CN1138873A - Use of polymers in liquid detergent compsn. containing brighteners for preventing fabric spotting - Google Patents

Use of polymers in liquid detergent compsn. containing brighteners for preventing fabric spotting Download PDF

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CN1138873A
CN1138873A CN 95191206 CN95191206A CN1138873A CN 1138873 A CN1138873 A CN 1138873A CN 95191206 CN95191206 CN 95191206 CN 95191206 A CN95191206 A CN 95191206A CN 1138873 A CN1138873 A CN 1138873A
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oxide
application
whitening agent
polymkeric substance
composition
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C·A·J·K·托恩
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Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3792—Amine oxide containing polymers

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
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Abstract

The present invention relates to the use of a polymer selected from polyamine N-oxide containing polymers and/or N-vinylimidazole N-vinylpyrrolidone in liquid detergent compositions for inhibiting fabric spotting associated with detergent compositions containing brighteners.

Description

In containing the liquid detergent composition of whitening agent, prevent the application of fabric spotting polymkeric substance
Technical field
The present invention relates to comprise the liquid detergent composition of white dyes.More specifically, the present invention relates in containing the detergent composition of whitening agent to use the polymkeric substance that contains polyamine N-oxide and/or N-vinyl imidazole N-vinylpyrrolidone copolymer to reduce and the relevant fabric spotting of this whitening agent of use.
Background of invention
Optical brightener also is called white dyes, is generally used for the liquid laundry additive.Whitening agent deposits on the fabric, in absorbing the uv-radiation energy herein and sending again with the form of blue light.Little yellow hue that this has has just reduced or eliminated fabric makes it to have the outward appearance of Bai Liang.
The specific question of following the liquid detergent composition that contains whitening agent is that undiluted whitening agent is used for fabric, and the whitening agent of high density becomes visible whitening agent spot on fabric.
The present invention is according to a discovery, promptly contains the polymkeric substance of polyamine N-oxide and/or the fabric spotting that N-vinyl imidazole N-vinylpyrrolidone copolymer suppresses whitening agent.What wash out from DYED FABRICS came off dyestuff before having an opportunity to be attached in the pulp washing on other thing, and this polymkeric substance just can make it to form coordination compound or with its absorption.
Common unsettled EP patent application is described a class for No. 92202168.8 and is comprised the dye transfer inhibiting composition that contains polyamine N-oxide pllymers.N-vinyl imidazole N-vinylpyrrolidone copolymer is described in such as DE 2814287-A to some extent at the prior art document, and the document relates to a class and comprises 0.1-10% (weight) water-soluble or water dispersible N-vinyl imidazole homopolymer or multipolymer and be mixed with negatively charged ion and/or the detergent composition of nonionogenic tenside and other washing composition batching.EP 372291 relates to the method for a kind of washing to the responsive fabric that fades.Washings contains anionic/nonionic tensio-active agent and the water-soluble polymers for example polymkeric substance or the multipolymer of N-vinyl imidazole, N-Yi Xi oxazolidinone or N-vinyl pyrrolidone.EP327927 describes a kind of comprising based on N-vinyl pyrrolidone and/or N-vinyl imidazole and/or the water-soluble high-molecular compound of N-Yi Xi oxazolidinone and the granular detergent additive of cation compound.DE 4027832-A discloses the no electrolytic liquid detergent composition that a class comprises zeolite A, nonionogenic tenside and dye transfer inhibiting polymers.Dye transfer inhibiting polymers is homopolymer and the multipolymer that is selected from N-vinyl pyrrolidone and/or N-vinyl imidazole and/or N-Yi Xi oxazolidinone.
According to the present invention, a kind of liquid detergent composition that comprises whitening agent is provided, said composition reduces or eliminates the fabric spotting of whitening agent when pre-treatment.
Summary of the invention
The present invention relates in liquid detergent composition to use the polymkeric substance that contains polyamine N-oxide and/or N-vinyl imidazole N-vinylpyrrolidone copolymer to suppress and the contained whitening agent bonded of detergent composition fabric spotting.
Detailed Description Of The Invention
The present composition comprises as a kind of whitening agent of basal component and a kind of polymkeric substance, and this polymkeric substance is selected from polymkeric substance and/or the N-vinyl imidazole N-vinylpyrrolidone copolymer that contains polyamine N-oxide.(a) contain the polymkeric substance of polyamine N-oxide P is a polymerizable unit in the formula, and the N-O group can be connected to this place or N-O group constitute polymerizable unit at this place a part, or both have concurrently.A is
Figure A9519120600042
, CO,
Figure A9519120600043
,-O-, -N-; X is 0 or 1.R is aliphatic series, aliphatic, the aromatics of oxyethyl group, heterocycle or alicyclic group or their any combination, and the nitrogen that the nitrogen of N-O group can be connected to this place or N-O group is the part of these groups at this place.
The N-O group can be represented with following universal architecture:
Figure A9519120600045
R in the formula 1, R 2And R 3Be aliphatic series, aromatics, heterocycle or alicyclic group or their combination, x or/and y or/and z is 0 or 1, and the nitrogen of the N-O group ammonia that can be connected to this place or N-O group constitutes the part of these groups at this place.
The N-O group can be that the part of polymerizable unit (P) maybe can be connected on the main polymer chain or both have concurrently.
The polyamine N-oxide that is suitable for, the part at this N-of place group formation polymerizable unit comprises the polymkeric substance that contains polyamine N-oxide, and wherein R is selected from aliphatic series, aromatics, alicyclic or heterocyclic group group.This polymkeric substance that contains polyamine N-oxide of one class comprises a group polyamine N-oxide, and the nitrogen of N-O group constitutes the part of R base at this place.The polymkeric substance that preferably contains poly-N-oxide compound be those wherein R be heterocyclic radical a such as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and their derivative.
This polymkeric substance that contains polyamine N-oxide of a class comprises a group polyamine N-oxide again, and wherein the ammonia of N-O group is connected on the R base.
Another kind of suitable polyamine N-oxide is that those N-O groups are connected to the polyamine oxide compound on the polymerizable unit.
The preferred classes of these polyamine N-oxide is that those have general formula (I), and R is aromatics, heterocycle family or alicyclic group in the formula, and the nitrogen of N-O functional group is the polyamine N-oxide of the part of this R base at this place.More than all kinds of examples be the polyamine oxide compound, wherein R is heterogeneous ring compound a such as pyridine, pyrroles, imidazoles and their derivative.
A preferred classes again of polyamine N-oxide is that those have general formula (I), and R is aromatics, heterocycle family or alicyclic group in the formula, and wherein the ammonia of N-O functional group is connected to the polymkeric substance that contains polyamine N-oxide on this R base.More than all kinds of examples be the polyamine oxide compound wherein the R base can be that aromatics is such as phenyl.
Any main polymer chain can use, in the amine oxide polymers that will form be water miscible and have the dye transfer performance.The example of the main polymer chain that is suitable for is polyvinyls, polyene, polyester, polyethers, polymeric amide, pi, polyacrylic ester, and their mixture.
The amine of amine n-oxide polymkeric substance of the present invention is generally 10 with the ratio of amine n-oxide: 1-1: 1,000,000.But the content that contains amine oxide in the polymkeric substance of polyamine oxide compound can change because of suitable copolyreaction or because of suitable N-oxidisability.The ratio of amine and amine n-oxide preferably 2: 3-1: 1,000,000.Be more preferably 1: 4-1: 1,000,000, most preferably 1: 7-1: 1,000,000.In fact polymkeric substance of the present invention comprises random or segmented copolymer, and a kind of here monomer is an amine n-oxide, another kind of monomer or amine n-oxide or be not.The unitary pKa of the amine oxide of polyamine N-oxide＜10, preferably pKa＜7 are more preferably pKa＜6.
The polymkeric substance that contains polyamine N-oxide almost can make with any polymerization degree.Requirement to the polymerization degree is not crucial, as long as material has predetermined water-soluble and dye suspension ability, molecular-weight average is usually at 500-1,000,000; Preferably 1,000-50,000, be more preferably 2,000-30,000, most preferably be 3,000-20 is within 000 scope.
The content that the present invention contains polyamine N-oxide pllymers is the 0.001-10% of dye transfer inhibiting composition weight normally, is more preferably 0.01-2%, most preferably is 0.05-1%.
The present composition is suitable for being used for laundry operation as the additive of conventional detergent composition.The present invention also comprises dye transfer inhibiting composition, and this thing will contain the washing composition batching thereby be used as detergent composition.The preparation method of polyamine N-oxide
The manufacture method of polyamine N-oxide can make the amine monomers polymerization make the polymkeric substance oxidation of gained then with suitable oxygenant earlier, perhaps makes the polymerization of amine oxide monomer own to make polyamine N-oxide.The synthetic example that is used as of the synthetic available polyethylene yl pyridines N-oxide compound of polyamine N-oxide.Be dissolved in advance and use peracetic acid solution (25g Glacial acetic acid, 6.4g 30% (volume) H in the 50ml acetate then available from poly--4-vinylpridine of Polysciences (mw.50,000,5.0g, 0.0475mol) 2O 2Solution and several H 2SO 4Make the 0.0523mol peracetic acid) handle by volumetric pipette.Mixture stirs more than 30 minutes down in room temperature (32 ℃).Oil bath was heated to 80-85 ℃ in 3 hours and shelves whole night then.The polymers soln of gained mixes with 1 liter of acetone under whipped state again, and the yellowish brown viscosity paste that forms in the bottom is used 1 liter of washing with acetone once more, makes a kind of pale asphyxia crystalline solid.This solid leaches by gravity, uses washing with acetone, uses P then 2O 5Drying, the amine of this polymkeric substance: the ratio of amine n-oxide is 1: 4.N-vinyl imidazole N-vinylpyrrolidone copolymer
The present invention comprises the polymkeric substance as a kind of N-of being selected from vinyl imidazole N-vinylpyrrolidone copolymer of basic detergent ingredients.The average molecular weight range of N-vinyl imidazole N-vinyl pyrrolidone polymer is 5,000-1,000,000, preferably 20,000-200,000.Be used for the polymkeric substance that detergent composition of the present invention polymkeric substance very preferably comprises a kind of N-of being selected from vinyl imidazole N-vinylpyrrolidone copolymer, wherein the average molecular weight range of this polymkeric substance is 5,000-50,000, be more preferably 8,000-30,000, most preferably be 10,000-20,000.See BarthH.G.and Mays J.W.Chemical Analysis Vol.113 " Modern Methods ofPolymer Characterization " with the description of light scattering determining molecular-weight average.The average molecular weight range of preferred N-vinyl imidazole N-vinylpyrrolidone copolymer is 5,000-50, and 000, be more preferably 8,000-30,000, most preferably be 10,000-20,000.
N-vinyl imidazole N-vinylpyrrolidone copolymer with above-mentioned average molecular weight range feature provides excellent dye metastasis inhibition performance, the washing usefulness of the detergent composition that unlikely harmful effect of while is made into thus.
The mol ratio of N-vinyl imidazole and N-vinyl pyrrolidone is 1-0.2 in the N-vinyl imidazole N-vinylpyrrolidone copolymer of the present invention, is more preferably 0.8-0.3, most preferably is 0.6-0.4.N-vinyl imidazole N-vinylpyrrolidone copolymer can be straight chain or side chain.The content of N-vinyl imidazole N-vinyl pyrrolidone is the 0.01-10% of detergent composition weight in the detergent composition, is more preferably 0.05-5%, most preferably is 0.1-1%.(b) whitening agent
A kind of basic batching of the present composition is a whitening agent.The whitening agent that is suitable for comprises the stilbene whitening agent.The stilbene whitening agent is the aromatic substance that a class has two aryl that separated by the alkene chain.They preferably have following structural: R in the formula 1Be hydrogen, halogen, alkyl, alkoxyl group or phenyl; R 2It is hydrogen or alkyl; M is hydrogen, basic metal or ammonium ion; N=0-2, but a SO must be arranged in the formula at least 3The M base; And m=1-2, when m=1, the substituting group on the bonded carbon is a hydrogen.
The stilbene whitening agent that is particularly suitable for here using is in US patent 4,309,316,4,298, describes to some extent in 490 and 5,035,825.
Effective to be with sulfonic bleach stable negatively charged ion whitening agent be preferred to cotton (Mierocrystalline cellulose).
The most preferred stilbene whitening agent that here uses is because its bleach stable is Tinopal RCBS-X, Phenylsulfonic acid, 2,2 '-((1,1 '-phenylbenzene)-4,4 '-two bases two-2,1-ethylene base) two-, disodium salt (CA index-name).Tinopal RThe CBX-X structural formula is:
Figure A9519120600071
Other operable whitening agent is hydrophobic, and its structure is: R in the formula 1, R 2, R 3And R 4Be independent selected anilino, hexamethylene amino, piperazinyl, phenyl diamino, toluene diamino, morpholino, and amino-phenol, but must make whitening agent contain no more than 1 morpholino base.
The whitening agent form that is suitable for comprises possible R 1-4Any combination of composition.The example of preferred whitening agent form is four anilinos, four piperazinyls, the own amino in Fourth Ring and their combination such as hexichol amido two piperazinyls and hexichol amido dicyclohexylamine base form.
Because the whitening agent stain is reduced to minimum, four anilino derivatives are very preferred, and it meets following formula:
4,4 '-two (4-anilino-6-anilino-S-triazine-2-yl) amino)-2,2 '-stilbene disulfonic acid sodium salt (A).Preferred within the scope of the present invention whitening agent system contains 40% (washing whitening agent total amount) at least and relates to the specific hydrophobic whitening agent that above is mixed with conventional washing whitening agent, for example, and two sulfonation hexichol amidos, dimorpholino stilbene whitening agent.
Mix the routine washing whitening agent that uses with hydrophobicity form mentioned above and comprise that general washing whitening agent comprises:
4,4 (2H-naphtho-s (1,2-d) triazole-2-yl)-2-stilbene sulfonate sodium; (i)
4,4 '-two (4-anilino-6 (N-2-hydroxyethyl-N-methylamino-)-S-triazine-2-yl) amino)-2,2 '-the stilbene disulfonic acid disodium salt; (ii)
4,4 '-two (4-anilino-6-morpholino-S-triazine-2-yl) amino)-2,2 '-the stilbene disulfonic acid sodium salt; (iii)
2,2-(4,4 '-biphenylene connection vinylene)-DAADBSA, disodium salt is (iv)
4,4 '-two (4-phenyl-2H-1,2,3-triazole-2-yl) disodium salt; (v)
4,4 '-two (4-anilino-6-morpholino-1,3,5-triazines-2-yl) amino)-2-stilbene sulfonate sodium is (vi)
Being present in the weight ratio that contains polyamine N-oxide pllymers and/or N-vinyl imidazole N-vinyl pyrrolidone and whitening agent in the detergent composition is 1/20-20/1, and preferably 1/10-12/1 is more preferably 1/1-12/1, most preferably is 2/1-7/1.The washing composition batching
In another embodiment of the invention, a kind of liquid detergent composition is provided, said composition comprises the dye transfer inhibiting composition with the washing composition batch mixes.The tensio-active agent of all kinds can both be used for detergent composition of the present invention.
Invest the typical catalogue of listing negatively charged ion, nonionic, both sexes and the zwitterionic classification and the form of these tensio-active agents in the US patent 3,664,961 of Norris on May 23rd, 1972.
The preferred anionic surfactants tensio-active agent comprises alkyl sodium sulfate ester herein, and this ester is ROSO 3The water-soluble salt of M or acid, R is C in the formula 10-C 24Alkyl preferably contains C 10-C 20The alkyl of alkyl component or hydroxyalkyl are more preferably C 12-C 18Alkyl or hydroxyalkyl, M is H or positively charged ion, alkali metal cation (for example sodium, potassium, lithium) for example, ammonium or replace ammonium (for example methyl-, dimethyl-and trimethyl ammonium positively charged ion and quaternary ammonium cation such as tetramethylammonium and nanophyn positively charged ion, and from the quaternary ammonium cation of alkylamine such as ethamine, diethylamine, triethylamine, and their mixture etc.).Usually, be used for low wash temperature (for example being lower than about 50 ℃), C 12-C 16Alkyl chain is preferred, is used for high wash temperature (for example being higher than about 50 ℃), C 16-C 18Alkyl chain is preferred.
Anion surfactant very preferably comprises alkoxylate alkyl sodium sulfate ester surfactant herein, and this ester is RO (A) mSO 3The water-soluble salt of M or acid.R contains C in the formula 10-C 24The not replacement C of alkyl component 10-C 24Alkyl or hydroxyalkyl, preferably C 12-C 20Alkyl or hydroxyalkyl are more preferably C 12-C 18Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is greater than 0, usually between about 0.5 and about 6, more preferably between about 0.5 and about 3, M is H or positively charged ion, can be metallic cation (for example sodium, potassium, lithium, calcium, magnesium etc.) for example, ammonium or replace ammonium cation.Ethoxylation alkyl sodium sulfate ester and propoxylation alkyl sodium sulfate ester are here gazed at.The object lesson that replaces ammonium cation comprise methyl-, dimethyl-, trimethyl ammonium positively charged ion and quaternary ammonium cation such as tetramethylammonium and nanophyn positively charged ion and from the quaternary ammonium cation of alkylamine such as ethamine, diethylamine, triethylamine, their mixture etc.Exemplary surfactants is C 12-C 18The many ethoxylations of alkyl (1,0) sulfuric ester (C 12-C 18E (1,0) M), C 12-C 18The many ethoxylations of alkyl (2,25) sulfuric ester (C 12-C 18E (2,25) M), C 12-C 18The many ethoxylations of alkyl (3.0) sulfuric ester (C 12-C 18E (3.0) M) and C 12-C 18The many ethoxylations of alkyl (4.0) sulfuric ester (C 12-C 18E (4.0) M) wherein M is suitable for being selected from sodium and potassium.
Other anion surfactant that is suitable for is to comprise C 8-C 20Carboxylic acid (being lipid acid) linear ester is at interior alkyl sulfonate surfactants, this ester gaseous state SO 3According to " The Journal of theAmerican Oil Chemists Society ", 52 (1975), the method sulfonation of pp.323-229.The starting material that is suitable for comprises tallow oil, palm wet goods natural fat material.
Preferred alkyl sulfonate surfactants, special in the washing purposes, comprise alkyl sulfonate surfactants with following structural: R in the formula 3Be C 8-C 20Alkyl, preferably alkyl or their combination, R 4Be C 1-C 6Alkyl, preferably alkyl or their combination, M is the positively charged ion that and alkyl ester sulfonate radical form insoluble salt.The salt-forming cation that is suitable for comprises metal such as sodium, potassium, and lithium and replacement or unsubstituted ammonium cation, such as monoethanolamine, diethanolamine, and trolamine.R 3C preferably 10-C 16Alkyl, and R 4Be methyl, ethyl or sec.-propyl.Particularly preferably be R in the methyl ester sulfonate formula 3Be C 10-C 16Alkyl.
Other anion surfactant that is used for washing purpose can be included in washing detergent compositions of the present invention equally.They can comprise soap salt (comprise sodium, potassium, ammonium, and the substituted ammonium salt class such as single, two-and triethanolamine salt), C 9-C 20Linear alkylbenzene sulfonate, C 8-C 22Uncle or secondary sulfonated alkane, C 8-C 24Sulfonated alkene, sulfonation poly carboxylic acid (this acid method for making is in English Patent 1,082, describes to some extent in 179, makes the pyrolysis product sulfonation of alkaline earth metal citrate), C 8-C 24Alkyl polyglycol ether sulfuric ester (containing the oxyethane below 10 moles); Alkyl glycerol sulphonate, fatty acyl group glycerine sulphonate, fatty oil acylglycerol sulfuric ester, alkylphenol oxygen Vinyl Ether sulfuric ester, paraffin sulfonate, alkyl phosphate, isethionic acid ester such as acyl group isethionic acid ester, N-acyl taurate, succinic diamide acid alkyl ester and sulfosuccinic acid alkyl ester, sulfosuccinic acid monoesters (especially saturated and undersaturated C 12-C 18Monoesters) and sulfosuccinic acid diesters (especially saturated and undersaturated C 6-C 12Diester), the sulfuric ester of the sulfuric ester of acyl group methylglycine ester, alkyl polysaccharide such as alkyl polyglucoside (nonionic non-sulfuric acid compound is described in down), branched primary alkyl moiety sulfuric ester and the many ethoxy carboxylates of alkyl such as general formula are RO (CH 2CH 2O) k-CH 2COO-M +The carboxylate salt formula in R be C 8-C 22Alkyl, k are the integers of 0-10, and M is the solubility salt-forming cation.Resinous acid and hydrogenated resin acid are suitable for equally, such as rosin, staybelite and be present in or from the resinous acid and the hydrogenated resin acid of Yatall MA.Other example is described in " Surface ActireAgentsomd Detergents " (Vol.I.and II by Schwartz, Perry and Berch) to some extent.Above-mentioned tensio-active agent various in style also briefly is disclosed in US patent 3,929,678 and goes to the 29th hurdle the 23rd from the 23rd hurdle the 58th row, and this patent is authorized Laughlin (being hereby incorporated by) on December 30th, 1975.
When wherein containing sometimes, the present invention does washing, and to comprise about 0.2%-usually about 40% for detergent compositions, about this analog anion surfactants of 20% weight of preferably about 0.5%-.
An effective in the present invention class nonionogenic tenside is the condenses of oxyethane and hydrophobic ingredient, and the scope of the average hydrophile-lipophile balance value of gained tensio-active agent (HLB) is 6-17, and preferably 8-17 is more preferably 9.5-14, most preferably is 12-14.On hydrophobic (oleophylic) constitutive property can be aliphatic series or aromatics, can regulate easily to make a kind of water-soluble cpds with the polyoxyethylene groups length of arbitrary specific hydrophobic group condensation, and the quality of balance between its hydrophilic group and the hydrophobic group is needed.
Preferred nonionic comprises C 9-C 13Primary alcohol ethoxylate, every mol of alcohol contains the 3-30 moles of ethylene oxide.
Other nonionogenic tenside that can use is C 13-C 15The primary alconol alcoxylates, it includes many oxyethyl groups block of 1-2 oxyethyl group, also includes many propoxy-block of 3-4 propoxy-.
Particularly preferred nonionogenic tenside is C 9-C 15Primary alcohol ethoxylate, it comprises 3-12 moles of ethylene oxide/mol of alcohol, particularly C 12-C 15Primary alconol, it comprises 5-8 moles of ethylene oxide/mol of alcohol.
Another class ionic surfactant pack contains the alkyl polyglucoside compound with following general formula:
RO (C nH 2nO) tZ xZ is the composition from glucose in the formula; R is a saturated hydrophobic alkyl that contains 12-18 carbon atom; T is 0-10, and n is 2 or 3; X is 1.3-4, and this compound comprises less than 10% unreacted fatty alcohol with less than 50% short-chain alkyl polyglucoside.This compounds and be disclosed in EP-B 0 070 077,0 075 966 and 0 094 118 in detergent application.
What be suitable for use as nonionogenic tenside equally is the polyhydroxy fatty acid amide surfactant of following formula:
Figure A9519120600101
R in the formula 1Be H, or R 1Be C 1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R 2Be C 5-31Alkyl, Z are many hydroxyl alkyls that straight-chain alkyl is arranged, and have three alkyl that directly are connected on the chain at least, or the alkoxy derivative of above-mentioned many hydroxyl alkyls.Preferably, R 1Be methyl, R 2It is straight chain C 11-15Alkyl or alkenyl chain such as cupraol alkyl or its mixture, Z is from reducing sugar such as glucose, fructose, maltose, the lactose of reductive amination reaction.
When wherein containing sometimes, the present invention washs detergent compositions, and to comprise about 0.5%-usually about 40%, and preferably about 0.5%-is about 20%, very preferably is this class nonionogenic tenside of 0.5%-10% weight.
Composition of the present invention also can comprise a kind of builder system.The builder system of any routine here all is suitable for, they comprise alumino-silicate materials, silicate, poly carboxylic acid and lipid acid, some materials are such as ethylenediamine tetraacetic acid (EDTA), metal ion chelation agent is such as aminopolyphosphonic acid ester, particularly ethylenediamine tetramethylene phosphonic acid and diethylenetriamine pentamethylenophosphonic acid(DTPP).Though because significantly environment reason is and little preferred, phosphate builders here can be used equally.
The washing assistant that is suitable for can be a kind of inorganic ion exchange material, and normally a kind of inorganic aquation alumino-silicate materials more specifically is that a kind of aquation synthetic zeolite is such as aquation zeolite A, X, B or HS.Another inorganic builders material that is suitable for is a layered silicate, for example SKS-6 (Hoechst company).SKS-6 is a kind of by water glass (Na 2Si 2O 5) crystalline layered silicate formed.
Here the polycarboxylate washing assistant of Shi Yonging comprises citric acid, preferably is the water-soluble salt state: formula R-CH (COOH) CH 2(COOH) succinic acid derivative, R is C in the formula 10-20Alkyl or alkenyl, preferably 12-16Or R can be replaced by hydroxyl, sulfo group, sulfoxide group or sulfuryl substituting group in the formula.Object lesson comprises succsinic acid lauric acid, succsinic acid myristin, succsinic acid palm ester, succsinic acid 2-dodecylene ester, succsinic acid 2-tetradecene ester.The succinate washing assistant preferably is its water-soluble salt state to be used, and comprises sodium, potassium, ammonium and alkanol ammonium salts.
The mixture that other polycarboxylate that is suitable for is oxo disuccinate and tartrate one succsinic acid and tartrate disuccinic acid is such as US4, described in 663,071.The liquid that is in particular is here made, and the lipid acid washing assistant of Shi Yonging is saturated or unsaturated C here 10-C 18Lipid acid and corresponding soap.Preferred saturated form has 12-16 carbon atom in alkyl chain.Preferred unsaturated fatty acids is an oleic acid.Another preferred liquid composition builder system is based on the succsinic acid dodecyl ester.
Other water-soluble organic salt that is suitable for is the acid of homopolymerization type or copoly type acid or their salt, and wherein poly carboxylic acid contains two at least each other by no more than two carboxyls that carbon atom separates.This base polymer is disclosed in GB-A1, in 596,756, the example of this salt be MW2000-5000 polyacrylic ester and with the multipolymer of maleic anhydride, the molecular weight of this analog copolymer is 20,000-70,000, particularly about 40,000.
The content of de-sludging builder salt is the 2%-80% of composition weight normally, 20%-70 preferably, and modal is 30%-60%.
Detergent composition of the present invention can comprise SYNTHETIC OPTICAL WHITNER.Be applicable to that SYNTHETIC OPTICAL WHITNER of the present invention can be a kind of activation or non-activated SYNTHETIC OPTICAL WHITNER.
One class available oxygen bleaching agent comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The suitable example of this class additive comprises magnesium salts, 4-amino in the ninth of the ten Heavenly Stems-4-perbutyric acid of a phthalic acid magnesium hexahydrate, metachloroperbenzoic acid and crosses two (dodecandioic acids).This class SYNTHETIC OPTICAL WHITNER is disclosed in US patent 4,483,781, US patent application 740,446, european patent application 0,133,354 and US patent 4,412,934.SYNTHETIC OPTICAL WHITNER very preferably also comprises US patent 4,634, and the 6-amino-6-in the ninth of the ten Heavenly Stems described in 551 crosses caproic acid.
Another kind of available SYNTHETIC OPTICAL WHITNER comprises halogen bleaching agent.The example of hypohalite SYNTHETIC OPTICAL WHITNER comprises for example TCCA (Trichloroisocyanuric acid) and dichloroisocyanuric acid sodium and potassium and N-chlorine and N-bromoalkane sulphonamide.The addition of this class material is the 0.5-10% of finished product weight normally, preferably 1-5%.
Be applicable to that SYNTHETIC OPTICAL WHITNER of the present invention preferably includes peroxygen bleach.The example of suitable water dissolubility solid peroxygen bleach comprises the hydrogen peroxide releasing agent such as perborate, for example perborate monohydrate, perborate tetrahydrate, persulphate, percarbonate, peroxydisulfate, superphosphate and hydrated peroxide.Preferred SYNTHETIC OPTICAL WHITNER is percarbonate and perborate.
The hydrogen peroxide releasing agent can and be used with bleach-activating agent; such as tetra acetyl ethylene diamine (TAED), nonanoyl hydroxy benzene sulfonate (NOBS, US4; 412; 934), 3; 5-trimethyl hexanol hydroxy benzene sulfonate (ISONOBSEP120; 591) or five acetyl glucose (PAG), this sugar all-hydrolytic forms peracid and bleaches form as activity, causes bleaching the raising of usefulness.The same activator that is suitable for is an acetylizad citrate (ATC) such as this additive that is disclosed in No. 91870207.7, the common unsettled european patent application.
A kind of preferred SYNTHETIC OPTICAL WHITNER is a hydrogen peroxide.Hydrogen peroxide can itself exist or can urge system (being enzyme and substrate thereof) by adding a kind of enzyme, and this system in the beginning of washing and/or rinse or time-continuing process hydrogen peroxide can take place.This kind of enzyme system of urging is disclosed in the EP number of patent application of submitting on October 9th, 1,991 91202655.6.
Be applicable to that other peroxygen bleach of the present invention comprises that organic peroxide acid is such as percarboxylic acids.
SYNTHETIC OPTICAL WHITNER except that oxygen bleaching agent also is as known in the art and can here uses.The valuable especially non-oxygen bleaching agent of one class comprises photoactivation SYNTHETIC OPTICAL WHITNER such as sulfonated zinc and/or aluminium phthalocyanine.This class material can be deposited on the substrate in the washing time-continuing process.When in the presence of oxygen with rayed such as clothes is hung up drying in daylight, sulfonated zinc phthalocyanine is activated, substrate thereby bleached.Preferred zinc phthalocyanine and photoactivation bleaching method are described in US patent 4,033,718 to some extent.Usually the content of sulfonation zinc phthalocyanine phthalocyanine is about 1.25% (weight) of about 0.0001%-in the detergent composition.In addition, have found that the polymkeric substance that contains polyamine N-oxide reduces or eliminates this photoactivation SYNTHETIC OPTICAL WHITNER and deposits on the fabric, the result does not have fabric spotting basically when pre-treatment and/or washing.
Other washing composition batching that can comprise is the de-sludging enzyme, and it is to remove protein-based, candy base or triglyceride level base stain for variety of applications comprises that this enzyme is included in the detergent formulations, for example, and prevents the dye transfer that splits away off.The enzyme of sneaking into comprises proteolytic enzyme, amylase, lipase, cellulase, reaches peroxidase and their mixture.The enzyme of other kind also can be included.They can be from any suitable origin, such as plant, animal, bacterium, mould and yeast.
The normally every gram composition of the addition of enzyme is enough to produce up to about 5mg, and more typical is to produce up to about the about 3mg organized enzyme of 0.05mg-.
The example of useful proteases is a subtilysin, and they are that specific bacterial strain from Bacillus subtilis and Bacillusilcheniforms obtains.The commercially availabie proteolytic ferment that is suitable for removing protein-based stain comprises with following trade name product sold: Alcalase, Sasinase and Esperase (NovoIndustsies A/S, Denmark) and Maxatase (International Bio-Synthetics, Holland) and FN-base (Geneucor), Optimase and Opticlean (MKC) Inc..
Especially valuable to liquid detergent composition in the proteolytic ferment is the enzyme that is called protease A and proteolytic enzyme B here.Protease A is described in european patent application 130,756 to some extent.Proteolytic enzyme B in European Patent Application No. 87303761.8 describe.Amylase comprises, amylase for example, and from specific enzymes strain B.licheniforms, this has more detailed description in English Patent 1,196 among 839 (Novo).Starch decomposing protein matter comprises, for example Rapidase, Maxamyl (Internafional Bio-Synthetics, Inc.) and Termamyl (Novo Indnstries).
Can be used for the cellulase that also comprises mould that cellulase of the present invention had both comprised bacterium.Their pH optimum value is preferably between 5 and 9.5.The plain enzyme of useful fiber is disclosed in the US patent 4,435,307, people such as Barbesgoard, this patent disclosure originate from the mould cellulase of Humicola insolens.The plain enzyme of useful fiber also is disclosed in GB-A-2, in 075,028, GB-A-2,095,275 and DE-OS-2,247,832.
The example of the plain enzyme of this fibrid is by bacterial strain Humicola insolens (Humicola grisea var.thermoidea), particularly the cellulase of Humicola strain DSM 1800 generations.The cellulase that produces with the mould that forms cellulase 212 that belongs to by mould Bacillus N or Aeromonas, and the cellulase that extracts from the liver pancreas of sea mollusk (Dolabella Auricula Solander).The plain enzyme of other useful fiber is the cellulase that results from Humicola Insulens, and the molecular weight of this enzyme is about 50KDa, and iso-electric point is 5.5, contains 415 amino acid.Describe to some extent in the co-pending European application that this cellulase was submitted on March 19th, 1993 numbers 93200811.3.The cellulase of particularly suitable is the cellulase that color protection benefit is arranged.The example of this cellulase is to describe to some extent in the European Patent Application No. 91202879.2 of Carezyme on November 6 (Novo) in 1991 submission.
The lipase that detergent use is suitable comprises the microorganism by Pseudonionas group, and such as the lipase that Pseudomonasstutzeri ATCC 19.154 produces, this enzyme is disclosed in English Patent 1,372,034.The lipase that is suitable for comprises by microorganism Pseudomonas fluorescent IAM 1057 and producing, and shows the lipase of positive immunological cross-reaction with lipase antibody.This lipase is by Amano PharmaceuficalCo.Ltd., Nagoya, and the Japan supply, trade name Lipase P " Amano " hereinafter is called " Amano-P ".The lipase of particularly suitable is the lipase such as M1 Lipase (Ibis) and Lipolase (Novo).
Peroxidase and oxygen source and usefulness, oxygen source is percarbonate, perborate, persulphate, hydrogen peroxide etc. for example.They are used for " solution bleaching ", prevent promptly during the laundry operation that the dyestuff that splits away off from substrate or pigment transfers to that other substrate gets in the washings.Peroxidase is as known in the art, for example comprises horseradish peroxidase, ligninase, and haloperoxidase such as chloro-and bromine peroxide enzyme.The detergent composition that contains peroxidase is disclosed in, for example in the European Patent Application No. 91202882.6 that PCT International Application No. WO 89/099813 and on November 6th, 1991 submit to.In liquid preparation, preferably use a kind of enzyme stabilising system.The enzyme stabilising method of aqueous detergent compositions are well-known in the art.For example, a kind of enzyme stabilising method in the aqueous solution comprise the free calcium ion of application from the calcium source, and the calcium source is such as lime acetate, calcium formiate and calcium propionate.Calcium ion can with short chain carboxy acid's salt, preferably formate and use.Check that for example the US patent 4,318,818.The mixture that has proposed to use polyvalent alcohol, alkoxyl alcohol, ethylene glycol bisthioglycolate alkyl oxide, polyvalent alcohol and multifunctional aliphatic amine as glycerine and sorbyl alcohol in addition (for example, such as diethanolamine, trolamine, diisopropanolamine (DIPA) etc.) and boric acid or alkali metal borate.The alcohol stabilising method disclose and are embodied in US patent 4,261,868, US patent 3,600,319 and european patent application 0199405, application number 86200586,5 in addition.Non-boric acid and borate stablizer are preferred.The enzyme stabilising system is also in US patent 4,261,868,3,600, describes to some extent in 319 and 3,519,570.
Other washing composition that is suitable for adding batching is the oxydasis scavenging agent, describes to some extent in the European Patent Application No. of determining in the common end that this agent was submitted on January 31st, 1,992 92870018.6.The example of this fermentoid oxidation scavengers is ethoxylation four ethylidene polyamines.
Can use those to be used for other component of detergent composition, prevent agent, tinting material and spices such as soil-suspending agent, soil releasing agent, abrasive, sterilant, tarnishing.Have been found that in addition the polymkeric substance that contains polyamine N-oxide prevents this colorant deposition to fabric, the result does not have fabric spotting basically when pre-treatment and/or washing.
Liquid composition of the present invention can also exist with " enrichment stage ".In this case, liquid detergent composition of the present invention is compared with the conventional liq washing composition, and water ratio is lower.
The water ratio of concentrated liquid detergent is more preferably less than 20% usually less than 30% of detergent composition weight, most preferably is less than 10%.
Have found that the present invention such as during pre-processing, when liquid washing agent directly contacts with fabric, is exceedingly useful.But the present invention is very suitable for being suppressed at the fabric spotting that takes place between the fabric washing operational period equally.
Method of the present invention can laundry operation before or during laundry operation, carry out.Laundry operation especially carries out under 20 ℃-60 ℃ preferably at 5 ℃-95 ℃.The pH of treatment solution is 2-10.5, and preferably 3.5-10.5 is more preferably 2-6.
Method and composition of the present invention can also add goods as the washing de-sludging.Laundry additive composition contains the tensio-active agent that is not more than 10% (weight) usually.Composition of the present invention is very effective when proving in being compounded in this laundry additive composition.This class is added goods and is used for improving conventional detergent composition usefulness.
Detergent composition of the present invention comprises the composition that is used to wash substrate such as fabric, fiber, crust, skin etc., for example hard surface detergent compositions (being with or without abrasive), laundry detergent compositions, automatic and nonautomatic dishwashing composition.
The following example is in order to illustrating the present composition, but might not limit the scope of the invention.
Liquid composition according to the present invention's preparation has following composition:
(a)
Polyethoxye propoxy-alcohol 1.00
Alkyl sodium sulfate ester 1.00
BHT (butylhydroxy methyl) 0.03
Spices (Miraflor) 0.10
Hydrogen peroxide 7.00
H 2SO 4To pH4
Distilled water
The % of detergent composition gross weight
Table 1
Eliminate the research of degree about whitening agent spot on 100% cotton fabric and carry out under multiple different condition, these conditions and possible goods working conditions are suitable.These goods working conditionss are as follows:
I) goods are applied on the fabric, are placed on washing (temperature: 40 ℃/washing time: 25 minutes) in the washing measuring apparatus after 10 minutes
II) goods are dry on fabric, are placed on washing (temperature: 40 ℃/washing time: 25 minutes) on the washing measuring apparatus then
III) goods are applied on the fabric, rinse after 10 minutes
IV) goods are dry on fabric, then rinse
Expert's scoring group is identified fabric spotting by visual inspection with following grade under daylight.
Psu0 be sure of not have the whitening agent spot
Psu1 seems to see a small amount of light spot but not necessarily
Psu2 be sure of to have a small amount of light spot
Psu3 be sure of spottiness
Psu4 has a large amount of dense spot experiment conditions:
A: according to the detergent composition of table 1, it does not contain whitening agent, does not contain poly-(4-vinylpridine N-oxide compound)
B: according to the detergent composition of table 1, it contains 0.06% (weight) whitening agent (Tynopal CBS-X), does not contain poly-(4-vinylpridine N-oxide compound)
C: according to the detergent composition of table 1, it contains poly-(4-vinylpridine N-oxide compound), and its molecular-weight average is about 10,000, and amine is 1: 5 (recording with NMR) with the ratio of amine n-oxide, does not contain whitening agent
D: according to the detergent composition of table 1, it contains whitening agent (Tynopal CBS-X) and 0.06% (weight) poly-(4-vinyl N-oxide compound), its molecular-weight average is about 10.000, and amine is that 1: 5 (recording with NMR) result is as follows with the ratio of amine N monoxide:
A B C D
I 0 2 0 0
II 0 3 0 1
III 0 2 0 0
IV 0 4 0 2
From above-listed result as seen, the interpolation of poly-(4-vinylpridine N-oxide compound) has obviously reduced the whitening agent spot.
Prepared following laundry liquid detergent compositions:
I II III IVC 12-C 15Alkyl sodium sulfate ester-19.0 21.0-C 12-C 15Ethoxyquin alkyl sodium sulfate ester 23.0 4.0 4.0 25.0C 12-C 14N-methyl glucose amide 9.0 9.0 9.0 9.0C 12-C 14Fatty alcohol ethoxylate 6.0 6.0 6.0 6.0C 12-C 16Lipid acid 9.0 6.8 14.0 14.0
Brightening agent 1.0 0.1 0.1 0.1N-vinyl imidazole NVP copolymers 0.5 0.5--it is poly-that (4-vinylpridine N-oxide)--0.5 0.5 hydrogen peroxide, 5555 anhydrous citric acid 6.0 4.5 3.5 3.5 diethylenetriamine pentamethylenophosphonic acids, 1.0 1.0 2.0 2.0 water and micro-thing are added to 100%
Above-listed composition (I-IV) is very good aspect performance washing usefulness, and fabulous color protection benefit is arranged, and does not form tangible fabric spotting on fabric.
Prepared following liquid scrubbing additive:
(a) (b) (c) (d) Dobanol R91-10--3 3Dobanol R23-3--1 1Dobanol R23-6.5--1 1Lutensol R0.2 0.2N-vinyl imidazole N-vinyl 0.3-0.3-pyrrolidones copolymer gathers (4-vinylpridine N-oxygen-0.3-0.3 compound) brightening agent 0.06 0.06 0.06 0.06 hydrogen peroxide 777 7H to A030--11 polyethoxy propoxyl group alcohol, 1 1--alkyl sodium sulfate ester 1 1--BHT (butylated hydroxytoluene), 1 1--spices (Miraflor), 111 1Isofol 16--2SO 4To pH4
Above-listed composition (a)-(d) is very good aspect demonstration washing usefulness, and fabulous color protection benefit is arranged, and does not form tangible fabric spotting on fabric.

Claims (15)

1. the application of polymkeric substance in containing the detergent composition of whitening agent, to reduce the whitening agent spot, this polymkeric substance is selected from polymkeric substance and/or the N-vinyl imidazole N-vinylpyrrolidone copolymer that contains polyamine N-oxide.
2. according to the application of claim 1, wherein this polymkeric substance that contains polyamine N-oxide is poly-(4-vinylpridine N-oxide compound).
3. according to the application of claim 1-2, wherein amine is 2 with the ratio of amine n-oxide: 3-1: 1,000,000, preferably 1: 4-1: 1,000,000, and most preferably be 17-1: 1,000,000.
4. according to the application of claim 1-3, the molecular-weight average that wherein contains the polymkeric substance of polyamine N-oxide is 500-1,000,000, preferably 1, and 000-50,000, be more preferably 2,000-30,000, most preferably be 3,000-20 is in 000 scope.
5. according to the application of claim 1, wherein this average molecular weight range that comprises N-vinyl imidazole N-vinylpyrrolidone copolymer is 5,000-50,000.
6. according to the application of claim 1 and 5, wherein the average molecular weight range of this multipolymer is 8,000-30,000.
7. according to the application of claim 1 and 5, wherein the average molecular weight range of this multipolymer is 10,000-20,000.
8. according to the application of claim 1-7, wherein being present in the polymkeric substance that contains polyamine N-oxide in the detergent composition and/or the weight ratio of N-vinyl imidazole N-vinylpyrrolidone copolymer and whitening agent is 1/20-20/1, preferably 1/10-12/1 is more preferably 1/1-12/1.
9. according to the application of claim 1-8, wherein this whitening agent is a kind of negatively charged ion whitening agent of bleach stable.
10. according to the application of claim 9, wherein this whitening agent is Tinopal RCBS-X.
11. according to the application of claim 1-10, wherein this detergent composition also comprises surfactant, washing assistant, enzyme and other conventional washing composition are prepared burden.
12. according to the application of claim 1-11, wherein the pH of this detergent composition is 2-6.
13. a detergent composition comprises:
(i) a kind of polymkeric substance that contains polyamine N-oxide and/or polymkeric substance of N-vinyl imidazole N-vinylpyrrolidone copolymer of being selected from;
(ii) a kind of whitening agent;
(iii) be less than 10% tensio-active agent.
14. according to the detergent composition of claim 13, said composition also comprises hydrogen peroxide.
15. according to the detergent composition of claim 13-14, said composition is a kind of laundry detergent additive.
CN 95191206 1994-01-13 1995-01-11 Use of polymers in liquid detergent compsn. containing brighteners for preventing fabric spotting Pending CN1138873A (en)

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