CN100491426C

CN100491426C - Hydrophobically modified polymers as laundry additives

Info

Publication number: CN100491426C
Application number: CNB2003801072628A
Authority: CN
Inventors: Z·宋; J·毛; H·罗韦; U·门格
Original assignee: Ciba Spezialitaetenchemie Holding AG
Current assignee: BASF Schweiz AG
Priority date: 2002-12-23
Filing date: 2003-12-15
Publication date: 2009-05-27
Anticipated expiration: 2023-12-15
Also published as: CN1729217A

Abstract

The present invention is directed to polymeric compounds comprising a main backbone derived from at least the following monomeric components: (1) 20 to 99.9% by weight, preferably 50% to 99% by weight, of at least one cationic monomer according to formula (I), and (II) 0.1 to 80% by weight of a hydrophobic unsaturated nonionic monomer that polymerizes in the presence of an initiator, optionally a water-soluble monomer (III) different from either monomer (I) and monomer (II), and optionally a crosslinking agent (IV). Said compounds are particularly useful to overcome the problem of dye bleeding and/or dye transfer in laundry processes.

Description

Hydrophobically modified polymers as laundry additive

Background technology

People have carried out various trials and have gone to overcome dyestuff bleeding and/or dye migration problem in the laundry processes.Term " dyestuff bleeding " thus typically referring in laundry processes some dyestuff comes off from fabric and causes the fact of fabric fading.For cellulosic fabric with nonactive dyestuff such as substantive dyestuff, vat dyes, azoic dyestuff and sulfur dyeing, such phenomenon as if outstanding more (D R.Warring and G.Hallas, " The chemistry and applicationof dyes ", Plenum Press, New York, 1990).The dyestuff that comes off from fabric is commonly called " gamut dyestuff " and the process that overcomes the dyestuff bleeding is commonly called " dyestuff fixing ".

On the other hand, also should be noted that from fabric and come off and be present in gamut dyestuff the washing lotion.Otherwise, cause look to pollute thereby such gamut dyestuff may be deposited on fabric face again.This process is commonly called " dye migration inhibition " and/or " staining inhibition ".

So existing adding after detergent for washing clothes and/or the rinsing in the product to help prevent the dyestuff bleeding on the fabric is the demand of fixed additive, perhaps exists preventing the gamut dyestuff demand of sedimentary material again.Be actually and overcome these problems and done a large amount of effort, the material that can help to address these problems is commonly called laking agent, dye transfer inhibitor, anti-deposition agent, dye scavenging agent and/or staining inhibitor.

For example, United States Patent (USP) 3694364 discloses the purposes of the uncle's polyamine that plays the effect of anionic dyestuff scavenging agent.On the surface of substrate material such as cellulose materials, described cellulose materials is gossypin, cellulose sponge of for example any type of cotton, purifying etc. to described polyamine by chemical fixation.For fixing polyamine, cotton substrate has been carried out modification by the phosphorylation and the chemisorption of polyamine.Uncle's polyamine and the quaternary ammonium compound purposes as the dye scavenging material is disclosed in relevant United States Patent (USP) 3673110.The Edwards patent disclosure of back other dye scavenging thinner is fixed to method on the cellulose materials matrix, it is undesirable with organic dye that described method also is used for controlling bath of liquid, for example in the time of the washing textiles.For example, the hydroxylation surface of cellulose materials by chemical modification to set up the anionic functional group.Each anionic functional group can both the Chemical bond nitrogen compound, for example above-mentioned disclosed dye scavenging immunomodulator compounds.

Except to loomage surface modification preventing the dye migration, also the expendable material that absorbs the gamut dyestuff can be joined in the laundry item, thereby prevents on valuable and the fabric paid close attention to deposition again.This material is made the form of fabric usually, and with it is believed that the various chemical treatments that can from washing lotion, attract dyestuff.Disclose a kind of dye scavenging goods in the United States Patent (USP) 3816321 of Kleinschmidt, described goods are used to remove the anionic dyestuff of the DYED FABRICS release that just is being washed, to prevent dye migration in laundry processes.These dye scavenging goods comprise support substrate such as polyurethane material, on support substrate chemical bonding the dye scavenging compound.Described dye scavenging compound comprises poly quaternary ammonium compound.

United States Patent (USP) 4380453 discloses N-three prevailingly and has replaced ammonium-2-hydroxyl-3-halopropyl compounds and the epoxypropyl ammonium salt purposes as the dye scavenging immunomodulator compounds.Preferred dye scavenging immunomodulator compounds is the glycidyl trimethyl ammonium chloride, and it is used for by the cellulose materials matrix absorption or is immersed in wherein.The cellulose materials matrix of gained is according to the conventional washing machine that openly is suitable for washing clothes, with eliminate from washing and the rinse water with organic dye, thereby eliminate undesirable clothing variable color that the dye migration owing to other clothing in washing machine causes.

United States Patent (USP) 5698476 discloses the goods that are used to eliminate the external free-pouring dyestuff of using from the laundry washing at random.This laundry article comprises two components, i.e. dye absorbent and dye transfer inhibitor, and they are incorporated in the washing water by support substrate.The dye absorbent chemistry is connected on the support substrate to keep relevant connection in the laundry washing is used.On the other hand, dye transfer inhibitor is discharged into the washing water from support substrate, with uniform distribution during using in the laundry washing.

United States Patent (USP) 5698476 discloses the material that is suitable as the laundry article dye absorbent, comprises that season N-replaces ammonium-hydroxyl-halogenated alkyl compounds such as 2-hydroxyl-3-chloropropyl trimethyl ammonium chloride; Poly quaternary ammonium compound; Amphiphilic polymers; Quaternized starch; Protein; Chitin or its hydrolysed form, chitosan; Lipotril; Polyvinylamine (PVAm); Polymine (PEI); And their combination.Dye transfer inhibitor comprises Polyvinylpyrolidone (PVP), polyvinyl alcohol, polyvinyl imidazol, polyamine-N-oxide compound, cationic starch, magnesium aluminate, hydrotalcite, protein, protein hydrolysate, polymine, Ju Yi Xi oxazolidinone, enzyme, oxygenant, cats product, amphoterics, the propylene oxide reaction product, polyamino acid, the segmented copolymer of alkylene oxide, polyamine, polymeric amide, methylcellulose gum, carboxyl alkyl cellulose, guar gum, natural gum, alginic acid, poly carboxylic acid, cyclodextrin and mixture.

Another method that solves undesirable dye migration problem is that described oxide catalyst can be removed the gamut dyestuff in the washing lotion, thereby prevents to deposit again by the use oxide catalyst.This catalyzer, for example the manganese complex through selecting can be used as special additive and joins in the detergent for washing clothes.

Some polymkeric substance also is found can be used in and prevents that the gamut dyestuff from depositing again.For example, will find in the reference below that polyvinyl pyridine and various derivative thereof and multipolymer are preventing the purposes of dyestuff in depositing again.

United States Patent (USP) 6348441 discloses the method for washing dirty fabric, and described method is used and is formulated as control dye migration and blistered nonaqueous detergent in efficient washer.United States Patent (USP) 5466802 discloses season polyvinyl pyridine derivative as the purposes of anti-dye migration agent.United States Patent (USP) 6306815 discloses season polyvinyl pyridine derivative as the purposes of anti-dye migration agent.United States Patent (USP) 5380447 discloses method and the fabric finishing composition that prevents deposition of dye in the textile finishing operation.United States Patent (USP) 6191098 discloses the polyvinyl pyridine derivative as anti-dye migration agent.United States Patent (USP) 6156829 discloses product and the method for preparing quaternized water soluble vinyl pyridine carboxylic acid salt polymkeric substance.United States Patent (USP) 6271386 discloses product and the method for preparing quaternized water soluble vinyl pyridine carboxylic acid salt polymkeric substance.United States Patent (USP) 6103831 discloses the water-soluble dye complex polymer.United States Patent (USP) 5863879 discloses the dye transfer inhibitor (BASF, vinyl-amine derivative) that is used for washing composition.United States Patent (USP) 6165969 discloses and has contained the unitary quaternary ammonium polymer of vinyl imidazole as the fixation of washing composition post-treatment agent and washing composition and the purposes of color transfer suppressant additive.United States Patent (USP) 5830884 discloses the dye transfer inhibitor of washing composition: the water-insoluble particle, contain the cross-linked polymer of 1-vinyl pyrrolidone and/or 1-vinyl imidazole polymerized unit.

Based on the various derivatives of vinyl pyridine, poly-(vinylpyridine-N-oxide compound) is found to be effective dye transfer inhibitor.United States Patent (USP) 6121223 and 5149456 has been put down in writing the preparation and the application of this compound.

Product based on amine is believed to provide the dye migration rejection.For example, United States Patent (USP) 5827813 has been studied N, N, and N ', N '-four-(2-hydroxypropyl) quadrol is as the purposes of dye transfer inhibitor.Other relates to based on the material of amine and comprises United States Patent (USP) 6251846,6156722 and 6140292 as the reference of the purposes of dye transfer inhibitor.

Except above-mentioned reference, the various enzymes (United States Patent (USP) 5855621) of also having mentioned polyglycosides (United States Patent (USP) 6159921) and having shown peroxidase activity are as dye transfer inhibitor.

With about comparing with a large amount of outwardly reference of various materials that the dye migration rejection is provided and uses thereof as detergent for washing clothes, seem considerably less about the reference that can help prevent dyestuff material of bleeding from the fabric.Among these considerably less quoting, United States Patent (USP) 5707949 has been reported and has been had the purposes of two of formaldehyde-(hydroxyphenyl) sulfone as dyestuff bleeding inhibitor.

Known that nitrogenous polymkeric substance is in the laundry applications purposes in detergency ability particularly.Disclosed PCT application WO-A-98/23714 discloses the water-soluble purposes of nitrogenous soil release polymer in Betengent product.In these polymkeric substance some be by acrylamide monomer form and and the amine of comonomer alkyl acrylate carry out polymerization.WO-A-98/23714 has described nitrogenous soil release polymer, and described polymkeric substance is formed by dicarboxylic acid monomer and secondary amine hydrophilic co-monomer, and described secondary amine contains (gathering) alkylene oxide ((poly) alkyleneoxy) group.Disclosed PCT application WO-A-98/23714 discloses by vinylformic acid alkylene ester monomer with end quaternary ammonium group and the polymkeric substance that comonomer forms, and described comonomer is (methyl) vinylformic acid or ester or its salt.Unique example is to be that methacryloyl amido oxypropyl trimethyl ammonium chloride (MAPTAC), anionic monomer are that vinylformic acid (AA) and neutral monomer are the polymkeric substance that isobutyl acrylate (IsoBuA) forms by cationic monomer.

The multipolymer that United States Patent (USP) 3749682 discloses Polyvinylpyrolidone (PVP) (PVP) and vinyl acetate is as the anti-soil dirt purposes of deposition agent again.

Disclosed PCT application WO-97/42285 discloses cotton soil release polymers, comprises polyamine main chain and quaternary ammonium cation group.

Disclosed european patent application 995791 discloses the carbonate polymer of large-scale hydrophobically modified, it is said that described polymkeric substance can be used for promoting the soil removability of the especially cotton and cotton-containing fabrics of fabric.This polymkeric substance can comprise maximum three part A, B and C, and wherein A is selected from one or more C ₃-C ₈The monomeric polymeric residues of monoene key unsaturated carboxylic acid, B is selected from one or more C ₃-C ₆₀(methyl) vinylformic acid C of (methyl) alkyl acrylate, ethoxylation ₁-C ₂₄The monomeric polymeric residues that the alkyl or aryl ether of alkyl ester and poly-(methyl) vinylformic acid alkylidene diol ester, polyalkylene glycol and corresponding list thereof and span come acid esters, C is the polymeric residues that is selected from one or more ethylene linkage unsaturated monomers of the monomer copolymerizable among energy and A and the B.

According to disclosed UK Patent Application 2104091, the multipolymer of negatively charged ion and cationic vinyl monomer can be used as the detergent builder compound of cleaning product, for example wash dishes, hard-surface cleaning, clean fabric and hair preparation on a large scale.

United States Patent (USP) 5783533 discloses the ampholyte copolymer as the rheology modifier of washing composition or make-up composition lamellar phase.

JP-A-59135293 discloses the detergent composition that comprises ampholyte copolymer, and described ampholyte copolymer is made up of the cationic vinyl monomer unit of at least 10 moles of %, 10 moles of % anionic vinyl monomeric units and 10 moles of % nonionic ethylene base monomeric units at least at least.The ratio of preferred cation vinyl monomer unit and anionic vinyl monomeric unit is the mol ratio from 1:2 to 2:1.

United States Patent (USP) 5413731 discloses water-soluble copolymer, and it can be used in the detergent formulation of automatic dish washer.These terpolymers comprise following polymerized unit: (a) one or more C of about about 30 weight % of 92- ₃-C ₆Monoene key unsaturated carboxylic acid, (b) one or more amino acryl derivatives of the about 50 weight % of about 5-and (c) about 25 weight % can with (a) and (b) one or more monoethylenically unsaturated monomers of polymeric.

Goal of the invention

A purpose provides and comprises cation group especially polymkeric substance and its one or more preparation methods of the hydrophobically modified of DADMAC part.Another purpose provides described polymkeric substance as the method for laundry additive, described laundry additive suppress the migration of dyestuff or with dyestuff fixing at fabric face to prevent bleeding.It is believed that having hydrophobic and polymkeric substance cation group simultaneously can strengthen the substantive dyeing of polymkeric substance to matrix, thereby improve the dyestuff fixing efficient that wherein needs most.Simultaneously, these polymkeric substance have rational water soluble/dispersible, and it can promote that described polymkeric substance and the dyestuff (gamut dyestuff) that has been shed in the washing soln are compound, thereby prevents that dye migration is to other fabric of same laundry item.

Another purpose provides the method for above-mentioned polymer application in following prescription, described prescription be used at home or other indoor environment treat surface to prevent staining.The example on described surface comprises plate during washing dish uses, carpet, timber, laminating material or by floor organic and other type that inorganic materials is made.

Another purpose of the present invention provides the prescription of various laundry care productss, described product comprise have positively charged ion and hydrophobic grouping polymkeric substance as additive.Described product includes but not limited to amendment after detergent for washing clothes, the rinsing, pretreating agent, roller drying sheet, washing back sprays etc.Can imagine that described goods can be liquid, particle, tablet or above-mentioned any bonded form.The manufacturing of above-mentioned prescription can use the whole bag of tricks well known by persons skilled in the art, machine to carry out.To one skilled in the art, can to pack with various forms with various wrapping material also be conspicuous to described product.

Another object of the present invention provides the method for the above-mentioned various forms of laundry care productss of preparation, but the performance of these products can further be strengthened by mixing other additive, and described other additive is for example tenderizer, perfume compound, soil release polymer, tinting material, sanitas, various active sterilant with anti-various microorganisms, wormer, drive the agent of dirt mite and/or other control agent, white dyes, the UV absorption agent, other light regime agent, ionizer, defoamer, various enzymes, SYNTHETIC OPTICAL WHITNER, oxide catalyst, zeolite, include but not limited to the smell inhibitor of cyclodextrin and various derivatives thereof.Other additive and/or reagent also can be incorporated in the laundry care products of arbitrary form, and this is apparent to one skilled in the art.The visible United States Patent (USP) 5744435 of outstanding description of typical case's detergent for washing clothes and other laundry care products, but be not to be limited in this patent, the content of this patent all is incorporated herein by reference here.

Summary of the invention

The present invention relates to polymkeric substance, described polymkeric substance comprises the main chain derived from following at least monomer component: (I) 20-99.9 weight %, the cationic monomer of at least a formula (1) of preferred 50-99 weight %

(II) the hydrophobic unsaturated non-ionic monomer of polymeric in the presence of initiator of 0.1-80 weight %; Optional up to 60 weight % with monomer (I) and monomer (II) water-soluble monomer (III) all inequality; With optional (IV), the linking agent of 0-10 weight %.

Theme described herein promptly has hydrophobic and polymkeric substance cation group, is considered to also have other purposes except the laundry nursing.Example can comprise before paper is with maintenance and fixing agent, the fabric textile dyeing that especially cellulosic fibre is made, in the dyeing and/or wet fastness improvement, personal care and cosmetics after the dyeing for example shampoo, amendment, hair dye, hair fixing product, skin clean product, skin care products example emulsion, lotion and toning agent.The application of motif material and the various prescriptions that contain this material will disclose in the separate case patent application.

Theme described herein promptly has hydrophobic and polymkeric substance cation group, and also being considered to can provide extra effect when being used for doing washing when nursing is used.Possible benefit can include but not limited to improve the friction between feel such as flexibility and the minimizing fabric face.Back one performance is believed to produce the appreciable claim of human consumer, for example but the appearance of fabrics that is not limited only to improve, wearing and tearing reduce etc.

Detailed Description Of The Invention

Made by polyblend in the presence of activator and have hydrophobic and polymkeric substance cation group, described polyblend comprises

(I) 20-99.9 weight %, the cationic monomer of at least a formula (1) of preferred 50-99 weight %

Wherein

R ₁And R ₂Be hydrogen or C independently of each other ₁-C ₄Alkyl;

R ₃And R ₄Be hydrogen or alkyl, hydroxyalkyl, carboxyalkyl, Carboxylamide alkyl or alkoxyalkyl group independently of each other with 1-18 carbon atom;

And Y ^-Represent negatively charged ion; With

(II) the hydrophobic unsaturated non-ionic monomer of polymeric in the presence of initiator of 0.1-80 weight %.

The water solubility value that hydrophobic monomer (II) has, under room temperature and pH7 preferably less than about 50g/100g water, be more preferably less than 5g/100g water.

The example of preferred cation monomer (I) comprise diallyldimethylammonium chloride (DADMAC), diallyl dimethyl brometo de amonio, diallyl dimethyl sulfate ammonium, diallyl dimethyl ammonium phosphate, diformazan for allyl dimethyl ammonium chloride, diethyl for allyl dimethyl ammonium chloride, diallyl two (beta-hydroxyethyl) ammonium chloride and diallyl two (β-ethoxyethyl) ammonium chloride.Most preferred cationic monomer is DADMAC.

The example of hydrophobic monomer (II) comprises selected compound and other unsaturated compound, for example ester of (methyl) vinyl cyanide and unsaturated polyfunctional group acid based on vinyl and (methyl) acrylate ad lib.

The example of the vinyl compound that is fit to of monomer (II) includes but not limited to vinylbenzene; C ₂-C ₁₈The vinyl ester of carboxylic acid, for example vinyl acetate and vinyl butyrate; C ₂-C ₁₈The N-vinylamide of carboxylic acid, for example N-vinyl acetamide etc.

(methyl) acrylate based compound that is suitable as monomer (II) includes but not limited to (methyl) acrylic acid ester and (methyl) acrylic acid acid amides.

(methyl) acrylic acid ester or (methyl) acrylate comprise:

Long-chain and short chain (methyl) alkyl acrylate, for example (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) vinylformic acid isopentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid 11 esters, (methyl) dodecyl acrylate, (methyl) lauryl acrylate, (methyl) octadecyl acrylate and (methyl) stearyl acrylate ester; (methyl) alkoxyalkyl acrylate, especially (methyl) vinylformic acid C ₁-C ₄Alkoxy C ₁-C ₄Alkyl ester, for example vinylformic acid butoxy ethyl ester and vinylformic acid ethoxy ethoxy ethyl ester; (methyl) vinylformic acid aryloxy alkyl ester, especially (methyl) vinylformic acid aryloxy C ₁-C ₄Alkyl ester, for example vinylformic acid phenoxy ethyl (for example Ageflex, Ciba Specialty Chemicals); Single and many ring ring-types fragrance or non-fragrant acrylate be cyclohexyl acrylate, benzyl acrylate, vinylformic acid Dicyclopentadiene (DCPD) ester, vinylformic acid two ring pentyl esters, vinylformic acid three ring esters in the last of the ten Heavenly stems, vinylformic acid norbornene ester, isobornyl acrylate (AgeflexIBOA for example for example, Ciba Specialty Chemicals), vinylformic acid tetrahydrofuran ester (SR285 for example, Sartomer Company, Inc.), caprolactone acrylate (SR495 for example, SartomerCompany, Inc.) and acryloyl morpholine; (methyl) acrylate of alcohol radical, for example polyoxyethylene glycol mono acrylic ester, polypropylene glycol mono acrylic ester, methoxyl group EDIA, methoxyl group polypropylene glycol acrylate, methoxy poly (ethylene glycol) acrylate, ethoxydiglycol acrylate and various alkoxylated alkyl group phenol acrylate, for example ethoxylation (4) nonylphenol acrylate (for example Photomer 4003, Henkel Corp); (methyl) acrylic acid acid amides is diacetone-acryloamide(DAA), isobutyl oxygen Methacrylamide and uncle's octyl acrylamide for example; With the ester of polyfunctional group unsaturated acid, for example maleic acid ester and fumarate.

About above-mentioned listed long-chain and short chain alkyl acrylate, the short chain alkyl acrylate is to have 6 or still less the alkyl group of carbon atom and long chain alkyl acrylate are the alkyl groups with 7 or more carbon atoms.Optimal monomer is commercially available or uses reaction scheme known in the art synthetic easily.For example, most of above-mentioned listed monomers can react by suitable alcohol or acid amides and vinylformic acid or acrylate chloride and prepare.

Object lesson example as the preferred compound of monomer (II) is as follows:

Wherein

R ₅Be H or CH ₃,

R ₆Be C ₁-C ₁₂Alkyl, C ₁-C ₁₂Alkoxyl group, can be by C ₁-C ₁₂Alkyl or C ₁-C ₁₂Alkoxyl group replaces 1-3 time C ₁-C ₆Alkyl phenyl or by the oxygen C of one or many at interval ₁-C ₆Alkyl phenyl, wherein phenyl group can be by C ₁-C ₁₂Alkyl or C ₁-C ₁₂Alkoxyl group or C ₁-C ₆Alkyl hydroxy replaces 1-3 time;

And X be-O-,-NH-or-NR ₇-divalent radical, R wherein ₇Be C ₁-C ₆Alkyl.

Preferred compound has following formula:

With

R wherein ₅With X as defined above and n be the number of 1-5, preferred 2 or 3.

Particularly preferred compound has following formula:

R wherein ₅Be H or CH ₃

Polyblend randomly also comprises water-soluble monomer (III), and described monomer (III) is the polymerisable monomer that is different from monomer (I) and monomer (II).The water solubility value that water-soluble monomer (III) has under room temperature and pH7 is preferably greater than 50g/100g water.

Water-soluble monomer (III) can be non-ionic, anionic or cationic.The example of monomer (III) comprises the ethenyl derivatives of vinyl-amine, vinyl formamide, vinyl alcohol, vinyl pyrrolidone, caprolactam, dimethyl siloxane, aminosiloxane and other derivative, various vinyl fluorocarbon, acrylic acid hydroxy alkyl ester for example vinylformic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxypropyl acrylate and vinylformic acid 2-hydroxy butyl ester; (methyl) acrylic-amino alkyl ester, for example vinylformic acid dimethylamino ethyl ester, dimethylaminoethyl methacrylate, vinylformic acid diethylamino ethyl ester, diethyl aminoethyl methacrylate and vinylformic acid 7-amino-3, the salt of 7-dimethyl monooctyl ester and they comprises their alkyl and benzyl quaternary ammonium salt; (methyl) vinylformic acid and their salt; Acrylamide, Methacrylamide and N, N-dialkyl group acrylamide, for example N,N-DMAA, N, N-diethyl acrylamide and N, N '-dimethylaminopropyl acrylamide and their salt.Though choose wantonly, the content of monomer (III) can account for the 0-60 weight % of whole monomer weights, preferred 0-20 weight %.

Polyblend also randomly comprises monomer (IV), and quantity is 0-10 weight %, and it is one or more linking agents.The preferred example of the linking agent that is fit to comprises methylene-bisacrylamide, two, three and pentaerythritol tetracrylate, Vinylstyrene, polyvinyl alcohol diacrylate and bisphenol a diacrylate.

More generally, the linking agent that is fit to can be the polyfunctional group ethylenically unsaturated monomers, it comprises oxyalkylated bisphenol a diacrylate ad lib, for example ethoxylation is 2 or the bisphenol a diacrylate of the ethoxylation of how preferred 2-about 30 (for example SR349 and SR601, can be from Sartomer Company, Inc.West Chester, Pa. obtain, with Photomer 4025 and Photomer 4028, can be from Henkel Corp. (Ambler Pa.) obtains), propoxylation is 2 or the propenoxylated bisphenol a diacrylate of how preferred 2-about 30; Alkoxylate and the many acrylate of not oxyalkylated TriMethylolPropane(TMP) for example ethoxylation be 3 or the Viscoat 295 of the ethoxylation of how preferred 3-about 30 (for example Photomer 4149, Henkel Corp., and SR499, Sartomer Company, Inc.), propoxylation be 3 or the propenoxylated Viscoat 295 of how preferred 3-30 (for example Photomer 4072, Henkel Corp., and SR492, Sartomer) and two trimethylolpropane tetra-acrylate (for example Photomer 4355, Henkel Corp.); Oxyalkylated glycerol tri-acrylate for example propoxylation be 3 or more propenoxylated glycerol tri-acrylate (for example Photomer 4096, Henkel Corp., and SR9020, Sartomer); Alkoxylate and not oxyalkylated many vinylformic acid pentaerythritol ester, pentaerythritol tetracrylate (SR295 for example for example, can be from Sartomer Company, Inc. the pentaerythritol tetracrylate of (WestChester Pa.) obtains), ethoxylation (SR494 for example, Sartomer Company, Inc.) and five vinylformic acid dipentaerythritol ester (Photomer4399 for example, Henkel Corp. and SR399, Sartomer Company, Inc.); The many acrylate of isocyanuric acid ester by suitable functionalized isocyanuric acid ester and vinylformic acid or acrylate chloride reaction formation, three-(2-hydroxyethyl) isocyanuric acid ester triacrylates (SR368 for example for example, Sartomer Company is Inc.) with three-(2-hydroxyethyl) isocyanuric acid ester diacrylates; Alkoxylate and not oxyalkylated many acrylic acid multielements alcohol ester, diacrylate tristane diformazan alcohol ester (CD406 for example for example, Sartomer Company, Inc.) and ethoxylation be 2 or the polyethyleneglycol diacrylate of the ethoxylation of how preferred about 2-30; Add to the hydroxy acrylate that bisphenol A diglycidyl ether (more than 4) etc. forms (for example Photomer3016, Henkel Corp.) by acrylate; And single and many cyclophanes are fragrant or the many acrylate of non-fragrance for example diacrylate Dicyclopentadiene (DCPD) ester and diacrylate two are encircled pentyl esters.

The preparation of polymkeric substance of the present invention can adopt various polymerization techniques to carry out, for example enforceable other technology of solution, emulsion, microemulsion, reversed-phase emulsion and/or mass polymerization and those skilled in the art.Obviously can exist at the various initiators of various concentration or non-existent situation under carry out polymerization.Multipolymer or ter-polymers also can use or not use polymerization regulator for example under the situation of the nitroxyl radical of nitryl ether or other type, make polymer architecture be random, block, alternately or nuclear-shell side formula prepare.

The preferred method for preparing polymkeric substance of the present invention is to use water soluble starter to carry out aqueous solution polymerization.The example of the initiator that is fit to comprises for example ammonium persulphate (APS) of persulphate; Superoxide is hydrogen peroxide, tertbutyl peroxide and peroxidation PIVALIC ACID CRUDE (25) tertiary butyl ester for example, azo initiator for example 2,2 '-azo two (2-amidine propane) dihydrochloride, 4,4 '-azo, two-4-cyanopentanoic acid and 2,2 '-Diisopropyl azodicarboxylate; With redox initiator system for example tertbutyl peroxide/Fe (II) and ammonium persulphate/hydrosulphite.The aqueous solution polymerization that uses ammonium persulphate (APS) is the method that preferred preparation has preferred cation DADMAC polymer of monomers.The quantity of the radical initiator that uses in polymerization process depends on used total monomer concentration and monomer type, can account for the about 5.0 weight % of about 0.2-of total monomer feeding quantity, so that obtain to surpass 99% total monomer conversion.

Hydrophobic monomer (II) is partially dissolved in aqueous phase at least and forms the polymkeric substance with positively charged ion and hydrophobic grouping with the copolymerization of preferred cation monomer, DADMAC.When hydrophobic monomer (II) the amount in the polymerization system of joining was higher than its water solubility, if sufficient stirring is provided, the monomer of plussage (II) can the droplet form form second phase.Do not intend being confined to this polymerization mechanism, the drop of monomer (II) can be used as the monomer holder that monomer (II) is provided to water.

When using water soluble starter, the copolymerization of monomer (I) and hydrophobic monomer (II) dissolving part is initiated at aqueous phase.The hydrophobicity or the water-soluble and concentration that depend on used monomer (II), so the polymkeric substance of the hydrophobically modified that forms may or can not be water-soluble.Resulting polymkeric substance can have surfactant properties and may exist with colloidal state with translucent appearance.

The monomer of required quantity (II) can all add when beginning, and progressively adding or continuous charging add in the reactor.The continuous charging of hydrophobic monomer (II) in water reaction medium can have such advantage, and promptly the multipolymer of Zhi Bei hydrophobically modified still less forms homopolymer or big homopolymerization segment.

Preferably do not having to carry out polymerization under the situation of oxygen.Can be by when stirring, vacuumizing or purging and from reaction medium, remove oxygen with rare gas element such as nitrogen or argon gas.Reaction can be carried out under the protection of this rare gas element then.

The molecular weight of the polymkeric substance of preparation can be in 1,000 to 1,000,000 scope.For example their molecular-weight average of having are in the daltonian scope of 1000-5000000.Polymkeric substance can have various forms, ie in solution, dispersion liquid, suspension, particle, powder, pearl, piece etc.Under the situation of liquid form such as solution, dispersion liquid, suspension etc., liquid phase can be water and/or nonaqueous phase for example soybean oil, ester and mineral oil.

Cleaning product comprises one or more tensio-active agents of polymerizable compound of the present invention and significant quantity.This cleaning product can be the form of detergent for washing clothes, fabric conditioner, pretreating agent, post-treatment agent or roller drying sheet with improved dyestuff fixing and dye migration rejection.They also can be the forms of washing the dish prescription.Cleaning product of the present invention comprises 0.001%-50 weight %, the polymerizable compound of the present invention of preferred 0.1%-5 weight %.

Laundry composition used herein can comprise the tensio-active agent that one or more are applicable to clothes washing and/or rinse products.The most generally speaking, these tensio-active agents can be selected from one or more soap and non-soap anionic, positively charged ion, nonionic, both sexes and zwitter-ion surface active cpd and composition thereof.Provided a lot of surface active cpds that are fit in the document and it has been described in detail for example " Surface-Active Agents and Detergents ", volume I and II, Schwartz, Perry and Berch.

For those work done in the manner of a certain author is clothes washing product combination thing, and preferred surfactant is selected from one or more soap and synthetic non-soap anionic and non-ionic compound.Be suitable for great majority automatically the detergent composition of fabric washing machines comprise non-soap surfactant of negatively charged ion or nonionogenic tenside usually or be fit to both combination of ratio arbitrarily, the optional soap that has.

For example, clothes washing composition of the present invention can comprise the linear alkyl benzene sulfonate anion surfactant, especially has C ₈-C ₁₅The linear alkyl benzene sulfonate of alkyl chain length.The content of preferred linear alkyl benzene sulfonate is 0-30 weight %, more preferably 1-25 weight %, most preferably 2-15 weight %.

Laundry cleaning composition of the present invention can be extraly or is alternatively comprised one or more other the anion surfactant of total amount corresponding to the percentage ratio described in the above alkylbenzene sulfonate.The anion surfactant that is fit to is known to one skilled in the art.They comprise primary and secondary alkyl-sulphate, particularly C ₈-C ₁₅Primary alkyl sulphates; Sulfated alkyl ether; Ethylenic sulfonate; Alkylxylene sulfonate; Dialkyl sulfosuccinates; And fatty sulfonate.Common particular certain cancers.

Some specific examples of these other anion surfactant comprise: formula R ₁₀₀-CH (SO ₃M)-COOR ₂₀₀Alkyl ester sulfonate, R wherein ₁₀₀Be C ₈-C ₂₀, preferred C ₁₀-C ₁₆Alkyl group, R ₂₀₀Be C ₁-C ₁₆, preferred C ₁-C ₃Alkyl group, and ammonium that M is alkali metal cation (sodium, potassium, lithium), do not replace or replace (for example methyl, dimethyl, trimethylammonium, tetramethyl-ammonium, lutidine etc.) or chain triacontanol amine derivative (monoethanolamine, diethanolamine, trolamine etc.); Formula R ₃₀₀OSO ₃The alkyl-sulphate of M, wherein R ₃₀₀Be C ₅-C ₂₄, preferred C ₁₀-C ₁₈Alkyl or hydroxyalkyl group, and M be hydrogen atom or positively charged ion as defined above and they on average have 0.5-30, preferred 0.5-10 EO and/or unitary vinyloxy group of PO (EO) and/or propenyloxy group (PO) derivative; Formula R ₄₀₀CONHR ₅₀₀OSO ₃The alkylamide vitriol of M, wherein R ₄₀₀Be C ₂-C ₂₂, preferred C ₆-C ₂₀Alkyl group, R ₅₀₀Be C ₂-C ₃Alkyl group, and M be hydrogen atom or positively charged ion as defined above and they on average have 0.5-60 EO and/or unitary vinyloxy group of PO (EO) and/or propenyloxy group (PO) derivative; C ₈-C ₂₄, preferred C ₁₄-C ₂₀Saturated or unsaturated fatty acid salt, C ₈-C ₂₂Uncle or secondary alkyl sulfonate, alkyl glycerol sulfonate, the sulfonated poly carboxylic acid of in English Patent 1082179, describing, sulfonated alkane, the N-acyl group, N '-alkylamino esilate, alkylphosphonic, isethionate, alkyl succinate, alkyl sulfo succinate, the monoesters of sulfosuccinate or dibasic acid esters, N-acyl sarcosinate, alkylglycoside vitriol, polyethoxye carboxylate salt, positively charged ion are basic metal (sodium, potassium, lithium), replace or unsubstituted ammonium (methyl, dimethyl, trimethylammonium, tetramethyl-ammonium, lutidine etc.) or chain triacontanol amine derivative (monoethanolamine, diethanolamine, trolamine etc.); Or sophorolipid, for example by the sophorolipid of deutero-acid of 17-isorpcinoleic acid or lactone form.

Clothes washing composition of the present invention can comprise nonionogenic tenside.The available ionic surfactant pack is drawn together primary and secondary alcohol ethoxylate, especially C ₈-C ₂₀Fatty Alcohol(C12-C14 and C12-C18) is with the product of the every mol of alcohol ethoxylation of average 1-20 moles of ethylene oxide, more particularly C ₁₀-C ₁₅The primary and secondary Fatty Alcohol(C12-C14 and C12-C18) is with the product of the every mol of alcohol ethoxylation of average 1-10 moles of ethylene oxide.The ionic surfactant pack of non-ethoxylatedization is drawn together alkyglycosides, glycerol monoethers and polyhydroxyamide (glucamide).

Some specific examples of this type of nonionogenic tenside are: poly-alkoxylation alkylphenol (being polyethyleneoxy, polypropylene oxygen base, polybutene oxygen base), and its alkyl substituent has 6-12 C atom and contains 5-25 alkoxylate unit; Example is Rohm﹠amp; The IGEPALNP2-NP17 that TRITON X-45, X-114, X-100 and X-102 that Haas Co. sells and Rhodia make; Contain the unitary C of 1-25 alkoxylate (vinyloxy group, propenyloxy group) ₈-C ₂₂The poly-alkoxylation Fatty Alcohol(C12-C14 and C12-C18); Example is the TERGITOL15-S-9 of Union Carbide Corp. sale and the NEODOL 45-9 that TERGITOL 24-L-6NMW, Shell Chemical Co. sell, NEODOL 23-65, NEODOL 45-7 and NEODOL 45-4, The Procter ﹠amp; DB and B that SYNPERONIC A3-A9, the Rhodia that KYRO EOB, the ICI and RHODASURFIT that Gamble Co. sells makes makes; Derive from the product of oxyethane or propylene oxide and propylene glycol, ethylene glycol condensation, molecular weight is in the 2000-10000 rank, for example the PLURONIC product sold of BASF; Derive from the product of oxyethane or propylene oxide and quadrol condensation, for example the TETRONIC product of BASF sale; Contain 5-25 vinyloxy group and/or the unitary C of propenyloxy group ₈-C ₁₈Oxyethyl group and/or propoxy-lipid acid; Contain 5-30 the unitary C of vinyloxy group ₈-C ₂₀Fatty acid amide; Contain 5-30 the unitary ethoxylated amine of vinyloxy group; Contain 1-50, preferred 1-25 is the unitary alkoxylate amido amine of 2-20 alkylidene group oxygen base (optimal ethylene oxygen base) especially; Amine oxide is alkyl C for example ₁₀-C ₁₈The oxide compound of dimethyl amine, alkoxy C ₈-C ₂₂The oxide compound of ethyl diethanolamine; The alkoxylate terpene hydrocarbons for example contains 1-30 vinyloxy group and/or the unitary ethoxylation of propenyloxy group and/or propenoxylated terpene hydrocarbon or firpene; (for example United States Patent (USP) 3598865 with uncle's Fatty Alcohol(C12-C14 and C12-C18) condensation (for example acid catalysis) by glucose; United States Patent (USP) 4565647; EP-A-132043; EP-A-132046) alkyl poly glucoside that obtains has C ₄-C ₂₀, preferred C ₈-C ₁₈Glucose unit average number in alkyl group and the every mole of alkyl poly glucoside (APG) is at 0.5-3, the alkyl poly glucoside of selling with the title of GLUCOPON 600 EC, GLUCOPON 600 CSUP, GLUCOPON 650 EC and GLUCOPON 225CSUP respectively that preferred 1.1-1.8 rank, particularly HENKEL are made: C with following alkyl and glucose unit ₈-C ₁₄Alkyl and every mole of average 1.4 glucose unit, C ₁₂-C ₁₄Alkyl and every mole of average 1.4 glucose unit, C ₈-C ₁₄Alkyl and every mole of average 1.5 glucose unit, C ₈-C ₁₀Alkyl and every mole of average 1.6 glucose units.

All the content of nonionogenic tenside is 0-30 weight %, and preferred 1-25 weight % is more preferably 2-15 weight %.

The another kind of suitable tensio-active agent that is used for master's washing composition of the present invention comprises some single-long-chain alkyl cats product.This type of cats product comprises that general formula is R ₁₀R ₂₀R ₃₀R ₄₀N ⁺X ^-Quaternary ammonium salt, wherein R is long or short hydrocarbon chain, is typically alkyl, hydroxyalkyl or ethoxylated alkyl group, and X is counter ion (R wherein for example ₁₀Be C ₈-C ₂₂Alkyl group, preferred C ₈-C ₁₀Or C ₁₂-C ₁₄Alkyl group, R ₂₀Be methyl group, and R ₃₀And R ₄₀(both can be identical or different) is the compound of methyl or hydroxyethyl groups); With cationic ester class (for example cholinesterase).

The selection of surface active cpd (tensio-active agent) and its quantity in clothes washing composition of the present invention will depend on the intended purpose of detergent composition.In fabric cleaning composition, known as the formulator of this area, for hand-washing product and can selecting different surfactant systems for the product that is intended for dissimilar washing machines.The total amount of the tensio-active agent that exists also will depend on predetermined end-use, for example at the fabric cleaning composition that is used for hand-washing, and can be up to 60 weight %.At the composition of the fabric that is used for machine-washing, the amount of 5-40 weight % is appropriate usually.Typically, composition will contain the tensio-active agent of at least 2 weight %, 2-60% for example, preferred 15-40%, and 25-35% most preferably.

Under the situation of clothing rinse composition of the present invention, tensio-active agent preferably is selected from fabric conditioner.In fact can use conventional fabric conditioner.These amendments can be positively charged ions or non-ionic.Wash detergent composition if the fabric-conditioning compound will be used for the master, then this compound typically can be non-ionic.If be used for rinse stage, typically they can be cationic.Their spendable amounts for example account for the 0.5-35 weight % of composition, and preferred 1-30 weight % is more preferably 3-25 weight %.

Preferably fabric conditioner has two chain alkyls or alkenyl, and each chain all has more than or equal to C ₁₆Mean chain length.Most preferably at least 50% chain alkyl or kiki alkenyl group have C ₈Or above chain length.The chain alkyl of preferred fabric amendment or kiki alkenyl group mainly are linear.

Fabric conditioner preferably provides the compound of good flexibility, and it is characterized in that its chain fusion L to L invert point greater than 25 ℃, is preferably greater than 35 ℃, most preferably greater than 45 ℃.

Largely insoluble fabric-conditioning compound is defined as solubleness at 20 ℃ of fabric-conditioning compounds in softening water less than 1 * 10 in scope of the present invention ^-3Weight %.Preferably the solubleness of fabric soft compound is less than 1 * 10 ^-4Weight % is most preferably less than 1 * 10 ^-8-1 * 10 ^-6The preferred cation fabric softener comprises that the water-fast substantially mean chain length degree that comprises is more than or equal to C ₂₀Single alkyl or the quaternary ammonium material of alkenyl long-chain, or be more preferably and comprise terminal polar group and mean chain length more than or equal to C ₁₄Two alkyl or the compound of alkenyl chain.

Preferably, cationic fabric softener is quaternary material or the quaternary material that contains at least one ester group.The quaternary ammonium compound that contains at least one ester group is meant the quaternary ammonium compound that ester connects here.

As used in the quaternary ammonium cation fabric softener, the term ester group comprises the ester group as linking group in the molecule.

Ester connects quaternary ammonium compound and preferably comprises two or more ester groups.In monoesters and dibasic acid esters quaternary ammonium compound, preferred ester group is the linking group between N atom and alkyl group.Preferred ester group is connected on the N atom by another hydrocarbyl group.

Equally preferably quaternary ammonium compound comprises at least one ester group, preferred two ester groups, wherein at least one higher molecular weight group comprises at least one ester group and two or three lower molecular weight groups are connected on the public nitrogen-atoms, thereby generation positively charged ion, and wherein the electrobalance negatively charged ion is halogen, acetate or lower alkyl sulfate radical (alkosulfate) ion, for example chlorion or methyl-sulfuric acid root.Higher molecular weight substituting group on the nitrogen preferably contains 12-28, preferred 12-22, the senior alkyl group of 12-20 carbon atom for example, the senior alkyl of cocounut oil alkyl, tallow alkyl, hydrogenant tallow alkyl or replacement for example, the lower molecular weight substituting group preferably has the low alkyl group of 1-4 carbon atom, for example methyl or ethyl, or the low alkyl group that replaces.One or more described lower molecular weight substituting groups can comprise aryl moiety or be replaced by aryl such as benzyl, phenyl or other suitable substituents.

Preferred quaternary material is to have by at least one ester linking group, and preferred two ester linking groups are connected to two C on the quaternary ammonium end group group ₁₂-C ₂₂The compound of alkyl or kiki alkenyl group, or comprise mean chain length and be equal to or greater than C ₂₀The compound of single long-chain.

More preferably, quaternary material comprises and has two mean chain lengths and be equal to or greater than C ₁₄Chain alkyl or the compound of alkenyl chain.Even more preferably each chain mean chain length is equal to or greater than C ₁₆Most preferably at least 50% each chain alkyl or kiki alkenyl group have C ₁₈Chain length.Preferred chain alkyl or kiki alkenyl group mainly are linear.

The ester that can be used for the most preferred type of clothing rinse composition of the present invention connects quaternary material as shown in the formula shown in (A):

Wherein T is

Or

Each R ⁵⁰Group is independently selected from C _1-4Alkyl, hydroxyalkyl or C _2-4Kiki alkenyl group; And each R wherein ⁵¹Group is independently selected from C _8-28Alkyl or kiki alkenyl group; Y ^-Be the counter ion that are fit to arbitrarily, i.e. halogen, acetate or lower alkyl sulfate ion, for example chlorion or methyl-sulfuric acid root;

W is the integer or 0 of 1-5; With

Y is the integer of 1-5.

Preferred especially each R ⁵⁰Group is that methyl and w are 1 or 2.

If quaternary material is biodegradable, it is favourable based on environment reason so.Preferred this type of material for example 1,2 two [hardened tallow acyloxy]-3-trimethyl ammonium propane chloride and preparation method thereof for example is described in the United States Patent (USP) 4137180.Preferably these materials comprise a spot of corresponding monoesters, and 1-hardened tallow acyloxy-2-hydroxyl-3-trimethyl ammonium propane chloride for example is described at United States Patent (USP) 4137180.

The another kind of preferred ester that is used for clothing rinse composition of the present invention connects quaternary material and can use following formula (B) expression:

Wherein T is

Or

With

R ⁵⁰, R ⁵¹And Y ^-As defined above.

To the compound of formula (B), two-(the tallow oxygen ethyl) alkyl dimethyl ammonium chlorides that can obtain from Hoechst are most preferred.Hoechst produce two-(hardened tallow base oxygen ethyl) alkyl dimethyl ammonium chloride and two-(tallow oxygen ethyl)-dimethyl hydroxyethyl metilsulfate also is preferred.

Another kind of preferred quaternary ammonium cation fabric softener defines as shown in the formula (C):

R wherein ⁵⁰, R ⁵¹And Y ^-As defined above.

The material of preferred formula (C) is two-hardened tallow-diethyl ammonium chloride, sells with trade mark ARQUAD 2HT.

As known in the art, optional ester connects quaternary material can comprise optional other component, particularly low molecular weight solvent, and for example Virahol and/or ethanol and promoting agent NON IONIC SOFTNER for example altogether are as lipid acid or sorbitan ester.

Washing assistant

Composition of the present invention when as the clothes washing composition, also comprises one or more washing assistants usually.The total amount of washing assistant in composition be 5-80 weight % typically, preferred 10-60 weight %.

The inorganic builders that can exist comprises yellow soda ash, if desired can be in conjunction with the lime carbonate crystal seed, as disclosed in GB 1437950 (Unilever); Crystal and amorphous aluminosilicate be the disclosed zeolite of GB1473201 (Henkel), the disclosed amorphous aluminosilicate of GB1473202 (Henkel) and GB1470250 (Procter ﹠amp for example; Gamble) disclosed blended crystal/amorphous aluminosilicate; Disclosed with lamellated silicate such as EP164541B (Hoechst).Inorganic phosphate builders, for example sodium orthophosphate, trisodium phosphate and tripoly phosphate sodium STPP also are suitable for the present invention.

The silico-aluminate washing assistant of the preferred sodium of composition preferred package alkali metal containing of the present invention.Usually the amount of the sodium silicoaluminate that can mix is 10-70 weight % (anhydrous basis), preferred 25-50 weight %.

Alkali metal aluminosilicate can be to have general formula 0.8-1.5Na ₂O.Al ₂O ₃.0.8-6SiO ₂Crystal or amorphous substance or its mixture.

These materials comprise some combination water and need have the calcium ion exchange capacity of 50mg CaO/g at least. and preferred sodium silicoaluminate comprises 1.5-3.5 SiO ₂Unit (in following formula).As in the literature fully as described in, can prepare amorphous easily and crystalline material by the reaction between water glass and the sodium aluminate.The crystalline silicon sodium aluminate ion-exchange washing assistant that is fit to is described in for example GB1429143 (Procter ﹠amp; Gamble) in.This type of preferred sodium silicoaluminate is known commercially available zeolite A and X and their mixture.

Zeolite can be the commercially available zeolite 4A that is widely used in now in the washing powder.But according to the preferred embodiments of the invention, the zeolite builders that mixes in the present composition is as describing and claimed maximum aluminium zeolite P (zeolite MAP) in EP384070A (Unilever).Zeolite MAP is defined as the alkali metal aluminosilicate of zeolite P type, and the silica alumina ratio that is had is no more than 1.33, preferably between 0.90-1.33, and more preferably between 0.90-1.20.

Particularly preferably be silica alumina ratio and be no more than 1.07, be more preferably about 1.00 zeolite MAP.The calcium-binding capacity of zeolite MAP is the every gram anhydrous material of 150mg CaO usually at least.

The organic washing-assisting detergent that can exist comprises the polycarboxylate polymkeric substance, for example polyacrylic ester, vinylformic acid/maleic acid and vinylformic acid phosphinates; Monomer polycarboxylate, for example citrate, gluconate, oxygen di-succinate, glycerine list, two and three succinates, carboxymethyl oxygen connection succinate, carboxymethyl oxygen connection malonic ester, pyridine dicarboxylate, hydroxyethyliminodiacetic acid ester, alkyl-and alkenyl malonic ester and succinate; With sulfonated soap.Above-mentioned enumerate do not intend limit all.Particularly preferred organic washing-assisting detergent is a citrate, and suitable consumption is 5-30 weight %, preferred 10-25 weight %; And acrylate copolymer, vinylformic acid/toxilic acid blend more specifically, suitable consumption is 0.5-15 weight %, preferred 1-10 weight %.

Inorganic and organic washing-assisting detergent is all preferably with an alkali metal salt, and particularly the form of sodium salt exists.

Clothes washing composition of the present invention can also suitably contain bleach system.Fabric cleaning composition can comprise the peroxy bleaching compound that can produce hydrogen peroxide in the aqueous solution, for example inorganic persalt or organic peroxide acid ideally.

The peroxy bleaching compound that is fit to comprises for example for example alkali metal perborate, percarbonate, superphosphate, persilicate and persulphate of urea peroxide and inorganic persalt of organo-peroxide.Preferred inorganic persalt is Sodium peroxoborate monohydrate and tetrahydrate and SPC-D.

Especially preferred is the SPC-D with moisture resistance moist lability supercoat.SPC-D with the supercoat that comprises sodium metaborate and water glass is disclosed among the GB 2123044B (Kao).

The amount that peroxy bleaching compound is fit to exist is 0.1-35 weight %, preferred 0.5-25 weight %.Peroxy bleaching compound can and bleach-activating agent (bleaching precursor) use together to improve the bleaching action when the cold washing.The amount that the bleaching precursor is fit to exist is 0.1-8 weight %, preferred 0.5-5 weight %.

Preferred bleaching precursor is a peroxycarboxylic acid precursors, more particularly peracetic acid precursors and n-nonanoic acid precursor excessively.Being suitable for particularly preferred bleaching precursor of the present invention is N, N, N ', N '-tetra acetyl ethylene diamine (TAED) and acyloxy sodium sulfonate in the ninth of the ten Heavenly Stems (SNOBS).Be disclosed among United States Patent (USP) 4751051 and United States Patent (USP) 4818426 (Lever Brothers Company) and the EP402971A (Unilever) novel quaternary ammonium He Phosphonium bleaching precursor and be disclosed in EP284292A and EP303520A (Kao) in the cationic bleach precursor also be interesting.

Bleach system can replenish or be substituted by peroxy acid with peroxy acid.Visible United States Patent (USP) 4686063 of the example of this type of peroxy acid and United States Patent (USP) 5397501 (Unilever).Preferred example is the imino-peroxycarboxylic acid class peroxy acid that is described among EP A 325288, EP A 349940, DE 3823172 and the EP325289.More preferred example is that phthaloyl imino is crossed oxy hexanoic acid (PAP).This type of peroxy acid compatibly exists with 0.1-12%, preferred 0.5-10%.

Bleaching stibilizer (transition metal sequestrant) also can exist.The bleaching stibilizer that is fit to comprises for example EDDS (ethylenediamine disuccinic acid) of ethylenediamine tetraacetic acid (EDTA) (EDTA), polyphosphonates such as DEQUEST (trade mark) and non-phosphoric acid ester stablizer.The removal that these bleaching stibilizers also can be used for stain is especially at the bleaching species that comprises low levels or do not contain in the product of bleaching species.

Particularly preferred bleach system comprises peroxy bleaching compound (preferred SPC-D, the optional bleach-activating agent that has) and as EP458397A, EP458398A and the described transition metal bleach catalyzer of EP509787A (Unilever).

Clothes washing composition of the present invention can also comprise one or more enzymes.The enzyme that is fit to comprises proteolytic enzyme, amylase, cellulase, oxydase, peroxidase and the lipase that is fit to mix detergent composition.Preferred proteolytic enzymes (proteolytic enzyme) is the protein material of catalytic activity, and it is degraded in hydrolysis reaction or changes the protein type of spot in the time of in being present in textile stains.They can have the source that is fit to arbitrarily, for example plant-derived, animal, bacterium or yeast.

Have a various characteristics to have active proteolytic ferment or proteolytic enzyme with the source and in the pH of different 4-12 scope all be available and can be used among the present invention.The example of the proteolytic ferment that is fit to is the subtilisin that derives from specific B bacterial strain Subtilwas B licheniformin, Gist Brocades N.V. for example, Delft, commercially available subtilisin MAXATASE (trade mark) that Holland provides and Novo Industri A/S, the ALCALASE that Copenhagen, Denmark provide (trade mark).

What especially be fit to is the proteolytic enzyme that derives from tooth born of the same parents Bacillaceae bacterial strain that has maximum activity in the pH8-12 scope, for example is purchased the A/S from Novo Industri with registrar name of an article ESPERASE (trade mark) and SAVINASE (trade mark).The preparation of these enzymes and similar enzyme is described among the GB 1243785.Other commercial protease is that (trade mark is from the Miles Kali-Chemie of Germany, Hannover) and SUPERASE (trade mark derives from the Pfizer of the U.S.) for KAZUSASE (trade mark derives from the Showa-Denko of Japan), OPTIMASE.

Detersive enzyme uses with the quantity of the about 3.0 weight % of about 0.1-with particle form usually.But the physical aspect of the enzyme that is fit to all is operable arbitrarily.

Composition of the present invention can comprise other optional ingredients, and for example the preferred yellow soda ash of alkaline carbonate is processed to increase detersive power and to be convenient to.Yellow soda ash can be compatibly with 1-60 weight %, and the quantity of preferred 2-40 weight % exists.But contain seldom or do not contain yellow soda ash composition also within the scope of the invention.

Powder flowbility can be improved by mixing the small quantities of powder structural agent, for example lipid acid (or fatty acid soaps), sugar, acrylate or acrylate/maleate copolymer or water glass.A preferred pulverized structure agent is a fatty acid soaps, and the amount that is fit to exist is 1-5 weight %.

Other material that may reside in the detergent composition of the present invention comprises water glass; Anti redeposition agent is cellulose polymer compound for example; Inorganic salt are sodium sulfate for example; Suitable Foam Control or suds booster; Proteolytic ferment and lipolytic enzyme; Dyestuff; Coloured speckle; Spices; Foam Control; White dyes and decoupling polymkeric substance.Above-mentionedly enumerate that not intend limit whole.

Other material that may reside in the detergent composition of the present invention comprises for example softening agent of other additive, spices, soil release polymer, tinting material, sanitas, various microorganisms had various active antiseptic-germicides, wormer, dirt mite expellent and/or other control agent, white dyes, uv-absorbing agent, other light regime agent, ionizer, defoamer, various enzymes, SYNTHETIC OPTICAL WHITNER, oxide catalyst, zeolite and the smell inhibitor that includes but not limited to cyclodextrin and various derivatives thereof.

Composition of the present invention, (in typical wash(ing)cycle) typically will make washing liq have 7-11 to washed product, the pH of preferred 7-10.5 when diluting with washing liq.With polymer treatment fabric according to an aspect of the present invention, can for example wash by the method that is fit to arbitrarily, immersion or rinsing carry out with positively charged ion and hydrophobic grouping.

Typically, handle to will be referred to washing or rinse method, for example in the main washing of washing machine or rinse cycle, handle, and relate to fabric is contacted with the water medium of the composition that comprises first aspect of the present invention.

The composition of another aspect of the present invention can be formulated into arbitrarily form easily, for example powder, liquid (aqueous solution or non-aqueous solution) or tablet.

Granular detergent composition can suitably prepare by the following method: the slurry of the hot insensitive composition that spraying drying is compatible will be not suitable for adding with injection or back feed-type by those compositions of slurry processing then.Skilled formulator which composition of decision should be included in the slurry and which can not the time will can not have any problem.

Granular detergent composition of the present invention preferably has the tap density of 400g/l at least, is more preferably 500g/l at least.Particularly preferred composition has the tap density of 650g/l at least, and being more preferably is 700g/l at least.

Back tower (post-tower) enrichment that this type of powder can be by spray-dried powders or the method by there not being tower fully such as dry mixed and granulation prepare; Advantageously can use high-speed mixer/tablets press in the above two kinds of cases.Use the method for high-speed mixer/tablets press for example to be disclosed among EP340013A, EP367339A, EP390251A and the EP420317A (Unilever).

Thereby liquid detergent composition can by mix with the order of any hope must composition and optional member provide the composition that comprises component that must concentration to make.Liquid composition of the present invention can be a conc forms also, this means with the conventional liq washing composition to compare, and this liquid composition comprises the more water of low levels.

Another embodiment of the present invention relates to the textile treatment preparation, and it comprises the aforesaid liquid of 0.001 weight %-50 weight % or the polymerizable compound of solid form.

The preferred embodiments of the invention relate to dyeing or printing auxiliary agent and/or the finishing composition that comprises described textiles preparation.

Another embodiment of the present invention relates to method for treating textile, be included in before the dyeing or the conditioning process of other type, among and add described textiles preparation afterwards, with the wet fastness of improving textiles with prevent to fade.

The following examples have been described embodiments more of the present invention, but the present invention is not restricted to this.Should be appreciated that, can carry out in a large number can not departing from the spirit and scope of the present invention at the change of disclosed embodiment according to content disclosed herein.Therefore these embodiment and not meaning that limit the scope of the invention.On the contrary, have only appended claim and equivalent thereof just to determine scope of the present invention.In these embodiments except as otherwise noted, all umbers that provide all are parts by weight.

Embodiment 1

In the 1 liter of reactor that has assembled condenser, thermometer, nitrogen inlet tube and top formula agitator, be added in monomer, DADMAC, 15.8g methyl methacrylate (MMA), 574.0g deionized water and 0.15g 20% Na of the 453.8g 66% in the water ₄EDTA solution.Polyblend is with nitrogen purging and under agitation be heated to 90 ℃.The aqueous solution that will contain 5.1g ammonium persulphate (APS) in 190 minutes slowly joins in the reactor.Temperature of reaction is raised to more than 100 ℃, remains on reflux temperature (100-110 ℃) then during APS adds.APS is reinforced finish after, temperature of reaction is reduced to 95 ℃ and kept about 30 minutes at 95 ℃.In 30 minutes, add the aqueous solution that contains 5.6g sodium metabisulfite (MBS) then.Make the interior material of reactor keep 30 minutes again to finish polymerization (transformation efficiency more than 99%) at 95 ℃.With enough water dilute polymer solutions to 35% solid content and cool to room temperature.The monomer total conversion rate surpasses 99.5% after measured.The brookfield viscosity of final product when 25 ℃ and 33.7% polymer solids content is 23400cps.

Embodiment 2

In the 1 liter of reactor that has assembled condenser, thermometer, nitrogen inlet tube and top formula agitator, be added in monomer, DADMAC, 15.8g ethoxylation vinylformic acid nonyl phenyl ester (ENPA), 574.0g deionized water and 0.15g 20% Na of the 453.8g 66% in the water ₄EDTA solution.Polyblend is with nitrogen purging and under agitation be heated to 90 ℃.The aqueous solution that will contain 5.1g ammonium persulphate (APS) in 190 minutes slowly joins in the reactor.Temperature of reaction is raised to more than 100 ℃, remains on reflux temperature (100-110 ℃) then during APS adds.APS is reinforced finish after, temperature of reaction is reduced to 95 ℃ and kept about 30 minutes at 95 ℃.In 30 minutes, add the aqueous solution that contains 5.6g sodium metabisulfite (MBS) then.Make the interior material of reactor keep 30 minutes again to finish polymerization (transformation efficiency more than 99%) at 95 ℃.With enough water dilute polymer solutions to 35% solid content and cool to room temperature.The monomer total conversion rate surpasses 99.5% after measured.The brookfield viscosity of final product when 25 ℃ and 33.7% polymer solids content is 15700cps.

Embodiment 3

This embodiment has proved by the reinforced hydrophobic monomer II that increases.Polymerization process is the same with embodiment 1, except when the APS initiator feeds in raw material beginning, adds the 15.8g methyl methacrylate at about 45 minutes in the clock time in reactor.With enough water dilute polymer solutions to 35% solid content and cool to room temperature.Measure the monomer total conversion rate and surpass 99.5%.The brookfield viscosity of final product when 25 ℃ and 35% polymer solids content is 19500cps.Compare with the emulsion appearance of embodiment 1 product, this final polymer product is transparent.

Embodiment 4: use: fixing before washing

Fixing:

Product is applied to painted pieces of fabric (" bleeding sheet ") from the aqueous solution go up and Rotary drying.

Washing:

Use the fabric and no yarn dyed fabric (" being subjected to color chips (Acceptor) ") that do not wash this processing together with the standard wash agent of any dye-fixing agent or dye transfer inhibitor.Rotary drying above-mentioned fabrics, clear water rinsing, Rotary drying and 60 ℃ of oven dry.All change new " being subjected to color chips " in cycle in each subsequent washing.

Absorption (delustring at the maximum absorption place) and the deposition of dye (δ E) on white " being subjected to color chips " fabric by stationary liquid, washings come assessed for performance.

Use the absorption of gained and the quantity that δ E value is calculated corresponding dyestuff.All results provide with the quantity of the dyestuff that comes off from the 1kg DYED FABRICS.

Application conditions:

At 40 ℃ of flowing fluid ratios is under the condition of 1:10, with containing the 2.5g/l of 1% polymer active material or 5g/l solution-treated 5g dyed cotton fabric (2.09% sun blue 78) 15 minutes.Fabric is shifted out from liquid, Rotary drying, and be the colourless cotton fabric washing 15 minutes that " is subjected to color chips " in 2.5g/l ECE77 detergent solution with 5g under the 1:10 condition at 40 ℃ of flowing fluid ratios.Extract above-mentioned fabrics, with the rinsing of mobile tap water, Rotary drying is also dried in 60 ℃ of baking ovens.

This step repeats twice to same " bleeding sheet ", and new " being subjected to color chips " all used in each washing.

The result:

[the dyestuff mg that every kilogram of DYED FABRICS came off]

Wherein Ex.2 is the multipolymer of DADMAC and acrylamide, and TINOFIX CL is the product that is purchased from CibaSpecialty Chemicals.

The above results shows, when before washing, using the DADMAC polymer treatment fabric of a small amount of hydrophobically modified, come off enter stationary liquid, washings and come off after deposit to and greatly reduced by the amount of the dyestuff on the color chips fabric; So, have the excellent performance that prevents the dyestuff bleeding.

Embodiment 5: use: fixing during washing

Use not with washing colored together fabric of the standard wash agent of any dye-fixing agent or dye transfer inhibitor (" bleeding sheet ") and no yarn dyed fabric (" being subjected to color chips ").Before application is about to begin, the dyestuff fixing polymkeric substance is joined in the washings.With the fabric Rotary drying, use the clear water rinsing, Rotary drying and 60 ℃ of oven dry." being subjected to color chips " all uses new replacement in each wash(ing)cycle below.

Absorption (delustring at the maximum absorption place) and the deposition of dye (δ E) on white " being subjected to color chips " fabric by washings come assessed for performance.

Application conditions:

5g dyed cotton fabric (2.09% sun blue 78) and the colourless cotton fabric of 5g " are subjected to color chips " in 2.5g/l standard wash agent ECE77 solution.Before application is about to begin, the dyestuff fixing polymkeric substance that accounts for washing composition 1 weight % is joined in the detergent solution.Flowing fluid ratio is 1:10, and wash temperature is 40 ℃.

Extract above-mentioned fabrics, with the rinsing of mobile tap water, Rotary drying is also dried in 60 ℃ of baking ovens.

The result:

[the dyestuff mg that every kilogram of DYED FABRICS came off]

Wherein SOKALAN HP56 and PVP K-30 are commercially available poly-(vinyl pyrrolidone) basic anti redeposition agents.

The above results shows, when the DADMAC of hydrophobically modified polymkeric substance when joining in the laundry detergent on a small quantity, the amount that enters the dyestuff in the liquid that comes off greatly reduces.In addition, this base polymer can also be to help prevent the deposition again of gamut dyestuff to commercially available anti-deposition agent such as SOKALAN HP 56 mode similar with PVP K-30.

Embodiment 6: it is poly-that the copolymerization by DADMAC and various hydrophobic monomers prepares hydrophobically modified Compound

Use the step of describing among the embodiment 1, by DADMAC and various amount, i.e. the copolymerization of the methyl methacrylate of 2.5%, 5% and 10% (w/w), butyl methacrylate, benzyl methacrylate prepares hydrophobically modified polymers.

Polymkeric substance		Total monomer conversion	Solid	Brookfield viscosity (25 ℃)
Polymkeric substance		Total monomer conversion	Solid	Brookfield viscosity (25 ℃)	Comparative Examples	(1)DADMAC(100％)	99.9％	35％	7,850
Embodiment 6A	(2)DADMAC:MMA(97.5:2.5)	>99％	35％	23,600	Comparative Examples	(1)DADMAC(100％)	99.9％	35％	7,850
Embodiment 6A	(2)DADMAC:MMA(97.5:2.5)	>99％	35％	23,600	Embodiment 6B	(3) DADMAC: methacrylic acid monoester (95:5)	>99％	32％	9,000
Embodiment 6C	DADMAC: butyl methacrylate (95:5)	>99％	35％	15,200	Embodiment 6B	(3) DADMAC: methacrylic acid monoester (95:5)	>99％	32％	9,000
Embodiment 6C	DADMAC: butyl methacrylate (95:5)	>99％	35％	15,200	Embodiment 6D	DADMAC: benzyl methacrylate (95:5)	>99％	35％	15,400

The application testing that employing describes below is studied the influence of the amount of the type of hydrophobic monomer and/or hydrophobic monomer to the color fixed performance.It should be noted that embodiment just for illustrative purposes, and the selection of hydrophobic monomer and use and do not limited by these embodiment.

Embodiment 7: use: used the methyl by DADMAC and various amounts before washing test The hydrophobically modified polymers of methacrylate monomer copolymerization preparation is fixed

The application conditions of this cover test and embodiment 4 be described change slightly.Just, by 100% cotton makes and with 2.09% sun blue and/or 3.0% direct red 227 painted respectively 5g bleeding sheet fabric rinsings in the aqueous solution of 1% polymers soln to be tested that comprises 5g/l.Above-mentioned rinsing is to carry out 30 minutes at 25 ℃ under 11 ° of dH situations in the flowing fluid ratio and the water hardness of 10:1.Carry out drying in room temperature.

The bleeding sheet that this pre-fixes washs with following material:

5g is subjected to 100% cotton fabric of color chips-bleaching

2.5g/l ECE77 standard wash agent

Flowing fluid ratio is 10:1,11 ° of dH of the water hardness

30 ℃, 15 minutes.

By the absorption of washings be subjected to the δ E value of color chips to calculate the amount of the dyestuff that comes off.

Following result is by get (result is expressed as the dyestuff mg that every kilogram of DYED FABRICS comes off) with the cotton of sun blue 078 dyeing

By the result's (result is expressed as the dyestuff mg that every kilogram of DYED FABRICS comes off) who gets with the cotton of direct red 227 dyeings

The result shows that the polymkeric substance of hydrophobically modified can provide the remarkable improvement to the dyestuff fixing performance, and the degree of improving depends on the amount of hydrophobic monomer in the multipolymer.

Embodiment 8: use: before washing test with by 95% DADMAC and 5% various The hydrophobically modified polymers of hydrophobic monomer polymerization preparation is fixed

In test the used polymkeric substance, all other test conditions identical with described in the embodiment 7.

By the result who gets with the cotton of sun blue 078 dyeing (result is expressed as the dyestuff mg that every kilogram of DYED FABRICS comes off)

The result shows that the polymkeric substance of hydrophobically modified can provide the remarkable improvement to the dyestuff fixing performance, and the degree of improving depends on the type of hydrophobic monomer in the multipolymer.

Claims

1. cleaning compositions, it comprises one or more tensio-active agents of significant quantity and by the polymerizable compound of forming derived from the main chain of following monomer component:

(I) cationic monomer of at least a following formula (1) of 20-99.9 weight %

Wherein

R ₁And R ₂Be hydrogen or C independently of each other ₁-C ₄Alkyl;

R ₃And R ₄Be hydrogen or alkyl, hydroxyalkyl, carboxyalkyl, Carboxylamide alkyl or alkoxyalkyl group independently of each other with 1-18 carbon atom; And Y ^-Represent negatively charged ion; With

(II) the hydrophobic unsaturated non-ionic monomer of polymeric 0.1-80 weight % in the presence of initiator, described monomer is selected from the ester based on the compound of (methyl) acrylate, (methyl) vinyl cyanide and unsaturated polyfunctional acid; With

(III) 0-60 weight % and monomer (I) and monomer (II) water-soluble monomer inequality and randomly

(IV) linking agent of 0-10 weight %.

2. the cleaning compositions of claim 1, wherein at least a cationic monomer (I) be selected from diallyldimethylammonium chloride, diallyl dimethyl brometo de amonio, diallyl dimethyl sulfate ammonium, diallyl dimethyl ammonium phosphate, diformazan for allyl dimethyl ammonium chloride, diethyl for allyl dimethyl ammonium chloride, diallyl two (beta-hydroxyethyl) ammonium chloride and diallyl two (β-ethoxyethyl) ammonium chloride.

3. the cleaning compositions of claim 1, wherein at least a cationic monomer (I) is a diallyldimethylammonium chloride.

4. the cleaning compositions of claim 1, wherein at least a hydrophobic monomer (II) is represented suc as formula (B)

R wherein ₅Be H or CH ₃, and R ₆Be C ₁-C ₁₂Alkyl, C ₁-C ₁₂Alkoxyl group, can be by C ₁-C ₁₂Alkyl or C ₁-C ₁₂Alkoxyl group replaces 1-3 time C ₁-C ₆Alkyl phenyl or by the oxygen C of one or many at interval ₁-C ₆Alkyl phenyl, wherein phenyl group can be by C ₁-C ₁₂Alkyl or C ₁-C ₁₂Alkoxyl group or C ₁-C ₆Alkyl hydroxy replaces 1-3 time; Represent with X-O-.

5. the cleaning compositions of claim 1, wherein hydrophobic monomer (II) is selected from

R wherein ₅Be H or CH ₃

6. the cleaning compositions of claim 1, wherein said polymerizable compound has the daltonian molecular-weight average of 1000-5000000.

7. the cleaning compositions of claim 1, it is detergent for washing clothes, fabric conditioner, pretreating agent, post-treatment agent or the roller drying sheet form with improved dyestuff fixing and dye migration inhibition.

8. the cleaning compositions of claim 1, it is for washing dish prescription form.

9. the cleaning compositions of claim 1 further comprises at least a following altered contents that is selected from: softening agent, spices, soil release polymer, tinting material, sanitas, various microorganisms are had various active antiseptic-germicides, wormer, dirt mite expellent and/or other control agent, white dyes, uv-absorbing agent, other light regime agent, ionizer, defoamer, various enzyme, SYNTHETIC OPTICAL WHITNER, oxide catalyst and zeolite.