide. In one aspect, C10-C18-dimethylalkylamine oxide, and C10-C18 acylamidealkyl dimethylamine oxide are used. Enzymes
[0127] As used herein, enzyme means any enzyme that has a beneficial cleaning, stain removal or other beneficial effect in a detergent composition. Preferred enzymes are hydrolases, such as proteases, amylases and lipases. Highly preferred for dishwashing are amylases and/or proteases, including both the current commercially available types and the improved types. Enzymes are normally incorporated into detergent compositions at instantaneous levels sufficient to provide an "effective amount of cleaning". The term "cleaning effective amount" refers to any amount capable of producing a cleaning, stain removing or soiling effect on substrates such as cutlery.
The compositions of this invention may comprise: from about 0.001% to about 20%, preferably from about 0.005% to about 10%, more preferably from about 0.01% to about 6%, in weight, of an enzyme stabilization system. Proteases
[0129] In the automatic dishwashing detergent composition of the invention a mixture of two or more proteases can be used. A blend of proteases can contribute to improved cleaning across a wider temperature and/or substrate range, and provide superior gloss benefits, especially when used in conjunction with the improved polymer.
[0130] Suitable proteases for use in association with the variant protease of the invention 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, vegetable or microbial origin. Microbial origin is preferred. Chemically or genetically modified mutants are included. The protease may be a serine protease, in one aspect an alkaline microbial protease or a chymotrypsin or trypsin-like protease. Examples of neutral or alkaline proteases include: (a) subtilisins (EC 3.4.2 1.62), especially those derived from Bacillus, such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amylolique-faciens, Bacillus pumilus and Bacillus gibsonii described in US 6,312,936 B 1 , US 5,679,630 , US 4,760,025 , and USPA 2009 / 0170745A1 . (b) trypsin or chymotrypsin-like proteases, such as trypsin (e.g., of porcine or bovine origin), the Fusarium protease described in USP 5,288,627 and the cellumonas-derived chymotrypsin proteases described in USPA 2008 / 0063774A1. (c) metalloproteases, especially those derived from Bacillus amyloliquefaciens described in USPA 2009/0263882 A1 and USPA 2008/0293610A1. Suitable commercially available protease enzymes include those sold under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Ovozyme®, Neutrase®, Everlase® and Esperase® by Novozymes A/S (Denmark), those sold under the trade names Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect OX®, FN3®, FN4®, Excellase® and Purafect OXP® by Genencor International (now Danisco US Inc.), and those sold under the trade name 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 + S 103A + V104I + G159S, hereinafter referred to as 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 from Henkel / Kemira; and KAP (Bacillus alkalophilus subtilisin with A230V + S256G + S259N mutations) from Kao. In one aspect, commercial proteases selected from the group consisting of Properase®, Purafect®, Ovozyme®, Everlase®, Savinase®, FN3® and Excellase® are used. Amylases
[0131] Amylase enzymes are additional enzymes that are useful in detergent compositions. Suitable amylases include those described in USPA 2009/0233831 A1 and USPA 2009 / 0314286A1. Suitable commercially available amylases for use herein include STAINZYME®, STAINZYME PLUS®, STAINZYME ULTRA® and NATALASE® (Novozymes A/S) and Spezyme Xtra™ and Powerase™. STAINZYME PLUS® and Powerase™ can be particularly helpful. Cellulases
[0132] In one aspect, the detergent composition of the present invention comprises a cellulase enzyme. This composition provides excellent results not only in terms of cleaning fabric, cutlery and other utensils, but also in terms of cleaning machines such as dishwashers.
[0133] Cellulase enzymes include endoglucanases derived from microbes that exhibit endo-beta-1,4-glucanase activities (EC 3.2.1 0.4), including an endogenous bacterial polypeptide for a member of the genus Bacillus that has a hair sequence less than 90%, 94%, 97% and even 99% identity with the amino acid sequence SEQ ID NO: 2 in US 7,141,403B2) and mixtures thereof. Suitable commercially available cellulases for the uses described herein include Celluzyme®, Celluclean®, Whitezyme® (Novozymes A/S) and Puradax HA® (Genencor International - now Danisco US Inc.). Other additional enzymes
[0134] Other additional enzymes suitable for use in the detergent composition of the present invention may comprise one or more enzymes selected from the group comprising hemicellulases, cellobiose dehydrogenases, peroxidases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, lyases pectate, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase and mixtures thereof.
[0135] In one aspect, this additional enzyme can be selected from the group consisting of lipases, including "first cycle lipases" which comprise a substitution of an electrically neutral or negatively charged amino acid with R or K, in any of the positions 3, 224, 229, 231 and 233 in the wild type of Humicola lanuginosa, the sequence of which is shown as SEQ ID No 1 on pages 5 and 6 of US Patent 6,939,702, B1, in one aspect, a variant comprising mutations T231R and N233R. One such variant is sold under the trade name Lipex® (NovoZymes A/S, Bagsvaerd, Denmark). Enzyme Stabilizer Components
[0136] Suitable enzyme stabilizers include oligosaccharides, polysaccharides and their inorganic divalent metal salts, such as alkaline earth metal salts, especially calcium salts. Chlorides and sulfates may be particularly suitable with calcium chloride, in one aspect, being an especially suitable calcium salt. Examples of suitable oligosaccharides and polysaccharides, such as dextrins, can be found in USPA 2008/0004201 Al. In the case of aqueous compositions comprising protease, a reversible protease inhibitor, such as a boron compound, including borate and 4-formyl acid phenyl boronic or a tripeptide aldehyde can be added to further improve stability.
[0137] The purpose of an enzyme stabilization system is to protect the enzymes in the composition between the time the composition is manufactured and the time the composition is used. It is preferred that the enzyme activity is maintained between about 60% and 100%, more preferably between about 70% and 100%, most preferably between about 80% and 100%. In one embodiment, the stabilized enzyme is a protease and the enzyme's activity is that of said protease.
[0138] The enzyme stabilization system can be any stabilization system that can be compatible with the detersive enzyme and the xanthan gum thickener - thus excluding boric acid, borax (sodium tetraborate decahydrate) and alkali metal borates . These stabilizer systems can comprise calcium ion, glycerin, propylene glycol, short chain carboxylic acid, and mixtures thereof. whiteners
[0139] Inorganic and organic bleaches are cleaning assets suitable for use in the present invention. Inorganic bleaches include perhydrate salts such as perborate, percarbonate, perphosphate, persulfate and persilicate salts. Inorganic perhydrate salts are usually the alkali metal salts. The inorganic perhydrate salt can be included as the crystalline solid, without further protection. Alternatively, the salt can be coated. Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates for use in the present invention. The percarbonate is most preferably incorporated into the products in a coated form which provides stability to the product. A suitable coating material that provides product stability comprises a mixed salt of a water-soluble alkali metal sulfate and carbonate. Such coatings along with coating processes have previously been described in US 4,105,827. The weight ratio of mixed salt coating material to percarbonate is in the range of 1:200 to 1:4, from 1:99 to 1:9, or from 1:49 to 1:19. In one aspect, the mixed salt is sodium sulfate and sodium carbonate which has the general formula Na2SO4.n.Na2CO3 where n is from 0.1 to 3, from 0.2 to 1.0 or from 0 .2 to 0.5. Another suitable coating material that provides product stability comprises sodium silicate of SiO2:Na2O ratio of 1.8:1 to 3.0:1, or 1.8:1 to 2.4:1, and/or metasilicate of sodium, in one aspect, applied at a level of 2% to 10%, (usually 3% to 5%) of SiO2 by weight of the inorganic perhydrate salt. Magnesium silicate can also be included in the coating. Coatings which contain silicate and borate salts, or boric or other inorganic acids, are also suitable.
[0140] Other coatings that contain waxes, oils, fatty soaps can also be used to advantage within the present invention.
[0141] Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility in the present invention.
[0142] Typical organic bleaches are organic peroxy acids, including tetracylperoxides and diacyl, especially diperoxydodecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecaoedioic acid. Dibenzoyl peroxide is a preferred organic peroxyacid herein. Mono- and diperbrasilic acid, mono- and diperazelaic acid, and Nphthaloylamine peroxycaproic acid are also suitable herein.
[0143] Diacyl peroxide, especially dibenzoyl peroxide, should typically be present in the form of particles with a weight average diameter of from about 0.1 to about 100 microns, from about 0.5 to about 30 microns, or from about 1 to about 10 microns. In one aspect, at least about 25%, at least about 50%, at least about 75%, or at least about 90%, of the particles are smaller than 10 microns, or smaller than 6 microns. Diacyl peroxides within the above particle size range have also been found to provide better stain removal, especially from plastic tableware, while minimizing unwanted deposition and filming during use in automatic dishwashers, than larger particles of diacyl peroxide. The better particle size diacyl peroxide thus allows the formulator to achieve good stain removal with a low level of diacyl peroxide, which reduces deposition and filming.
[0144] More typical organic bleaches include peroxy acids, specific examples being alkylperoxy acids and arylperoxy acids. Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives such as alkylperoxybenzoic acids, but also peroxy-a-naphthoic acid and magnesium monoperphthalate, (b) aliphatic or substituted aliphatic peroxy acids such as peroxylauryl acid, acid peroxystearic acid, ε-phthalimideperoxycaproic acid [hthaloimineperoxyhexanoic acid (PAP)], O-carboxybenzamidoperoxycaproic acid, N-nonenylamide peradipic acid and N-nonenylamidepersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1-diperoxycarboxylic acid 1, , 9-diperoxyazelaic, diperoxysebacic acid, diperoxybrasilic acid, diperoxyphthalic acids, 2-decyldiperoxybutane 1,4-dioic acid, N,N-terephthaloyldi (6-amine-percaproic acid).
[0145] The formulations may comprise bleaching agents and bleach activators, if appropriate. Bleachs are subdivided into oxygen bleaches and chlorine bleaches. Use as oxygen bleach is found for alkali metal perborates and their hydrates, and also alkali metal percarbonates. Preferred bleaches in this context are sodium perborate, in the form of the tetra- or monohydrate, sodium percarbonate or sodium percarbonate hydrates. Likewise, usable as oxygen bleaches are hydrogen peroxides and persulfate. Typical oxygen bleaches are also organic peracids, such as perbenzoic acid, peroxy-alpha-naphthoic acid, peroxylauryl acid, peroxystearic acid, phthalimidoperoxycaproic acid, 1,12-diperoxidodecanedioic acid, 1,9-diperoxyazelaic acid, or diperoxyphthalic acid or acid 2 -decyldiperoxybutane-1,4-dioic. In addition, for example, the following oxygen bleaches may also find use in detergent formulation: cationic peroxyacids which are described in US Pat. No. 5,422,028, No. 5,294,362 and No. 5,292,447; sulfonylperoxy acids which are described in US Pat. No. 5,039,447. Oxygen bleaches are used in amounts of generally 0.5 to 30% by weight, preferably 1 to 20% by weight, more preferably 3 to 15% by weight, based on the general detergent formulation. Likewise, chlorine bleaches and the combination of chlorine bleaches and peroxide bleaches can be used. Known chlorine bleaches are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, dichloramine T, chloramine B, N,N'-dichlorobenzoylurea, dichloro-p-toluene-sulfonamide or trichloroethylamine. Preferred chlorine bleaches are sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, magnesium hypochlorite, potassium or sodium dichloroisocyanurate. Chlorine bleaches are used in amounts of generally from 0.1 to 20% by weight, preferably from 0.2 to 10% by weight, more preferably from 0.3 to 8% by weight, based on the formulation. of detergent in general. Furthermore, small amounts of bleach stabilizers, for example phosphonates, borates, metaborates, metasilicates or magnesium salts, can be added. They are described in U.S.Pat. No. 8,262,804.
[0146] Although any chlorine bleach compound can be used in the compositions of this invention, such as, dichloroisocyanurate, dichloro-dimethyl hydantoin, or chlorinated TSP, alkali metal or alkaline earth metal, for example, potassium, lithium, magnesium and especially sodium , hypochlorite is preferred. The composition should contain a sufficient amount of chlorine bleach compound to provide 0.2 to 4.0% by weight of available chlorine, as determined, for example, by acidifying 100 parts of the composition with excess hydrochloric acid. A solution containing 0.2 to 4.0% by weight of sodium hypochlorite contains or provides nearly the same percentage of available chlorine. 0.8 to 1.6% by weight of available chlorine is especially preferred. For example, sodium hypochlorite (NaOCl) solution from 11 to 13% of available chlorine in amounts of 3 to 20%, preferably 7 to 12%, can be used to advantage. bleach activators
[0147] Bleach activators are normally precursors of organic peracids which enhance the bleaching action in the course of cleaning at temperatures of 60°C and below. Bleach activators suitable for use in the present invention include compounds which, under perhydrolysis conditions, generate aliphatic peroxycarboxylic acids having 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally perbenzoic acid substituted. Suitable substances carry O-acyl groups and/or N-acyl groups of the specified number of carbon atoms and/or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular, tetracetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahodro-1,3,5-triazine (DADHT), acylated glycoluril, in particular , tetracetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular, n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or isoNOBS), carboxylic anhydrides, in particular phthalic anhydride, polyalcohols -acylated hydrics, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran, and also triethylacetyl citrate (TEAC). Bleach activators, if included in the automatic dishwashing detergent compositions of the invention are at a level of from about 0.1% to about 10%, or from about 0.5% to about 2% by weight. , of the total composition. Bleaching Catalyst
[0148] Preferred bleach catalysts for use in the present invention include manganese triazacyclononane and related complexes (US-6602441, US-7205267, US-A-5227084); Co, Cu, Mn and Fe bispyridylamine complexes and related complexes (US-A-5114611); and cobalt(III) pentamine acetate and related complexes (US-A-4810410). A full description of bleach catalysts suitable for use in the present invention can be found in USP 6,599,871, pages 34, line 26 to page 40, line 16. Bleaching catalysts if included in the detergent compositions of the invention are at a level of from about 0.1% to about 10%, or from about 0.5% to about 2% by weight, of the total composition. builders
[0149] In addition to polymers improved as a primary builder, other co-builders are suitable to be included in the compositions of this invention to help control mineral stiffness and dispersibility, with the exception of phosphate builders. Inorganic builders as well as organic ones can be used. One embodiment of the present invention relates to a gel detergent composition, wherein the builder may be selected from the group consisting of carbonate builders, polycarboxylate compounds, citrate, methyl glycine diacetic acid and/or its glutamic salts, acids and/or diacetic salts thereof and mixtures thereof.
[0150] Examples of carbonate builders are alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published November 15, 1973. The various grades and types of sodium carbonate and sesquicarbonate sodium can be used, some of which are particularly useful as carriers for other ingredients, especially: detersive surfactants.
[0151] Suitable organic detergent builders for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
[0152] Preferred phosphate builders include monophosphates, diphosphates, tri- or polyphosphates or oligomeric polyphosphates are used. The alkali metal salts of these compounds are preferred, in particular the sodium salts. An especially preferred builder is sodium tripolyphosphate (STPP).
[0153] Other useful detergency builders include hydroxypolycarboxylate ether, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3,5-trihydroxy-benzene-2, 4, 6-trisulfonic acid, and carboxymethyloxysuccinic acid, the various alkali metals I, ammonia and substituted ammonia salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilatriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and its soluble salts.
[0154] Citrate builders, for example, citric acid and its soluble salts (particularly sodium salt), are suitable builders present here, due to their availability from renewable resources and their biodegradability.
[0155] Methylglycinediacetic acid (MGDA) and/or its salts can also be used as builders in the present composition. A preferred MGDA compound is a salt of glycinediacetic acid. Suitable salts include the diammonium salt, the dipotassium salt and preferably the disodium salt.
[0156] Glutamic diacetic acid and / or its salts (GLDA) can also be used as builders in the present composition. A preferred GLDA compound is a glutamic diacetic acid salt. Suitable salts include the diammonium salt, the dipotassium salt and preferably the disodium salt.
[0157] Chelating Agents - The compositions of this invention may also optionally contain one or more selective transition metal sequestrants, "chelants" or "co-chelating agents", e.g. iron and/or copper and/or chelating agents of manganese. Chelating agents suitable for use in the present invention can be selected from the group consisting of aminocarboxylates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof. Commercial chelating agents for use in the invention include the BEQUEST™ series, and chelating agents from Monsanto, DuPont and Nalco, Inc.
[0158] The formulations can comprise other co-builders. It is possible to use both water-soluble and water-insoluble builders, whose main task is to bind calcium and magnesium. The other adjuvants used can be, for example: low molecular weight carboxylic acids, and their salts, such as alkali metal citrates, in particular anhydrous trisodium citrate or trisodium citrate dihydrate, alkali metal succinates, malonates of alkali metals, fatty acid sulfonates, oxydisuccinate, alkyl or alkenyl disuccinates, gluconic acids, oxadiacetates, carboxymethyloxysuccinates, monosuccinate tartrate, disuccinate tartrate, monoacetate tartrate, diacetate tartrate, alpha.hydroxypropionic acid; oxidized starches, oxidized polysaccharides; polycarboxylic homo- and copolymeric acids and their salts, such as polyacrylic acid, polymethacrylic acid, copolymers of maleic acid and acrylic acid; graft polymers of mono- and/or dicarboxylic acids monoethylenically unsaturated monosaccharides, oligosaccharides, polysaccharides or polyaspartic acid; aminopolycarboxylates and polyaspartic acid; phosphonates, such as 2-phosphono-1, 2,4-butanetricarboxylic acid, aminotri-(methylenephosphonic acid), 1-hydroxyethylene (l,1-diphosphonic acid), ethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid or diethylenetriaminepentamethylenephosphonic acid; silicates such as sodium disilicate and sodium metasilicate; water-insoluble builders such as zeolites and crystalline silicates in sheets.
[0159] In addition, the formulations may contain one or more complexing agents. Preferred complexing agents are selected from the group consisting of nitrilatriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentacetic acid, diethylenediaminetriacetic acid, hydroxyethylethylenediaminetriacetic acid, and methylglycinediacetic acid, diacetic acid, glutamic acid, iminadisuccinic acid, diacetic acid, diacetic acid aspartic acid, and its salts.
[0160] A class of optional compounds for use in this invention includes chelating agents or mixtures thereof, in combination with the improved polymers of the invention. Chelating agents can be incorporated into the compositions of this invention in amounts ranging from 0.0% to 10.0% by weight of the total composition, preferably from 0.01% to 5.0%.
[0161] Phosphonate chelating agents suitable for use in this invention may include an alkali metal 1-hydroxy ethane diphosphonate (HEDP), poly alkylene (alkylene phosphonate), as well as amine phosphonate compounds, including aminatri (methylene phosphonic acid) (ATMP), trimethylene nitrile phosphonates (NTP), tetra methylene ethylene diamine phosphonates, and penta methylene diethylene triamine phosphonates (DTPMP). The phosphonate compounds can be present in their acidic form or as salts of different cations in some or all of their acidic functionalities. Preferred phosphonate chelating agents to be used herein are diethylene triamine pentamethylene phosphonates (DTPMP) and 1-hydroxy ethane diphosphonates (HEDP). Such phosphonate chelating agents are commercially available from Italmach Chemicals under the tradename DEQUEST™.
Polyfunctionally substituted aromatic chelating agents may also be useful in the compositions of this invention. See U.S. Pat No. 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
[0163] Co-builders for use in the present invention include phosphate builders and free phosphate builders. If present, builders are used at a level of from 5% to 60%, from 10% to 50%, or even between 10% and 50% by weight of the detergent composition. In some embodiments, the detergent product comprises a mixture of phosphate and non-phosphate builders. Drying Aids
[0164] In another embodiment, the detergent composition according to the invention comprises a drying aid. By "drying aid" is meant herein an agent capable of decreasing the amount of water left in washed articles, in particular plastic articles which are more prone to getting wet after the washing process, due to their hydrophobic nature. Suitable drying aids include polyesters, especially anionic polyesters derived from terephthalic acid, 5-sulfoisophthalic acid or a salt of 5-sulfoisophthalic, ethylene glycol or polyethylene glycol, polypropylene glycol or propylene glycol, and polyalkylene glycol monoalkyl ethers, optionally together with other monomers with 3 to 6 functionalities that are favorable to polycondensation, specifically acid, alcohol or ester functionalities. Polyesters suitable for use as drying aids are disclosed in WO 2008/110816, and preferably have one or more of the following properties: (a) a number average molecular weight of from about 800 Da to about 25,000 Da , or from about 1,200 Da to about 12,000 Da. (b) a softening point greater than about 40°C from about 41°C to about 200°C, or even 80°C to about 150 °C; (c) a solubility of greater than about 6% by weight in German 3° water at 200°C.
[0165] At 30°C, the solubility will typically be greater than about 8% by weight, at 40°C and 50°C, the solubility will typically be greater than about 40% per measurement in 3°German water.
[0166] Other suitable drying aids include specific polycarbonate-, polyurethane- and/or polyurea polyorganosiloxane compounds or their urea-type reactive cyclic carbonate precursor compounds, as described in USPA 2010/0041574 Al and USPA 2010/0022427 Al Improved drying can also be achieved by using nonionic surfactants such as: (a) Ri0-[CH2CH(CH3)0]x[CH2CH20]y[CH2CH(CH3)0]zCH2CH(OH)- R2 R1 represents a straight or branched chain aliphatic hydrocarbon having from 4 to 22 carbon atoms or mixtures thereof and R represents a straight or branched hydrocarbon having from 2 to 26 carbon atoms or mixtures thereof, x and z represent integer numbers of 0 to 40, ey represents an integer from at least 15, or from 15 to 50. See, for example, such as WO 2009/033972; or (b) RO-[CHCH(R')0]i|CH2CH20]m|CH2CH(R1)0|„C(0)-R2, where R is a branched or unbranched alkyl radical having from 8 to 16 atoms of carbon, Ra and R1 independently of one another are hydrogen or a branched or unbranched alkyl radical having from 1 to 5 carbon atoms, R2 is an unbranched alkyl radical having from 5 to 17 carbon atoms; 1 and n are independently of one another an integer from 1 to 5, and m is an integer from 13 to 35, as described in USPA 2008/016721.
[0167] Examples of suitable materials include Plurafac LF731 or Plurafac LF-7319 (BASF) and the Dehy quart® CSP and poly quart® (Cognis).
[0168] In one aspect, the detergent composition of the present invention comprises from about 0.1% to about 10%, from about 0.5% to about 5% and especially from about 1% to about 4% by weight of the composition of a drying aid. Rheology Systems
[0169] Various homopolymers, copolymers and carboxyvinyl polymers which are commercially available from Lubrizol Advanced Materials Inc. Cleveland, Ohio, under the trade name CARBOPOL® are suitable. These polymers are also known as carbomers or polyacrylic acids. Carboxyvinyl polymers useful in the formulations of the present invention include CARBOPOL® 941 having a molecular weight of about 1.250,000, and CARBOPOL 934, 940, 676, 674, having molecular weights of about 3,000,000 and 4,000,000, respectively. The CARBOPOL® series which uses ethyl acetate and cyclohexane in the manufacturing process is also useful, including but not limited to, for example, CARBOPOL® 690, 691, ETD 2691, ETD 2623, EZ-2, EZ-3 , and EZ-4.
[0170] The composition may also comprise a soluble silicate or an associative thickener to solve any texture problems that may arise with the use of a xanthan gum thickening agent. Semi-synthetic thickeners such as cellulosic type thickeners: hydroxyethyl and hydroxymethyl cellulose (ETHOCEL® and METHOCEL® available from Dow Chemical) can also be used. Mixtures of inorganic clays (eg, aluminum silicate, bentonite, fumed colloidal silica) are also suitable for use as a thickener referred to herein. The preferred clay thickening agent can be naturally occurring or synthetic. A suitable synthetic clay is that described in US 3,843,598. Natural clays include some attapulgite and smectite clays as described in U.S. 4,824,590.
[0171] Polysaccharide polymers suitable for use in the present invention include substituted cellulosic materials such as carboxymethylcellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxymethyl cellulose, polysaccharide polymers that occur naturally and succinoglycan such as xanthan gum, gellan gum, guar gum, locust bean gum, tragacanth gum, succinoglucan gum, or derivatives thereof, or mixtures thereof. Xanthan gum is commercially available from Kelco under the trade name Kelzan T™.
[0172] Rheology modifiers and thickeners may be present at levels between 0.1% and 5% by weight of the total composition, more preferably 0.5% to 2%, even more preferably 0.8% to 1.2% . metal care agents
[0173] Metal care agents can prevent or reduce tarnishing, corrosion or oxidation of metals such as aluminum, stainless steel and non-ferrous metals such as silver and copper. Suitable examples include one or more of the following: (A), benzotriazoles including benzotriazole or bis-benzotriazole and substituted derivatives thereof. Benzotriazole derivatives are those compounds in which the available substitution sites on the aromatic ring are partially or completely replaced. Suitable alkyl groups include straight or branched chain C 1 -C 20 alkyl groups and hydroxy, thio, phenyl or halogen, such as fluorine, chlorine, bromine and iodine. (b) metal salts and complexes chosen from the group consisting of salts and/or complexes of zinc, manganese, titanium, zirconium, hafnium, vanadium, cobalt, gallium and cerium, the metals found in one of the oxidation states II, III, IV, V or VI. In one aspect, suitable metal salts and/or complexes may be chosen from the group consisting of salts of Mn(II) sulfate, Mn(II) citrate, Mn(II) stearate, Mn(II) acetylacetonate, K2TiF6 , K2ZrF6, CoSO4, Co(NO3)2 and Ce(NO3)3, zinc salts, for example zinc sulfate, zinc acetate or hydrozincite; (c) Silicates, including sodium or potassium silicate, sodium disilicate, sodium metasilicate, crystalline phyllosilicate and mixtures thereof. Other suitable organic and inorganic redox-active substances that act as silver/copper corrosion inhibitors are disclosed in USP 5,888,954.
[0174] In one aspect, the detergent composition according to the invention comprises from 0.1% to 5%, between 0.2% and 4% or between 0.3% and 3% by weight of the total composition of a metal care agent.
[0175] The corrosion inhibitors used can, for example, be silver protectors from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminatriazoles, alkylaminatriazoles and the salts of transition metals or complexes. Particular preference is given to the use of benzotriazole and/or alkylaminetriazole. In addition, active chlorine-containing agents that can markedly reduce surface corrosion of silver often find use in detergent formulations. In chlorine-free detergents, preference is given to the use of organic redox-active compounds containing oxygen and nitrogen such as di- and trihydric phenols, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol and derivatives thereof classes of compounds. Inorganic compounds of the complex and salt type, such as the metal salts of Mn, Ti, Zr, Hf, V, Co and Ce are often also used. Preference is given in this context to transition metal salts which are selected from the group of manganese and/or cobalt salts and/or complexes, more preferably from the group of cobalt (amine) complexes, cobalt complexes (acetate), and cobalt (carbonyl) complexes, cobalt or manganese chlorides, and manganese sulfate. It is also possible to use zinc compounds or bismuth or sodium silicate compounds to prevent corrosion on the tableware.
[0176] The formulations may also contain one or more material care agents that are effective as corrosion inhibitors and/or anti-fog aids. solvents
[0177] The improved polymers of the present invention are particularly useful for water-based formulations, water-free formulations, powders, and formulations containing water miscible auxiliary solvents, but are not limited thereto. Useful solvents typically used are typically liquids, such as water (deionized, distilled or purified), alcohols, polyols and the like, and mixtures thereof. Non-aqueous or hydrophobic auxiliary solvents are commonly used in substantially water-free products such as propellant aerosol sprays, automotive and household surface cleaners, or for specific functions such as removing oily soils, tallow, stains, or for colorants for dissolution, fragrances, and the like, or are incorporated into the oil phase of an emulsion. Non-limiting examples of auxiliary solvents, other than water, include, linear and branched alcohols such as ethanol, propanol, isopropanol, hexanol, and the like; aromatic alcohols such as benzyl alcohol, cyclohexanol, and the like; C12-C30 saturated fatty alcohol, such as lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, and the like. Non-limiting examples of polyols include polyhydroxy alcohols such as glycerine, propylene glycol, butylene glycol, hexylene glycol, C2-C4 alkoxylated alcohols, and C2C4 alkoxylated polyols such as ethoxylated ethers, propoxylates, butoxylated alcohols with some alcohols, from 2 to about 30 carbon atoms and 1 to about 40 alkoxy units, polypropylene glycol, polybutylene glycol, and the like. Non-limiting examples of non-aqueous auxiliary solvents include silicones and silicone derivatives such as cyclomethicone and the like; ketones such as acetone and methyl ethyl ketone; natural and synthetic oils and waxes, such as vegetable oils, plant oils, animal oils, essential oils, mineral oils, C7-C40 isoparaffins, alkyl carboxylic esters, such as ethyl acetate, amyl acetate, ethyl lactate, and the likes, jojoba oil, shark liver oil and the like.
[0178] Organic solvent - An embodiment of the present invention relates to a composition comprising an organic solvent selected from the group consisting of low molecular weight aromatic or aliphatic alcohols or, low molecular weight alkylene glycols, ethers of low molecular weight alkylene glycol, low molecular weight esters, low molecular weight alkylene amines, low molecular weight alkanol amines, and mixtures thereof.
[0179] Some of the above non-aqueous auxiliary solvents may also be diluents, solubilizers, emulsifiers and conditioners. Fills
[0180] The fillings allow the adjustment of the active matter in the detergent to the doses used. Fillers include powdered sodium sulfate, water and liquid solvents. Silicates
[0181] Suitable silicates are sodium silicates such as sodium disilicate, sodium metasilicate and crystalline silicates. Silicates, if present, are at a level of from about 1% to about 20%, or from about 5% to about 15% by weight of the automatic dishwashing detergent composition. pH Adjusting Agents
[0182] A pH adjusting agent can be added to a formulation that contains an improved polymer. Thus, the pH adjusting agent can be used in any amount necessary to obtain a desired pH value in the final composition. Non-limiting examples of alkaline pH adjusting agents include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; ammonia hydroxide; organic bases such as triethanolamine, diisopropylamine, dodecylamine, diisopropanolamine, aminomethyl propanol, cocamine, oleamine, morpholine, triamylamine, triethylamine, tromethamine (2-amine-2-hydroxymethyl)-1,3-propanediol), and tetrakis (hydroxypropyl) ethylenediamine; and alkali metal salts of inorganic acids, such as sodium borate (borax), sodium phosphate, sodium pyrophosphate, and the like, and mixtures thereof. Acidic pH adjusting agents can be organic acids, including amino acids and inorganic mineral acids. Non-limiting examples of acidic pH adjusting agents include acetic acid, citric acid, fumaric acid, glutamic acid, glycolic acid, hydrochloric acid, lactic acid, nitric acid, phosphoric acid, sodium bisulfate, sulfuric acid, tartaric acid, and the like , and its mixtures. Conditioning Aids
[0183] The improved polymers of the present invention can be used in combination with silicone oils. The most common class of silicone polymers are linear polydimethylsiloxanes with the general formula CH3-(Si(CH3)2-O)w-Si(CH3)3 where w stands for an integer greater than 2. Silicones can also be branched materials in which one or more alkyl groups in a polymer are replaced with an oxygen atom to create a branch point. Silicone oils are typically water-insoluble oils that have a viscosity in the range of a few mPas to hundreds of thousands of mPas.
[0184] One class of silicones are so-called silicone gums, as described, for example, in Pat. No. 4,902,499, incorporated herein by reference, which generally have a viscosity (at about 20°C.) of greater than about 600,000 mPas and have a weight average molecular weight of at least about 500,000 Daltons , as determined by measuring intrinsic viscosity.
[0185] Another class of silicone materials that are particularly useful in combination with the polymers of the present invention are volatile silicones. Volatile silicones include cyclic and linear polydimethylsiloxanes, and the like. Cyclic volatile silicones typically contain about 3 to about 7 silicon atoms, alternating with oxygen atoms, of a cyclic ring structure. Each silicon atom is also replaced with two alkyl groups, usually methyl groups. Linear volatile silicones are silicone oils, such as those described above, with viscosities of no more than about 25 mPas. A description of volatile silicones is found in Todd and Byers, "Volatile Silicone Fluids for Cosmetics", Cosmetics and Toiletries, Vol. 91 (1), pp. 2732 (1976), and in Kasprzak, "Volatile Silicones," Soap/Cosmetics/Chemical Specialities, pp. 40-43 (December 1986), each incorporated herein by reference.
[0186] Other silicone oils include dimethicone copolyols, which are linear or branched copolymers of dimethylsiloxane (dimethicone) and alkylene oxides. Dimethicone polyols can be random or block copolymers. A generally useful class of dimethicone polyols are block copolymers with blocks of polydimethylsiloxane and blocks of polyalkylene oxide, such as blocks of polyethylene oxide, polypropylene oxide, or both. Silicone fluids, including volatile silicones, silicone gums, and silicone copolymers, are available from a variety of commercial sources, such as Dow Corning, Momentive, Wacker Chemie, Shin Etsu, and Lubrizol Advanced Materials.
[0187] Other oily materials that are useful in combination with the improved polymers of the present invention include, for example, acetylated lanolin alcohols; lanolin alcohol concentrates; lanolin fatty acid esters, such as the isopropyl fatty acid esters of lanolin; polyol fatty acids; ethoxylated alcohols such as ethoxylated castor oils; sterols; sterol esters; ethoxylated sterols; and similar materials. Many of the aforementioned esters and ethoxylates are also useful as nonionic surfactants.
[0188] Various ingredients are known in the art as conditioning and wetting agents, and in addition to those discussed above, non-limiting examples include PCA (DL-pyrrolidone carboxylic acid) and its salts such as lysine PCA, aluminum PCA, PCA copper, PCA chitosan, and the like, allantoin; urea; hyaluronic acid and its salts; ceramides; sorbic acid and its salts; sugars and starches and their derivatives; MEA lactamide; and the like. Color
[0189] Improved polymers can also be used in colored compositions. Therefore, they can comprise a dye or a mixture thereof. Perfume Additives
[0190] Non-Flowering Perfumes and Perfumes - Perfumes and perfumery ingredients useful in the present compositions and processes comprise a wide variety of natural and synthetic fibers, chemical ingredients, including, but not limited to, aldehydes, ketones, esters, and others similar. Buffers
[0191] Alkalinity buffers that can be added to the compositions of the invention include monoethanolamine, triethanolamine, borax and the like.
[0192] Other materials such as clays, particularly of the water-insoluble types, can be useful additives in the compositions of the present invention. Particularly useful is bentonite or Laponite. This material is primarily montmorillonite, which is a hydrated aluminum silicate in which about 1/6 of the aluminum atoms can be replaced by magnesium atoms, and with which varying amounts of hydrogen, sodium, potassium, calcium, etc., can be freely combined. Bentonite in its most purified form (ie free of any grain, sand, etc.) suitable for detergents contains at least 50% montmorillonite, and thus its cation exchange capacity is at least about 50 to 75 meq per l00g of bentonite. Particularly preferred bentonites are Wyoming or Western US bentonites which have been sold as Thixo-Jels 1, 2, 3 and 4 by the Georgia Kaolin Co. These bentonites are known to soften fabrics, as described in British Patent No. 401, 413 for Marriott and British Patent No. 461, 221.
[0193] In addition, various other detergent additives or adjuvants may be present in the detergent product to give it additional desired properties, whether functional or aesthetic in nature.
[0194] Improvements in the physical stability and anti-settling properties of the composition can be achieved by adding a small effective amount of an aluminum salt of a higher fatty acid, eg, aluminum stearate, to the composition. The aluminum stearate stabilizing agent can be added in an amount of 0 to 3%, preferably 0.1 to 2.0% and more preferably 0.5 to 1.5%.
[0195] Minor amounts of soil-suspending or anti-redeposition agents, eg polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose, may also be included in the formulation. A preferred anti-redeposition agent is sodium carboxymethylcellulose with a 2:1 CM / MC ratio which is sold under the trade name Relatin DM 4050.
[0196] Fluorescents may also be included in formulations, such as, for example, 4,4'-di[(4-aniline-6R, 1,3,5triazin-2-yl)amine]stilbene 2,2'disulfonate, or 4,4-di(2-sulfostyril)bi-phenyl. unit dose
[0197] In one aspect, the detergent composition according to the invention is in unit dose form. Detergent products in unit dose form include tablets, capsules, sachets, packets, pods, etc. Detergent compositions can be in the form of a liquid, gel or powder. In one aspect for use in the present invention are tablets wrapped with a water soluble film and water soluble packets. The weight of the composition of the invention is from about 10 to about 25 grams, from about 12 to about 24 grams, or even from 14 to 22 grams. These weights are extremely convenient for adjustment in the detergent container. In cases of unit dose products with a water soluble material which involve the detergent composition, the water soluble material is not considered to be part of the composition. In one aspect, the unit dose form is a water-soluble pack (i.e., water-soluble film surrounding the detergent composition), in one aspect, a multi-compartment pack with a plurality of films forming a plurality of compartments. . This setting contributes to composition flexibility and optimization. It allows for the separation and controlled release of different ingredients. In one aspect, one compartment contains the detergent composition in solid form and another compartment contains the detergent composition in liquid form.
[0198] In one aspect, the films of these two compartments have different dissolution profiles, allowing the release of the same or different agents at different times. For example, agent from one compartment (the first compartment) can be delivered early in the wash process to aid in the removal of dirt, and a second agent from another compartment (the second compartment) can be delivered in at least two minutes, or even , at least five minutes later, from the first compartment agent.
[0199] A multi-compartment package is formed by a plurality of water-soluble surrounding materials, which form a plurality of compartments, one of the compartments containing the automatic detergent composition of the invention, another compartment may contain a liquid composition, wherein the liquid composition may be aqueous (i.e. comprise greater than 10% water by weight of the liquid composition) and the compartment may be made of hot water soluble material. In some embodiments, the compartment comprising the detergent composition of the invention is made of cold water soluble material. It allows for the separation and controlled release of different ingredients. In other embodiments, all compartments are made of hot water soluble material. PROCESS OF POWDER DETERGENTS FOR WASHING CLOTHES:
[0200] A process for the preparation of a detergent composition of bulk density, high active, as well as the composition itself, in which the process comprises the steps of (i) introduction of a binder component, which comprises a neutralized or neutralized surfactant. partially neutralized, surfactant precursor, improved polymer, and/or salts thereof, and a solid component of initial particle size from submicron to 500 µm in a high shear mixer to thereby form a mixture of particles and (ii) binding from said mixture to a high shear mixture and thus granulating the components so as to form granules of a dimension within the range of 1 to 1200 µm. Preferably, after this mixing, a coating agent such as zeolite is added to the mixer.
[0201] The detergent composition is suitably a complete detergent composition. The term "complete" is used to refer to a detergent composition that comprises sufficient surfactants, builders, and alkalinity source to function as an effective fabric washing powder. Alkalinity source refers to sodium carbonate or phosphates. The term "complete" does not restrict the addition of certain minor components, in conventional amounts, for example, with weights less than 5%. Such minor components include enzymes, bleach, perfume, anti-fouling agent, or colorant to improve the performance of the washing powder.
[0202] The particulate detergent composition can, if desired, be used as a raw material in a detergent production process. For example, a liquid component surfactant such as the nonionic surfactant can be sprayed onto the composition and can then be coated with, for example, zeolite. If the detergent composition is used as a raw material, it is preferable that it be the direct product of the process of the present invention. That is, additional components are not incorporated into the detergent particles prior to their use as a raw material. However, if desired, the particles can be mixed with separate particles that comprise other materials. This provides the advantage of allowing the detergent composition to be produced in one location, in a single-step process and optionally mixed with separate particles and then transported to a remote location for further storage or processing, such as wanted.
[0203] As a result of this increase in viscosity, the process appears to be more easily controlled, resulting in better powder properties for the detergent composition.
[0204] Examples of said viscosity-increasing components are water, and in particular fatty acids in combination with a stoichiometric amount of alkaline material (such as caustic soda) sufficient to neutralize the fatty acid which obviously results in soap formation.
[0205] In the process, a solid component that may comprise detergency building agents, such as water-soluble alkaline inorganic materials (eg, sodium carbonate distributed with calcium carbonate), zeolite, sodium tripolyphosphate, other inorganic materials soluble in water, such as sodium bicarbonate or silicate, fluorescent agents, polycarboxylate polymers, anti-redeposition agents and fillers, is mixed with a binder component, which in addition to a neutralized or partially neutralized surfactant, may comprise water, solution of silicate, liquid polymer components, polyethylene glycols, perfumes, fatty acids and other materials. In the context of the present invention, the term binder component includes any component that is susceptible to plastic deformation under conditions encountered during the process.
[0206] Examples of materials that can be further dosed into the composition include enzymes, bleaches, bleach precursors, bleach stabilizers, suds suppressors, perfumes and dyes. The liquid or pasty ingredients can conveniently be absorbed into the generally inorganic, porous solid particles, which can then be further dosed into the composition obtained by the process of the invention.
[0207] The process is very flexible with regard to the chemical composition of the starting materials. Phosphate as well as zeolite building compositions can be made. The process is also suitable for the preparation of compositions containing calcite/carbonate.
[0208] The particulate solid component has an initial particle size of 0.1 to 500 µm, preferably 1 to 350 µm, more preferably 0.1 to 300 µm. The solid component preferably comprises from 5 to 95% of detergency builders, more preferably from 10 to 80%, more preferably from 20 to 60% by weight.
[0209] Preferably, the binder component also comprises the improved polymers and/or their salts. Preferably, the binder component comprises a mixture of neutralized or partially neutralized or unneutralized surfactants, for example a mixture of sulfonic acid or primary or linear alkylbenzene sulfonate containing from 11 to 14 carbon atoms and a C12 to C15 primary alcohol ethoxylated with 3 to 7 moles of ethylene oxide per mole of alcohol, in an anionic to nonionic weight ratio of 3 to 1, or a mixture of a C14 to C17 primary or secondary alcohol sulfate with an ethoxylated primary alcohol C12 to C15, with 3 to 7 moles of ethylene oxide per mole of alcohol, in a weight ratio of 2 to 1.
[0210] The high shear mixer advantageously used to carry out the process is preferably a Littleford (TM) FM 130D mixer. This apparatus essentially consists of a large, static hollow cylinder with its longitudinal axis horizontal. Along this axis is a rotating axis with several different types of blades mounted. Preferably, when used to carry out the process of the present invention, the tip speed is between 1 m/sec. and 20 m/sec., more preferably 1 m/sec. and 12 m/sec. The mixer can be equipped with one or more high speed cutters, and preferably these are operated at peripheral speeds of 15 m/sec. to 80 m/sec, more preferably from 20 m/sec. at 70 m / sec. Other mixers suitable for the process of the invention are Lodige™, Eirich™ RVO2, Powrex™ VG100, Zanchetta™, Schugi™ and Fukae™.
[0211] In the process, the solid component is fed into the mixer followed by the binding component, which is sprayed onto the solid component or pumped into the mixer. The components are mixed for a total residence time preferably from 0.2 to 8 minutes, more preferably from 0.25 to 5 minutes. Excellently, after this time, a mixture of a coating agent such as zeolite can be added to the mixer, and the mixer operated with the main shaft only for 20 to 60 seconds. The granules produced by the process preferably have a bulk density of between 600 g/liter to 1150 g/liter and a particle size (measured by Rosin-Rammler) of 300 to 1200 µm more preferably 400 to 800 µm.
[0212] The ratio of binder component to solid component is preferably in a weight ratio of 3:2 to 2:3, more preferably 1:1 to 2:3.
[0213] The process is operated at a temperature from ambient temperature to 60°C, more preferably from ambient temperature to 40°C. PREPARATION OF DETERGENT FOR DRY WASHING CLOTHING BY SPRAYING
[0214] An aqueous alkaline laundry detergent suspension comprising: water, alkyl benzene sulfonate, sodium silicate; improved polymer (eg acrylic/itaconic acid copolymer), sodium sulfate, sodium carbonate, magnesium sulfate, and other optional ingredients is prepared. This aqueous suspension is sprayed in a countercurrent spray drying tower, and spray dried to produce spray dry laundry detergent powder.
[0215] The amount of each chemical component described is presented exclusive of any solvent or diluent, which may be habitually present in the commercial material, that is, in an active chemical basis, unless otherwise indicated. However, unless otherwise indicated, each chemical or composition referred to herein is to be construed as being a commercial grade material that may contain the isomers, by-products, derivatives, and others of such materials that are commonly understood to be present in commercial scale.
[0216] It is known that some of the materials described above can interact in the final formulation, so that the components of the final formulation may be different from those that are initially added. For example, metal ions (from, for example, a detergent) can migrate to other anionic or acidic sites of other molecules. The products so formed, including the products formed above, which utilize the composition of the present invention in its intended use, may not be susceptible to easy description. However, all such modifications and reaction products are included within the scope of the present invention; the present invention encompasses the composition prepared by mixing the above-described components. EXAMPLES Test Methods Viscosity
[0217] Brookfield rotary shaft method (all viscosity measurements referred to herein are performed by the method, whether mentioned or not): Viscosity measurements are calculated in mPa-s using a Brookfield rotary viscometer, Model RVT (Brookfield Engineering Laboratories , Inc.), at about 20 revolutions per minute (rpm), at an ambient temperature of about 20 to 25°C (hereinafter referred to as viscosity). Shaft sizes are selected in accordance with the manufacturer's usual operating recommendations. Generally, shaft sizes are selected as follows:

[0218] Shaft size recommendations are for illustrative purposes only. The artisan skilled in the art will select an appropriately sized shaft for the system to be measured. turbidity tests
[0219] The turbidity of a composition containing a polymer of the invention is determined in Nephelometric Turbidity Units (NTU) using a nephelometric turbidity meter with distilled water (NTU = 0) as standard. Molecular Weight Determination
[0220] The average molecular weights mentioned herein are measured by GPC using a Waters Model 515 pump, Waters Model 717 WISP autosampler with Waters Model 2410 with a refractive index @ 40°C. About 0.01 g of polymer sample is dissolved in 10 ml of 97.5% 0.1 M sodium nitrate with 2.5% tetrahydrofuran (THF). The test sample solution is gently shaken for approximately two hours and filtered by passing the sample solution through 0.45 µm of a PTFE disposable filter disc. The chromatographic conditions are as follows: Mobile phase: 97.5% 0.1 M Sodium Nitrate / 2.5% THF (pH = 10), 0.7 ml / min. Sample Size: 100 µl Column: TOSOH Guard + 2 x TSKgel GMPWxl (13U), 300 x 7.8mm, @ 35°C. Waters Empower Pro LC/GPC software is used to analyze the results and to calculate Mw of the polymers of the invention.
[0221] The molecular weight calibration curve was established with the polyacrylic acid standards contained in the "PSS-PAAKIT" of Polymer Standards Service-USA. Acrylic acid with MW = 94 Daltons was added to a standard. The calibration curve covered an Mp range from 94 to 1.10 x 106Daltons. 1H NMR
[0222] Nuclear magnetic resonance (NMR) is an analytical technique that can help to determine, among other things, detailed information about the structure, molecular dynamics, and chemical environment of molecules. 1H NMR spectra mentioned here are measured by dissolving the samples in D2O solvent in 5mm NMR tubes and observed by 1H NMR on the Bruker AV500.
[0223] The 1H NMR spectra mentioned here are measured by dissolving the samples in D2O solvent in 5mm NMR tubes and observed by 1H NMR on the Bruker AV500. residual monomers
[0224] Residual monomers such as itaconic acid, acrylic acid and AMPS are measured by HPLC using a Varian 5020 with UV detector, Spectra-Physics 4100 data analyzer and modified silica C-18 column such as Phenomenex Jupiter 5u C-18 300A, 4.6mm ID x 25 cm at 20°C. The mobile phase is the 0.01M KH2PO4 solution with a flow rate of 1 ml/minute. Monomer detection limit is < 5 ppm. Cl2 retention
[0225] Percent chlorine retention data is generated using a simplified formulation containing 1% total solid polymer in water with sodium hypochlorite (1% active from CL2) and adjusting the final pH of the formulation with 18% NaOH to pH> 12. The following titration procedure is used to calculate % by weight of Cl2 retention. The result equals 1.00 for 100% Cl2 retention. Title Preparation
[0226] Titration is carried out as follows: 1) While the chlorine bleach solution is mixed, dissolve 1.99 to 2.01 g of potassium iodide in 50 mL of DI water using a 250 mL Erlenmeyer flask. 2) Add approximately 2 ml of HCl (37% assay) using a pipette and mix thoroughly. 3) Now weigh 2.5 to 2.7 g of the chlorine bleach solution into the flask, and record the amount to 3 decimal places. The solution will turn reddish brown. 4) Start titration with 0.1N sodium thiosulfate. Continue until it turns a straw yellow color. 5) Now add about 5 mL of Starch Indicator Solution. The chlorine bleach solution will now be blue / black. 6) Continue with 0.1N sodium thiosulfate slowly until the chlorine bleach solution is clear. Wait a few minutes after the solution becomes clear, to see if it turns dark again. If so, add more titrant. If not, record amount used in mL. 7) Use the following formulation to calculate % by weight of Cl2 retention. Calculation (titration in ml) (0.3546) = % by weight Cl2 weight of sample. Calcium binding capacity:
[0227] The calcium chelation capacity of polymers is measured using Thermo Orion Ion Selective Electrode (ISE) connected to an Orion Start Plus meter. The instrument is calibrated using four standard solutions (calcium chloride (CaCl2) with concentrations of 0.0001 M, 0.001 M, 0.01 M and 0.1 M. 1% of the chelating solution is prepared in deionized water and its pH is adjusted to desired value using NaOH solution.
[0228] The following procedure is used for a typical titration sample: Burette is filled with 1% chelator solution. • In a 250 ml container containing a magnetic stir bar, 100 ml of 0.01 M CaCl2 solution is placed. 2 ml of ionic strength adjuster (ISA) is added. • The ISE and reference electrodes are washed with distilled water, dried and placed in solution. • The chelating solution is titrated from the burette, and the Ca2+ concentration is monitored on the Orion Star Plus meter. • The chelating solution is added gradually until the meter shows a 0.00M concentration of Ca2+. • The titration endpoint is used to calculate the calcium capacity of the binding polymer in mg of CaCO3 / g of polymer with the following equation:
where M = starting molarity of the CaCl2 solution and BR = burette reading, mL at the end point of the titration. abbreviations
[0229] The following abbreviations and trade names are used in the examples. ABBREVIATIONS and Trade Names Abbreviation Chemical Name IA Itaconic Acid AA Acrylic Acid AMPS™ Monomer 2-acrylamide-2-methylpropane sulfonic acid (Lubrizol Advanced materials, Inc.) SPS Sodium Persulfate FF6 Reducing (mixture of a disodium salt of 2-hydroxy acid -2-acetic acid and sodium sulfite) available from Brüggolit NaOH Sodium hydroxide STPP Sodium tripolyphosphate EDTA Ethylenediaminetetraacetic acid PAA Low molecular weight polyacrylic acid (Source: AcusolTM445 from DowTM(“CL1”); NoveriteTM K-752 from LubrizolTM ("CL2"); Noverite K-7058 from Lubrizol ("CL3"); Noverite K-732 from Lubrizol ("CL4"); SokalanTMPA 25 from BASFTM ("CL5") PIA Poly-itaconic acid (Source: ItaconixTMDSP-2K (“CL6”) MGDA Methylglycinediacetic acid, sodium salt (Source: TrilonTMM from BASF (“CL7”) GLDA Glutamic diacetic acid, tetrasodium salt (Source: DissolvineTMGL from Akzo Nobel (“CL8”)) PAA/SA Polyacrylic acid copolymer / sulfonic acid (Noverite K-775 from Lubrizol ("CL9"); Acusol Dow 588 ("CL10")) P(AA/MA) Acrylic acid/maleic acid copolymer (Sokalan CP-45 ("CL11"); Sokalan CP-5 from BASF ("CL12"); Acusol 460N from Dow (“CL13”)) EDDS Ethylenediaminedisuccinate Hybrid Polymer (based on natural and synthetic monomers) (Source: AlcogaurdTMH 5941 from Akzo Nobel (“CL14”)) Sample 1: poly-itaconic acid
[0230] In a stirred reactor equipped with 250 grams of deionized (D.I.) water, 250 grams of itaconic acid are added under nitrogen atmosphere and mixed at 300 rpm. The reactor contents are heated to about 60°C, with mixing, agitation (300 rpm), under a nitrogen atmosphere for 30 minutes. When the reactor contents reach a temperature of approximately 60°C, 30 grams of FF6 solution (0.084% aqueous solution weight / weight) and 26.25 grams of sodium persulfate solution (38 percent aqueous solution weight / weight) are injected into the heated IA solution within 10 minutes. After 30 minutes, the reaction temperature is increased to 80 to 85°C. When the reactor contents reach a temperature of about 80 to 85°C, 28.5 percent of the sodium persulfate solution (weight/weight aqueous solution) is also measured at 0.44 ml/minute into the mixture of reaction for 75 minutes. The reaction temperature is maintained at about 80 to 85°C for an additional period of four hours to complete the polymerization. The resulting polyitaconic acid product is cooled to room temperature and the product pH is adjusted from <1.0 to 2.5 with 50% NaOH before discharge from the reactor. Samples 2-4: polyitaconic acid
[0231] Sample 1 is repeated to make samples 2-4 with pre-neutralized itaconic acid, as mentioned in Table 1, to investigate the neutralizing effect on the AI isomerization as well as its conversion. A 50% NaOH neutralization solution, at different percentages, based on the acid groups of the IA monomer, is added along with IA and is referred to as the percentage of degree of neutralization (%DN). Samples 2 to 4 contain 5, 10 and 20% DN neutralizing solution, respectively. Comparative Sample I
[0232] A polyitaconic acid polymer is prepared in water using the procedure of Example I, in US Patent No. 7,910,676, at 50% DN using 70% HPtB initiator under reflux conditions. Example 1
[0233] Polymer samples 1 to 4 and Comparative Sample I are characterized by % total solids, pH, product viscosity, conversion (by HPLC), and AI isomerization by 1H NMR. The results are shown in Table 1 below. A significant amount of citraconic acid (IA isomer) is noted by the presence of cis- and trans-CH3- peak at 2.1 and 1.97 ppm and cis- and trans-methine -CH- peak at 5.8 and 6.55 ppm, as shown in Figure 1 in Comparative Sample I, as well as the poor AI conversion. Samples 1-4 are markedly free of IA isomer with better conversion. Table 1: Poly-itaconic acid made with different pre-neutralization conditions (%DN)
Sample 5: 90/] .0 mol% itaconic acid/acrylic acid copolymer
[0234] In a stirred reactor containing 225 grams of deionized water (DI), 235.5 grams of itaconic acid are added under a nitrogen atmosphere and mixed at 300 rpms. The reactor contents are heated to about 60°C, with mixing agitation (300 rpm), under a nitrogen atmosphere for 30 minutes. When the reactor contents reach a temperature of approximately 60°C, 30 grams of FF6 solution (0.084% aqueous solution weight/weight) and 26.25 grams of sodium persulfate solution (38% aqueous solution weight/weight) ) are injected into the heated IA solution within 10 minutes. After 30 minutes, the reaction temperature is increased to 85°C. When the reactor contents reach a temperature of approximately 85°C, the 28.5% sodium persulfate solution (weight/weight aqueous solution) is also measured at 0.44 ml/minute in the reaction mixture for 75 minutes. At the same time, the comonomer solution, made from 14.5 grams of AA monomer mixed with 12.5 grams of water, is also gradually measured (0.43 g/min.) in the reactor over a period of about 60 minutes to react with the AI. The reaction temperature is maintained at about 85°C for an additional four hours to complete the polymerization. The resulting copolymer of itaconic acid and acrylic acid product is cooled to room temperature and the product pH is adjusted to 2.5 with 50% NaOH prior to reactor discharge. Samples 6-12: itaconic acid / acrylic acid copolymers
[0235] Polymers 6 to 12 are also synthesized as set forth in Sample 5. A neutralizing solution of 50% NaOH at 5% based on the acid groups of the total monomers (5% DN) is added along with the IA in samples 11 and 12. The monomeric components for these samples are shown in Table 2 below. Comparative Sample II
[0236] A 90/10 mol% IA/AA copolymer is prepared using the procedure of Example 2B in US Patent No. 4,485,223 under reflux conditions, at about 20% by weight (0.1 mol%) of initiator. Example 2
[0237] Polymer 6 to 12 and Comparative Sample II samples are characterized by % total solids, pH, product viscosity, IA conversion and isomerization by 1H NMR. The results are shown in Table 2 below. The combination of both the high level of initiator and the high temperature (reflux) conditions in the preparation of Comparative Sample II causes the initiator to decompose rapidly, resulting in 1) a polymer solution that has a dark color and odor of undesirable sulfur, with oxidized and sulfurized itaconic acid impurities along with unreacted monomers (Figure 2), and 2) poor chlorine retention performance. Surprisingly, the combination of both the lower temperature (<85°C) and redox initiator (oxidant-SPS and reducer-FF6), used in samples 5 to 12, yield cosmetically acceptable color and odor, and relatively pure copolymer products (Figure 3) with desirable Mn and other properties. Furthermore, the use of less than 5% equivalent pre-neutralization (referred to as DN) eliminates the problem of dangerous corrosion due to the low pH < 1 of the final product and subsequently makes the process suitable for commercial production options .

Samples 13 to 22: AI Copolymers and Terpolymers with AMPS Monomer
[0238] Polymers 13 to 22 are also synthesized as set forth in Sample 5 (for example, at a reaction temperature of 85°C and with 0% DN), except for a monomer sodium salt of AMPS which is used in place of AA or in combination with AA. The monomeric components for these samples are shown in Table 3 below.

Sample 23
[0239] In spray dryers, the raw material in suspension, solution or paste form is sprayed through a pressure nozzle or centrifugal discs, in a drying chamber with high temperature air flowing in a parallel or parallel direction. of the counter. Buchi mini spray dryer is used to dry the product. It operates on the nozzle principle, spraying in parallel flow (sprayed product and drying air flow in the same direction). A polymer solution, with about 55% - 70% net content is prepared and pumped into the dryer at 8 g/min., at a temperature of 130°C to 170°C, more preferably at 150°C. The room temperature aqueous polymer solution is pumped and atomized through a nozzle into a drying chamber with air flowing in the same direction at a temperature of 150°C. The dry powder leaving the air spray drying tower is transported to a cyclone, where the product is separated from the air stream. The temperature of the powder leaving the spray dryer is less than 150°C with loss on drying (LOD) less than 10% by weight. The morphology of the powder changed from fluffy white powder to free-flowing particle with increasing liquid content in polymer solution. Sample 24
[0240] In a stirred reactor containing 500 grams of deionized water (DI), 365 grams of itaconic acid and 15 grams of 50% NaOH were added under nitrogen atmosphere and mixed at 300 rpm. The reactor contents were heated to about 60°C with mixing agitation (300 rpm) under an atmosphere of nitrogen for 30 minutes. When the reactor contents reached a temperature of approximately 60°C, 71 grams of FF6 solution (7% aqueous solution weight/weight) and 52.2 grams of sodium persulfate solution (3.83 % aqueous solution weight) / weight) were injected into a heated AI solution within 10 minutes. After 30 minutes the reaction temperature was raised to 85°C. When the reactor contents reached a temperature of approximately 85°C, 8.6 grams of 35% H2O2 was added as batches in 2 additions and was followed by the metered addition of 28.5% sodium persulfate solution ( aqueous solution weight/weight) at 0.43 ml/minute into the reaction mixture for 135 minutes. At the same time, the comonomer solution made from 135 grams of AA monomer mixed with 25 grams of water, was also gradually dosed (1.27 g/min.) into the reactor over a period of about 120 minutes to react with the AI. The reaction temperature was maintained at about 85°C for an additional four hours to complete the polymerization. About 17 grams of 35% H2O2 was added in 2 additions at 60 minute intervals as a further treatment. The resulting copolymer of acrylic acid and itaconic acid product was cooled to room temperature and the pH of the product was adjusted to 7 - 8 with 50% NaOH prior to reactor discharge. Sample 25
[0241] In a stirred reactor containing 500 grams of deionized water (DI), 317.5 grams of itaconic acid and 15 grams of 50% NaOH were added under nitrogen atmosphere and mixed at 300 rpm. The reactor contents were heated to about 60°C with mixing agitation (300 rpm) under an atmosphere of nitrogen for 30 minutes. When the reactor contents reached a temperature of approximately 60°C, 71 grams of FF6 solution (7% aqueous solution weight/weight) and 52.2 grams of sodium persulfate solution (3.83 percent aqueous solution) weight/weight) were injected into the heated AI solution at 10-minute intervals. After 30 minutes, the reaction temperature was raised to 80°C. When the reactor contents reached a temperature of approximately 80°C, 8.6 grams of 35% H2O2 were added as batches in 2 additions and followed by the metered addition of 28.5% sodium persulfate solution (solution aqueous weight/weight) at 0.43 ml/minute into the reaction mixture for 135 minutes. At the same time, the comonomer solution made from 87.5 grams of AA monomer mixed with 181.64 grams of AMPS 2403 monomer, was also measured gradually (1.93 g/min.) in the reactor over a period of about 120 minutes to react with the AI. The reaction temperature was maintained at about 80°C for an additional four hours to complete the polymerization. About 17 grams of 35% H2O2 was added in 2 additions at 60 minute intervals as a further treatment. The resulting copolymer of itaconic acid and acrylic acid product was cooled to room temperature and the pH of the product was adjusted to 7-8 with 50% NaOH prior to reactor discharge. Sample 26
[0242] In a stirred reactor containing 700 grams of deionized water (DI), 317.5 grams of itaconic acid and 15 grams of 50% NaOH were added under nitrogen atmosphere and mixed at 300 rpm. The reactor contents were heated to about 60°C with mixing agitation (300 rpm) under a nitrogen atmosphere for 30 minutes. When the reactor contents reached a temperature of approximately 60°C, 71 grams of FF6 solution (7% aqueous solution weight/weight) and 52.2 grams of sodium persulfate solution (3.83 % aqueous solution weight) / weight) were injected into the heated AI solution at an interval of 10 minutes. After 30 minutes, the reaction temperature was increased to 65°C to 70°C. When the reactor contents reached a temperature of approximately 70°C, 8.6 grams of 35% H2O2 was added as a batch in 2 additions and followed by the metered addition of 28.5% sodium persulfate solution (solution aqueous weight/weight) at 0.43 ml/minute in the reaction mixture for 135 minutes. At the same time, the comonomer solution made from 87.5 grams of AA monomer mixed with 181.64 grams of AMPS 2403 monomer, was also measured gradually (1.93 g/min.) in the reactor over a period of time. about 120 minutes to react with the AI. The reaction temperature was maintained at about 80°C for an additional four hours to complete the polymerization. About 17 grams of 35% H2O2 was added in 2 additions at 60 minute intervals as a further treatment. The resulting copolymer of acrylic acid and itaconic acid product was cooled to room temperature and the pH of the product was adjusted to 7 - 8 with 50% NaOH and followed by an enzyme treatment using Terminox Ultra 200L (Novozyme) at 0 .00125%. The final product was heated for one hour at about 40°C-85°C to deactivate the enzyme and then cooled to room temperature before discharge from the reactor. Sample 27
[0243] Powder versions of samples 24 and 25 were made. Spray drying of polymer samples 24 and 25 was performed in a Buchi 190 mini spray dryer or 2.5 ft Niro spray dryer. A polymer solution, with about 60-65% net content was prepared and pumped into the dryer at 5-10 g/min., at a temperature of 130°C to 190°C, more preferably at 150°C to 170°C. The dry powder exiting the air spray drying tower was charged to a cyclone, where the product was separated from the air stream. The temperature of the powder leaving the spray dryer was less than 150°C with loss on drying (LOD) less than 10%. The exhaust air temperature was from 85°C to 105°C, more preferably at 90°C. Sample powder properties are given in the table below. Powder Properties
Sample 27c
[0244] The effect of different powder binders (spray dried) on particle size was also studied. Polymeric binders such as polyvinyl alcohol, polyvinylpyrrolidone as well as a non-ionic surfactant were used at a level of 1% to 5% by weight, preferably 3% to 5% by weight. The addition of non-ionic surfactant affected the particle size of the powder generated after spray drying. For example, spray dried powder generated from liquid containing 1.5-3% by weight nonionic surfactant had about 90% powder >250 microns with about 55% powder >500 microns in size. Sample 28
[0245] Granular versions of polymer have also been prepared by drum drying and spray granulation techniques. Material from the drum drying process was flaky, and had very low density. However, the spray granulation product (in Glatt-Powder-Coater-Granulator (GPCG) 3.1) of polymer sample 25 (the granular version is from sample 28 in the table below) was the free-flowing granular material with size of particle between 200-1000 microns. About 12% of particles in the product were < 200 microns. It should be noted that the spray granulation process was a continuous process, and the fine particles (<200 microns) would be recycled to obtain the product with bulk density (500-1200 kg/m3). Granular properties of the granular sample are given in the table below. granular properties
Sample 29
[0246] In a stirred reactor containing 520 grams of deionized water (DI), 520 grams of isopropyl alcohol and 474.5 grams of itaconic acid were added under nitrogen atmosphere and mixed at 300 rpm. The reactor contents were heated to about 82°C with mixing agitation (300 rpm) under a nitrogen atmosphere for 30 minutes. When the reactor contents reached a temperature of approximately 82°C, 97.5 grams of FF6 solution (6.66% aqueous solution weight/weight), 106.6 grams of sodium persulfate solution (26.7% of aqueous solution weight/weight), 18.7 grams of 35% H2O2 were injected into the heated AI solution. Immediately, a metered addition of 26.8% sodium persulfate solution (weight/weight aqueous solution) was started at 0.85 ml/minute into the reaction mixture for 105 minutes. Along with the calibrated initiator, the comonomer solution, made up of 175.5 grams of AA monomer, is also gradually fed (1.86 g/min.) into the reactor over a period of about 90 minutes to react with the IA . The reaction temperature was held at about 82-85°C for a further four hours to complete polymerization, and was followed by solvent exchange with water at 65°C. The resulting copolymer product was cooled to room temperature and adjusted to pH 3.0 - 3.5 with 50% NaOH prior to reactor discharge. The final product was identified as a copolymer of itaconic acid and acrylic acid with partial esterification of IPA based on proton NMR (a peak at 1.24 ppm IPA ester content). In addition, the final product contains lactone structures (peaks at 1.47 and 1.39 ppm), which can come from itaconic acid as well as acrylic acid. Samples 30-32
[0247] Polymer samples from 30 to 32 were also synthesized for reproducibility as set forth in Sample 29. The monomeric components for these examples were shown in the Table below. All polymers contained partial esterification and traces of lactone structures in the main part.
Sample 33
[0248] In a stirred reactor containing 475 grams of deionized water (DI), 475 grams of isopropyl alcohol, 456.25 grams of itaconic acid were added under nitrogen atmosphere and mixed at 300 rpm. The reactor contents were heated to about 82°C with mixing agitation (300 rpm) under a nitrogen atmosphere for 30 minutes. When the reactor contents reached a temperature of approximately 82°C, 37 grams of 4.43% t-butyl perpivalate solution in 1:1 w/v deionized water and isopropyl alcohol, 46.8 grams of t-butyl perpivalate solution FF6 (6.66% aqueous solution weight/weight), 101.6 grams of sodium persulfate solution (26.7% aqueous solution weight/weight), 17.8 g of 35% H2O2 were injected into the solution heated AI. Immediately, a metered addition of 26.8% sodium persulfate solution (weight/weight aqueous solution) is started at 0.88 ml/min. in the reaction mixture for 105 minutes. Along with the calibrated initiator, the comonomer solution made from 168.75 grams of AA monomer was also gradually dosed (1.86 g/min.) into the reactor over a period of about 90 minutes to react with the AI. The reaction temperature was maintained at about 82-85°C for an additional period of four hours to complete the polymerization. The resulting copolymer product was cooled to room temperature and the pH of the product was adjusted to 3.0 - 3.5 with 50% NaOH before discharge from the reactor. The final product was identified as a copolymer of itaconic acid and acrylic acid with partial esterification of IPA based on proton NMR (a peak at 1.24 ppm IPA ester content). Furthermore, the structures of the final product contained lactone (peaks at 1.47 and 1.39 ppm), which can be originated from itaconic acid and acrylic acid. Samples 34-43
[0249] Polymer samples 34 to 43 were also synthesized as established in sample 33, varying the proportions of both monomer and solvent. The monomeric components for these samples are shown in the Table below. All polymers contained partial esterification and traces of lactone structures in the main part.
Sample 45
[0250] In a stirred reactor equipped with isopropyl, and 571.5 grams of itaconic acid were added under nitrogen atmosphere and mixed at 300 rpm. The reactor contents were heated to about 82°C with mixing agitation (300 rpm) under a nitrogen atmosphere for 30 minutes. When the reactor contents reached a temperature of approximately 82°C, 71.5 grams of FF6 solution (10.0% aqueous solution weight/weight), 133.2 grams of sodium persulfate solution (27.0% solution aqueous weight/weight), 15.4 g of 35% H2O2 were injected into the heated AI solution. Immediately, a metered addition of 25.1% sodium persulfate solution (weight/weight aqueous solution) is started at 1.15 ml/min. in the reaction mixture for 105 minutes. Along with the calibrated initiator, the comonomer solution made from 157.5 grams of AA monomer, and 328.2 grams of AMPS 2403 monomer, which was also gradually dosed (4.69 g/min.) into the reactor over a period of about 90 minutes to react with the AI. The reaction temperature was held at about 82-85°C for a further four hours to complete polymerization followed by solvent exchange with water at 65°C. The resulting product derived from acrylic acid / itaconic acid / AMPS was cooled to room temperature and adjusted to pH 3.0 - 3.5 with 50% NaOH prior to reactor discharge. The final product was identified as a terpolymer of itaconic acid, acrylic acid and AMPS with partial esterification of IPA based on proton NMR (a peak at 1.24 ppm IPA ester content). In addition, the final product structures contained lactone (peaks at 1.47 and 1.39 ppm), which can come from both itaconic acid and acrylic acid. Sample 46
[0251] Polymer sample 46 was also synthesized as described in sample 45, varying solvent and solvent proportion. The monomeric components for these samples are shown in the Table below. All polymers contained partial esterification and traces of lactone structures in the main part.
Example 3
[0252] The calcium binding capacity of homopolymers of itaconic acid at various pH levels of 11.5, 9.5 and 8.5 of calcium was tested. Higher Ca-binding numbers are preferred for chelation. The data show that pH plays a role in the Ca-binding capacity of polymers. Improved polymers show comparable or improved performance to comparative polymers and chelators.
[0253] Table 4 shows the Ca-binding capacities of the improved polymers prepared at different pH levels. Higher Ca-binding capacities are preferred. Sample 1 polymer has better binding capacity than commercial CL6 itaconic acid polymer.
[0254] Table 5 shows the Ca-binding capacities of the IA-AA copolymers at pH 8.5, 9.5 and 11.5. Sample 5 has much higher binding capacities compared to comparative sample II at pH 11.5.
[0255] Ca-binding capabilities of commercially available chelators are shown in Table 6.
[0256] The chelate precipitation behavior is markedly different depending on the polymer composition. The precipitate of homopolymers AA (CL1-CL5) after chelation with Ca is viscous and undesirable, whereas the precipitated chelate from the titration of the IA/AA copolymer is powder.
[0257] Table 7 shows the Ca-binding capabilities of IA-AA-AMPS terpolymers. Although the Ca-binding capacities of terpolymers are less than the capacities of AA-IA copolymers at pH 11.5, these polymers show very little precipitation after chelation with Ca. other terpolymers and copolymers IA-AA at pH 8.5. Table 4
Table 5


[0258] The binding capacity of Ca2+ at pH 10.5 for partially esterified itaconic acid copolymers is summarized below in the table. All copolymers of the invention at a pH of 10.5 have superior Ca-binding capabilities compared to commercial PAA polymers (CL1 and CL2). Copolymer samples from 1 to 16 showed equal or superior performance compared to commercial CL11 and CL12 copolymers. Table 5A
Table 6: Commercial chelators

Table 7
Example 4 - automatic dishwashing formulations: 4A. Liquid detergent gel for automatic dishwashing
[0259] Formulations D1-D6 listed in Tables 8 and 9 are various liquid automatic dishwashing detergent formulations. Table 8 contains bleach formulations. Table 9 contains formulations with enzymes. These formulations are prepared by the following general process: 1) Add water to a mixing tank 2) Sieve through Carbopol 676 polymer while mixing until hydrated 3) Add the comparative or inventive chelator during mixing 4) Add NaOH solution during the mixture 5) Add sodium carbonate, sodium bicarbonate, sodium sulfate, sodium citrate, propylene glycol, and sodium silicate during mixing 6) Add Sodium Hypochlorite if necessary 7) Premix CaCl2 solution with enzymes and add the pre -mixing to tank during mixing, where enzymes are used 8) Subsequent dose of bleaching system and corresponding enzyme(s) mixed. Proceed with quick mixing to ensure good distribution of ingredients.
[0260] The automatic dishwashing liquid (ADL) formulations in Table 8 are prepared by using 2.0 - 5.0% by weight of active polymer or reference builders and 1% by weight of chlorine.

* The formulation separated in 48h, has already been used in the performance test by a good mixture before each cycle; Table 9
1 Suitable amylases can be purchased from Novozymes, eg amylase sold under the tradename Stainzyme Plus® or from Genecor, sold under the tradename Powerase®
[0261] Dishwashing Test Using ADL (Automatic Dishwashing Liquid) - US Conditions
[0262] ADLs containing copolymers are selected to test the ability to detect and prevent stains on plastic cups and utensils during machine dishwashing in 300 ppm water. Testing is done according to "CMSA Detergents Test Methods Compendium" Third Edition, 1995; ASTM D3556-85(2009) "Standard Test Method for Deposition on Glassware during Mechanical Dishwashing", as described below.
[0263] Utensils: Clear glass cups without design (4), Clear plastic cups without design (4), 10 inch diameter Dinner Plates (6), 7 inch saucer (4), Knives (6), Forks (6), Spoons (6), Non-fat Milk Powder, Margarine, Dishwashers, Laboratory Scale (0.1 gram sensitivity), Citric Acid, Calcium Chloride Solution. All items are thoroughly cleaned and ensured to be stain free before starting a new test.
[0264] Procedure: The dirt is made up of 80% margarine and 20% powdered milk. The margarine is heated until melted (no more than 100°F). Powdered milk is slowly sifted into the melted margarine and mixed well. 5 grams of dirt are distributed on each of the 6 dinner plates by spreading with your fingers or a spatula. In the lower basket of the dishwasher, 6 dirty dinner plates and 4 saucers are evenly distributed. In the top basket, the cups are evenly distributed. All cutlery is placed in a closed basket. The main container of the dishwasher is filled with 60 grams of detergent and the prewash container is filled with 18 grams of detergent. The dishwasher is started to run on a normal cycle with hot water (52°Celsius). After washing is complete, the glass and plastic cups are removed wearing gloves and checked in a light box made especially for stains and films. A system determined by the method classifies the cups for stains and skin:

* Taken from CSMA Detergents Division Test method Compendium - Third Edition - 1995 - p. 1-6. The test is repeated 5 times with each ADL using the same set of articles. Lower ranking indicates better performance on a particular attribute.
[0265] Table 10 shows the rates for stains and films on the glass cups after the fifth wash cycle in 300 ppm hard water. Table 10
*tested using 45ml of total detergent in the main wash and no prewash
[0266] Table 10 shows that the performance of the chlorine gel formulation in self-cleaning dishes (D5) with 2.5% of the Sample 8/CL9 combination is better than the gel of (D4) with 3.5% of the combination CL3 + CL9 in plastic and glass. The performance of gel with 2% of sample 19 is significantly better than with gel D4 with 3.5% of CL3 + CL9 combination under similar conditions.
[0267] From the tables presented above, it is evident that the performance of the ADL formulation in dishwasher tests of 300 ppm is affected by the type of chelating agent and the level of use. The improved polymer of the present technology shows significantly better performance in glass and plastic compared to the CL6 comparative sample in D3 at 3.5% use level. It performs better on glass than on plastic with barely visible stains and films after cycles of 4 or 5 washes. Powdered detergent for automatic dishwashing 4B
[0268] Formulations D7-D12, listed in Table 11 are various automatic dishwashing detergent powder formulations containing detergent with or without enzymes. These formulations are prepared through the following process: 1) Add sodium carbonate and sodium sulfate to a granulator. A food processor is used for these examples. 2) Gradually add IA-AA copolymer (Sample 7 or Sample 8) of the present invention to selected granulator under operating condition until desired particle size is reached 3) Add powdered sodium silicate 4) Add SLF-18 followed by by rapid mixing 5) Drying and/or optional screening of the granules 6) Post-dose of the bleaching system and corresponding enzyme(s) mixed together. Proceed with quick mixing to ensure good distribution of ingredients. Table 11 (% by weight)

Suitable 1 amylases can be purchased from Novozymes, for example amylase sold under the tradename Stainzyme Plus® or from Genencor sold under the tradename Powerase®. 4C Liquid Detergent Tablet for automatic dishwashing
[0269] The D13-D16 formulations listed in Table 12 are various automatic dishwashing liquid detergent tablet formulations with or without enzymes. These formulations are prepared by the following process: 1) Mix dipropylene glycol, SLF-18, glycerine, amine oxide, until homogeneous 2) Add IA-AA copolymer of the present invention during mixing 3) Sieving Carbopol 674 Polymer while mix until hydrated 4) Add Triethanolamine while mixing 5) Add all remaining ingredients and mix well. 6) Fill the PVA packages with 20 grams of product Table 12 (% by weight)
Suitable 1 amylases can be purchased from Novozymes, for example, amylase sold under the tradename Stainzyme Plus® or from Genencor, sold under the tradename Powerase®.
[0270] Additional unit dose of automatic dishwashing detergent powder was prepared by dry blending the ingredients shown in table 13. Plurafac SLF 180 liquid was pre-mixed with sodium carbonate and sodium sulfate. When liquid builders were used, the amount was calculated based on the active level in the desired formulation.

Performance tests for automatic dishwashing (European conditions):
[0271] The unit dose formulations were tested in GE dishwashers using hard water at 400 ppm. The temperature of the water supplied to the dishwasher was 48-52°C. The calcium:magnesium ion ratio was 2:1 in hard water. The dishwasher was loaded with glass cups and plastic cups, 6 plates, 4 saucers and cutlery (4 spoons, 4 forks, 4 knives). 1) 25 grams of IKW Ballast Dirt (CFT DM-SBL) was placed in a glass, and placed on the top shelf of the dishwasher. 2) a dose of detergent was placed in the detergent compartment. 3) 'Normal' cycle with 'dry-heated' option has been selected. 4) After each wash, photos of all glasses were taken in a light box, and the glasses were sorted for stains and films according to the procedure set out above for liquid automatic dishwashing detergent. 5) The same dishwasher was used to complete all 5 wash cycles with one formulation. 6) After washing was completed, the glass and plastic cups were removed wearing gloves and checked in a light box made especially for stains and films. A system determined by this method classifies the glasses for films and stains:
* Taken from CSMA Detergents Division Test method Compendium - Third Edition - 1995 - p. 1-6. The test is repeated 5 times, with each unit dose of ADW using the same set of articles. The data presented in the tables below are the sum of the ratings for spots and skins. Lower ranking indicates better performance on a particular attribute.
[0272] Table 14 presents the sum of ratings for stains and glass and plastic films after 5 washes for P1-P6 powder formulations (unit dose size = 20g) Table 14: Automatic dishwashing performance results after 5 washes for formulations shown in table 19

[0273] Table 14 shows that for automatic dishwashing formulation chassis containing 15% or 30% sodium citrate, the performance for stains and films improves with an increase of 3% to 13% of Sample 27b. Table 15: 15% Citrate, 3% Polymer
Table 16: 15% Citrate, 3% Polymer

[0274] The performance of formula P1 with sample 27b, as indicated in tables 15 and 16, is better than formula CP1 with CL4 (acrylate polymer builder) and CL9 (anti-film polymer) for stain and film on glass and plastic.

Table 18: 30% Citrate, 13% Polymer


[0275] Based on the formulations and data in tables 17 and 18, P6 has better performance for films and stains on glass; and for stains on plastic compared to CP6A which contains CL4 + CL9 at the 13% level. It also performs better compared to the CP6B comparative formulation containing CL6.
[0276] Table 19 shows comparative formulations CP3a to CP3e containing 13% of comparative builders and 0.3% of CL13. CL13 has been incorporated as a polymeric anti-redeposition agent. The formulations were comparative examples for P3 which is a formulation with 13% Sample 27B and 15% citrate. Table 19: Comparative examples of formulations containing competitive builders for self-cleaning performance testing

Table 20: Results for stains and films on plastic and glass after 5 washes in self-dishwashing performance test using formulations from Table 19. (Comparative examples for P3)

[0277] Tables 19 and 20 show that formulation P3 with 13% of Sample 27B is superior in self-cleaning performance compared to comparative builders CP3a to CP3e. The addition of anti-redeposition polymer CL13 is expected to improve performance in the dishwasher. But the combination of builders with CL13 does not show improvement over a similar formulation containing only Sample 27B as a multifunctional builder. Table 21: Solvent polymerized copolymer vs. CL6

Table 22: Performance for ADW powder stains and films with Sample 45 and CL6 after 5 dishwashing cycles

[0278] Tables 21 and 22 show that the ADW powder formulation with Sample 45 provides better performance for stains and films on glass compared to a commercially available CL6 formula.
[0279] The formulations in Table 23 were prepared by dry blending the ingredients. Commercially available polymer builder solutions were spray dried to create a fine polymer powder for incorporation into the formula.


[0280] P8-P12 automatic dishwashing powder formulations are examples of high performance formulations for European dishwashing conditions. P8 and P9 were formulations with polymers of the invention and citrate with 5% nonionic surfactant. P10 was a formulation that contained the polymer of the invention, in combination with citrate and CL7. P11 is an example that contains the polymer of the invention and citrate with a reduced level of non-ionic surfactant and no phosphonate. P12 contains inventive polymer (Sample 27b) at 20% use level and no phosphonate. CP8 is a comparative example for P8, with CL10. These examples and the results in Table 24 help to demonstrate the various combinations of ingredients commonly used with the polymer of the invention to achieve better cleaning performance on various substrates in multiple cycle film tests.
[0281] Multiple cycle film tests were performed on each prototype using 20 g unit dose per wash cycle. Standard Method Fresenius 2009 Version 01 was used to test the prototypes on a continuous Miele machine. The hardness of the water was 21°d and the temperature was 65°C. 50 g of a standard frozen ballast soil consisting of tomato ketchup, mustard sauce, potato starch, benzoic acid, egg yolk, margarine, milk and water was used in each wash. The machine was loaded with glass cups, melamine and glass plates, and stainless steel cutlery. Each prototype was rated in 30 wash cycle tests, and film was rated on glass, cutlery and plates every 10, 20 and 30 wash cycles, using the 8-point rating scale, where 8 indicates no skin and 1 indicates strong skin presence.

[0282] The results in Table 24 show that prototype formulations performed better than commercial finished products after 30 wash cycles. In addition, P8 performed better than CP8 after 10, 20, and 30 glass cup and plate washing cycles. Enzyme Gel Formulations
[0283] Enzyme containing self-dishwashing gel was prepared using the formulation in Table 25. Table 25: Enzyme containing self-dishwashing gel "E1"


[0284] The enzyme gel from table 25 was tested in hard water at 400 ppm using IKW ballast dirt. The rating for stains and films after 5 wash cycles is shown in table 26 (a smaller number is preferable). Table 26: Performance for stains and films on glass and plastic after 5 washing cycles

[0285] Table 26 shows the washing performance of ADW from table 25, compared to a dishwashing product containing similar enzyme containing CL8. ADW Powder Formulation for Efficient Tea Stain Removal
[0286] Uniform automatic dishwashing powders were prepared by mixing the ingredients shown in Table 27. Plurafac SLF 180 liquid was premixed with sodium carbonate and sodium sulfate.


[0287] Tea stain removal method: Strips pre-stained with tea (DM-11 from the Center for Testmaterials (CFT, Netherlands) were used for this test. Unit dose formulations were tested in GE dishwashers using 400 ppm hard water. The temperature of the water supplied to the dishwasher was 48-52°C. The Calcium:magnesium ion ratio was 2:1 in the hard water. The machine was loaded with glass cups and plastic cups, 6 plates, 4 saucers, and silverware (4 spoons, 4 forks, and 4 knives. 1) The L*, a*, b* color values of the tea strips were measured beforehand using a Hunter colorimeter. ) a stained strip of tea was placed on the top shelf of the dishwasher. 3) 25 grams of IKW Ballast Dirt (CFT DM-SBL) was placed in a glass, and placed on the top shelf of the dishwasher. 4) a dose of detergent was placed in the detergent compartment. 5) 'Normal' cycle with 'dry by heat' option has been selected and the dishwasher has been started. 6) After washing, L*, a*, b* values were measured using Hunter Colorimeter. 7) Each formulation was tested 3 times using the steps above with a new tea-stained strip each time.
[0288] Index spot removal for each strip was calculated using the following equation: RI = V[(LI - Lz)2 + (at - af}2 + - bz)2] Where RI = removal index of tea stain and ief subscripts denote initial and final readings of L*, a*, b* from the Hunter colorimeter. Table 34 shows the average stain removal for each formulation. Table 28

[0289] Tables 27 and 28 show that the use of Mn-based bleach catalyst, with sodium percarbonate in the formulation, efficiently removes tea stain in the dishwasher. Tea stain removal from formulations with MnOx (P14, CP14) and MnTACN (P15 and CP15) indicate that stain removal is better when Sample 27b is present in the formulation as the builder, versus the CL7 builder. Color care in dishwashers:
[0290] It is desirable that prolonged use of detergent for self-cleaning dishes does not damage the colored patterns on the glass cups. Some builders may cause color fading or smearing which may become evident after continuous use of 50, 100 or 200 wash cycles. The color care property of the polymer of the invention and CL7 as a comparative material was determined using the following method: 1.) 1% chelator solution was prepared in deionized water. Sample 27b and CL7 powder were used. 2.) 2 identical glass glasses with exactly the same colored design of red, yellow, orange and green stripes are cleaned with mild soap and water. The cups were 5 inches high. 3.) Each cup was soaked in 1 L of chelating solution in a beaker. The precipitate cups were placed in the oven at 45°C for 5 days. These conditions were made to accelerate the harmful effects of the builder / chelator. 4.) After 5 days, the cups were removed from each solution, washed with water and analyzed visually and by light microscopy. Thin polymeric coating was stripped from colored stripes and analyzed by scanning electron microscopy (SEM) and energy dispersion X-ray spectroscopy (EDS).
[0291] Table 29 summarizes the visual and microscopic analysis of the surfaces of glass cups soaked in aqueous solution of CL7 and polymer 27b of the invention after 5 days at 45°C.
*A piece of film that did not cover the pigmented stripe was also analyzed by EDS as a baseline, and was found to be clean, without any pigment or metal.
[0292] Microscopy and elemental analysis confirm the etching ability of CL7 color by interacting with the pigments and/or metals in the pigments. The inventive polymer 27b is significantly lighter in color, which can translate to the durability of colored designs after prolonged use in the dishwasher. Example 5 - Hard surface cleaner
[0293] Hard surface cleaner: The best polymers of the present invention can be used as a chelating agent in a hard surface cleaner as shown in Table 30. The formulation is prepared by the following process.
[0294] In deionized water, Novethix L-10 polymer is added and mixed well. Sample 7 of polymer is added and the formulation is neutralized to a pH of 88.5 using triethanolamine. Surfactants and remaining ingredients are added during mixing. Table 30. All Purpose Cleaner Formula

[0295] Example 6 - laundry detergents Composition Powder Base for Laundry Detergent by Dry Spray 6A
[0296] Examples L1-L4 listed in Table 31 are various laundry detergent powder formulations. The other components such as enzymes, bleaching agent, fragrance, coloring and other minor ingredients can be mixed with the base powders. Powder suspensions of these formulations were prepared by the following process: 1) Add water, IA / AA copolymers of the present invention, alkylbenzene sulfonic acid, and coconut fatty acid to a mixing tank 2) Neutralize the system with NaOH solution 3) Add all remaining ingredients while mixing until smooth. 4) Pump the slurry into the spray drying tower to form the detergent powder. For the laboratory process, the paste from step 3 was placed in a non-metal container and microwaved until dry; followed by grinding to the desired size. (Powders prepared by the laboratory process have higher bulk density than spray dried powder. But it is good for evaluating detergency) 5) Add more doses of other ingredients such as enzyme granules(s), bleaching agent , perfumes, dyes or other beneficial ingredients. Follow with quick mixing to ensure good distribution of ingredients. 6) The product from step 5 can be further processed to be compressed into tablets or packaged in PVA packages. Table 31

Base Powder Composition for Laundry Detergent Using Agglomeration 6B
[0297] The L5-L8 formulations listed in Table 32 are various base powder formulations for laundry detergent. The other ingredients such as enzymes, bleaching agent, perfume, dye and other minor ingredients can be powders mixed with the base powder. Suspensions of these base powder formulations were prepared by the following process: 1) Add sodium carbonate, sodium sulfate to a food processor: mix briefly for good distribution 2) Add IA-AA copolymer of the present invention, sulfonic acid of alkylbenzene, ethoxylated fatty alcohol and coconut fatty acid, one at a time, while mixing to the desired particle size. 3) Add powdered sodium silicate, maleate/acrylate copolymer powder and mix: mix briefly until smooth 4) Add more doses of other ingredients such as enzyme granules(s), bleaching agent, perfume, dyes or other beneficial ingredients. Followed by quick mixing to ensure good ingredient distribution. 5) The product from Step 4 can be further processed to be compressed into tablets, or packaged in PVA packages. Table 32


[0298] Laundry detergency tests: Laundry powder formulations containing copolymers of the invention are selected to test cleanability, either under different washing conditions or with low efficiency washing products in 300 ppm hard water , using a Tergotometer. The test formulations were used to wash pre-soiled "test fabrics" together under standard conditions. Soiled fabrics were used to provide dirt to the system and also to measure the cleaning effectiveness of the formulations. After washing, the test fabrics were rinsed, dried, and their reflectance measured. Table 33: Powder Detergent Formulations
5 of Stepan
[0299] Hard water stock solution - Prepare a hard water stock solution by dissolving 4.41 g of calcium chloride dihydrate (CaCl2-2H2O) and 2.03 g of magnesium chloride hexahydrate (MgCl2-6H2O) in deionized water to a volume of 1 L. This solution contains 4000 ppm hardness (expressed as calcium carbonate) with a Ca:Mg molar ratio of 3:1. The 300 ppm solution is made by taking 75 ml of the main solution and diluting with water to 1 L.
[0300] Test Fabrics: Test soiled fabrics (detergency monitors) were STC EMPA 101, 3 in. X 4 in. on cotton samples soiled with olive oil and carbon black. Three soiled test fabrics were included in each wash test container. Wash Test Procedure 1) Allow bath in Tergotometer to equilibrate to 88-90°F 2) Add 1L of 300 ppm wash water hardness to each container and allow to equilibrate to 88-90F 3) Add 10 g of detergent into each container and shake for 1 minute 4) Add measured samples to each container 5) Wash samples for 10 minutes 6) Pour out the wash water and squeeze the samples 7) wash the container and use DI water 8) Add 1L to 300 ppm of hard water for each container and allow to equilibrate to 88-90F 9) Open the samples and place in the same previous container 10) Wash for three minutes 11) Squeeze the samples, unfold and allow to dry 12) Measure the samples again during drying
[0301] The reflectance values of the samples are measured (full spectrum with ultraviolet excluded) before and after washing. Each sample was measured three times and then averaged.
[0302] Particular Dirt Removal Assessment (Measurement of Dirt Removal Index ("SRI"), from ASTM D3050-05): The dirt particle removal evaluation was performed from a single wash in hot water to 32.2°C (90°F). A Hunter reflection meter was used to measure L, a, and b. These values were considered to calculate SRI Index values with the following equation: SRI = 100 - [(Lc-Lu)2 + (ac - aw)2 + (be- M2]1/2 Where: L = reflectance ( white / black), a = redness / green, b = shade of yellow / shade of blue, C = fabric without dirt, and W = fabric dirty.
[0303] Table 34 shows the SRI values after completing the washing of soiled EMPA 101 cotton samples. The higher SRI number indicates that the detergent formulation (Lll) with the polymer of the invention (Sample 7) is significantly better than the comparative detergents L9 (non-chelating) and L10 (with STPP) for removing dirt in hard water at 300 ppm. Table 34

6C - Paste formulation for washing clothes
[0304] Clothes washing (LS) paste formulations containing copolymers of the invention are selected to test multifunctional (processing aid / chelating) capability. Table 35 summarizes the formulation composition of all pastes at 40% water content.
[0305] Procedure to produce the paste: To the mixture of surfactant and water, polymer was added and neutralized with NaOH. After the polymer was completely neutralized, sodium carbonate was added in order to prevent the formation of CO2. The rest of the ingredients were then added and carefully mixed, while the temperature was maintained between 40°C and 50°C, preferably at 45°C. Viscosity was measured by a TA AR-G2 Rheometer with parallel plate.

*Large amount was redone and resulted in different % solids from those cited in the example preparation
[0306] From the above data, polymer samples 6 and 8 were observed to significantly reduce viscosity at 25°C, 40°C and 50°C, compared to the control slurry without polymer addition. All IA / AA copolymers of the present technology (5, 6, 8 and 19) in Table 35 had a viscosity lower than 25°C than the control paste at room temperature, while the LS5 paste with CL11 polymer had a viscosity much larger than that of the polymer-free control paste. This indicates that IA/AA copolymers in this invention may have an advantage in handling pulp as a processing aid at the lower temperature.
[0307] Table 36 summarizes the viscosity and formulation composition of all pastes tested at various shear rates at 50°C.

*Large amount was redone and resulted in different % solids from those cited in the example preparation
[0308] The viscosity data in table 36 show that the pastes with IA / AA copolymers (5-8, 19 and 22) had a lower viscosity at a shear rate of 100 1 / s, 250 1 / s and 500 1 / sa 50°C than the polymer-free control slurry (LS control). Lower viscosity of suspensions under different shear rates can make slurry treatment easier. loop test results
[0309] To investigate the change in viscosity and stabilization of pastes, a loop test with 2 complete cycles was performed at 60°C using the concentric concentric cylinders at a shear rate of 1 (1 / s) to 500 (1 / s) at 60°C
*Large amount was redone and resulted in different % solids from those cited in the example preparation
[0310] The results in Table 37 show that the IA/AA polymer from Sample 8 had a lower viscosity compared to CL12 in the loop test. The control slurry (no polymer) had a higher viscosity and increased viscosity throughout the cycles, indicating a potential slurry instability problem.
[0311] Pastes using alkylbenzenesulfonic acid (linear alkylbenzene sulfonic acid - "LAS acid") to form sodium alkylbenzenesulfonate in situ with an aqueous NaOH solution were made. Following are the results of suspensions prepared from LAS acids. The water level in the suspensions was less than 33%.

*Large amount was redone and resulted in different % solids from those cited in the example preparation
[0312] The results in Table 38 show that the suspensions with IA / AA copolymers (Samples 6, 8 and 19) showed much lower viscosity than the control paste. The suspensions with polymers of the invention also had a lower viscosity compared to CL6 and CL2.
[0313] Formulation of laundry paste with esterified polymer:
[0314] Clothes washing paste (LS) formulations containing copolymers of the invention are selected to test multifunctional capability (processing aid / chelating). Table 39 summarizes the formulation composition of all pastes at a water content of <35%.
[0315] Procedure for making the paste from LAS acid: to a mixture of water and NaOH, polymer was added. After the polymer was neutralized, LAS acid was gradually added to form sodium detersive LAS, followed by addition of sodium carbonate. The remainder of the ingredients was then added and carefully mixed, while the temperature was maintained between 40°C and 50°C, preferably at 45°C. loop test results
[0316] To investigate the change in viscosity and stabilization of pastes, a loop test with 2 complete cycles was performed at 60°C using concentric concentric cylinders from 1 to 500 1 / s to 60°C, two cycles. Table 39



[0317] The results in Table 39 show that samples 30, 32 and 34 of partially esterified IA / AA polymer had a lower viscosity compared to the control (no polymer) in the loop test. The viscosity of the control slurry (without polymer) increased over the cycles, indicating a potential problem of slurry instability. The suspensions with polymers of the invention also had a lower viscosity compared to CL2.
[0318] Table 40 below summarizes the viscosity data of pastes that have 25% H2O.





[0319] The results in tables 40A and 40B show that samples 31, 37, 38, 40, 42 and 44 of the partially esterified IA / AA copolymers had lower viscosity compared to the control (ELS00 or ELS000 - without polymer). Pastes with polymers of the invention also had a lower or equal viscosity when compared to CL1.
[0320] Table 41 below presents a summary of the viscosities of pastes with a lower water content of 20% H2O. Table 41: Viscosity of pastes with 20% H2O

Example 6d: Dispersion of hydrophobic and hydrophilic particles
[0321] The dispersibility was tested through the use of hydrophobic carbon black particles and hydrophilic kaolin clay particles at room temperature. Water hardness is 120 ppm as CaCO3 and polymer concentration is 10 ppm. To a glass vial, both the polymer solution and the hard water solution were added and mixed to obtain the correct concentration and then particulate dirt was added. The solution was mixed for 5 min. to form dispersion. Then, the transmission (T%) or Turbidity (NTU) of the dispersion over a given period of time was measured. The lower at%, the greater the dispersability. With NTU, a higher NTU value indicates greater scattering capability. The results are listed in Table 42. Table 42: Stability of Dispersion at Ambient Temperature
Water hardness is 120 ppm and polymer concentration is 10 ppm
[0322] Samples 32 and 37 showed better carbon black dispersion capacity than CL6 and CL4, and sample 32 showed better kaolin clay dispersion capacity than CL6 and CL4. Example 6e: Anti-fouling
[0323] As an Anti-scaling index, the inhibition of growth of CaCO3 crystals was evaluated at room temperature by measuring turbidity. Polymer solution and Na2CO3 solution were mixed together, and then hard water was added to generate the final solution which has a water hardness of 300 ppm and 0.15% Na2CO3. The solution was kept mixed, and turbidity was monitored over time. The lower the turbidity (NTU), the greater the CaCO3 crystal growth inhibition effectiveness. Some results are listed in the Table below. Evidently, the polymer of the invention showed better crystal inhibition of CaCO3 than CL6 and CL5. Table 43: Antifouling (Crystal Growth Inhibition)

[0324] Each of the above documents is hereby incorporated by reference, including all prior uses, whether or not listed above, from which priority is claimed. Mention of any document does not constitute an admission that such document qualifies as prior art, or constitutes general knowledge of the person skilled in the art, in any jurisdiction. Except in the Examples, or where otherwise explicitly indicated, all numerical quantities in this specification that specify quantities of materials, reaction conditions, molecular weight, number of carbon atoms, and the like, are to be understood as modified by the word "about in". It is to be understood that the upper and lower amounts, ranges, and limits set forth herein may be independently combined. Likewise, ranges and amounts for each element of the present invention may be used in conjunction with ranges or amounts for any of the other elements. As used herein, the transitional term "comprises", which is synonymous with "including", "containing", or "characterized by", is inclusive and does not exclude method steps or additional unquoted elements. However, in each citation of "comprising" referred to herein, the term is also intended to cover, as alternative modalities, the terms "consist essentially of" and "consisting of", where "consisting of" excludes any element or step unspecified, and "consisting essentially of" allows the inclusion of additional unnamed elements, or steps that do not materially affect the basic and novel characteristics of the composition or method under consideration.

权利要求:
Claims (13)
[0001]
1. Itaconic acid copolymer characterized by comprising monomeric units derived from itaconic acid and comonomer units derived from at least one of acrylic acid, methacrylic acid or salts, esters and anhydrides thereof, 2-acrylamido-2-methylpropane sulfonic acid (AMPS ) or salts thereof, and combinations thereof, wherein said copolymer comprises less than 0.5% by mol, based on the number of monomeric units in the copolymer, of tri-substituted vinyl monomer impurities, and wherein no more than that 5% by mol of the total carboxylic acid groups from all monomers are neutralized, and that additionally the copolymer has a number average molecular weight (Mn) of 500 to 100,000.
[0002]
2. Polymer according to claim 1, characterized in that it comprises more than 25% by mole of monomers derived from itaconic acid and less than 75% by mole of monomers derived from at least one of acrylic acid, methacrylic acid or salts, esters and anhydrides thereof, AMPS or salts thereof and combinations thereof.
[0003]
3. Polymer according to any one of the preceding claims, characterized in that it comprises monomeric units derived from itaconic acid from 35% to 60% in mol and monomeric units derived from acrylic acid from 40% to 65% in mol.
[0004]
4. Polymer, according to any one of the preceding claims, characterized in that it comprises monomeric units derived from itaconic acid from 60% to 70% in mol and monomeric units derived from acrylic acid from 30% to 40% in mol.
[0005]
5. Polymer according to any one of the preceding claims, characterized in that it comprises monomeric units derived from itaconic acid and (meth)acrylic acid from 90% to 99.9% in mol and monomeric units derived from AMPS from 0.1% to 10 % by mol.
[0006]
Polymer according to any one of the preceding claims, characterized in that the copolymer is from 0.1% to 60% esterified.
[0007]
7. Process for preparing a polymeric solution of itaconic acid copolymer, as defined in any one of the preceding claims, characterized in that it comprises: preparing, in an aqueous medium, a monomeric solution of itaconic acid and at least one of the comonomers, as per defined in claim 1, and polymerize, at a polymerization temperature greater than 60°C, in the presence of 0.01% to 5% by mol of polymerization initiator, based on the total amount of said monomers, wherein the mixture of The reaction is free of metallic promoters, and which additionally comprises a step of pre-neutralizing said monomeric solution with less than 5% by mol of a neutralizer per total acid group present in the monomeric solution.
[0008]
8. Process for preparing a polymeric solution of itaconic acid copolymer, as defined in any one of claims 1 to 6, characterized in that it comprises: preparing, in an aqueous medium, a monomeric solution of more than 25% by mol of itaconic acid monomer , with less than 75% by mol of a comonomer composition comprising acrylic acid, AMPS or a mixture thereof, wherein said comonomer composition is added to said itaconic acid monomer, over a period of 2 to 16 hours, at a polymerization temperature greater than 60°C in the presence of 0.01% to 5% by mol of polymerization initiator, based on the total amount of said monomers, wherein the reaction mixture is free from metallic promoters, said comonomer composition and at least half of said initiator being added separately and essentially continuously, over said period to said itaconic acid monomer, in solution in said medium, and comprising the additionally a step of pre-neutralizing said monomeric solution with less than 5% by mol of a neutralizer per total acid group present in the monomeric solution.
[0009]
9. A polymeric formulation characterized in that it comprises a copolymer as defined in any one of claims 1 to 6.
[0010]
A polymeric formulation according to claim 9, characterized in that it comprises less than 0.5% w/w of unreacted monomer, based on the total weight of copolymer present in the solution.
[0011]
11. Polymeric formulation according to any one of claims 9 or 10, characterized by a pH greater than 1.8.
[0012]
12. Dishwashing detergent, a laundry detergent, a hard surface cleaner or a cosmetically acceptable formulation characterized by comprising the polymeric formulation as defined in any one of claims 9 to 11.
[0013]
13. Method to chelate metal ions from a solution characterized in that it comprises adding to a solution containing metal ions, or subject to containing metal ions, a copolymer of itaconic acid, as defined in any one of claims 1 to 6.

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法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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

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2020-11-03| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-07-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-09-14| 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 14/03/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201361792244P| true| 2013-03-15|2013-03-15|

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US61/792,244|2013-03-15|

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PCT/US2014/027879|WO2014143773A1|2013-03-15|2014-03-14|Itaconic acid polymers|

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