CN1224456A - Detergent compositions comprising modified polyamine polymers and cellulase - Google Patents

Detergent compositions comprising modified polyamine polymers and cellulase Download PDF

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CN1224456A
CN1224456A CN 97196106 CN97196106A CN1224456A CN 1224456 A CN1224456 A CN 1224456A CN 97196106 CN97196106 CN 97196106 CN 97196106 A CN97196106 A CN 97196106A CN 1224456 A CN1224456 A CN 1224456A
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R·K·帕南迪克
C·K·高希
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Procter and Gamble Co
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Abstract

A detergent composition comprising cellulase enzymes and water soluble and/or dispersible, modified polyamines having functionalized backbone moieties which provide depilling benefits is provided. The cellulase enzymes are present in an amount capable of degrading cellulose. In addition, at least about 0.1 % by weight of the detergent composition is a surfactant.

Description

The detergent composition that contains modified polyamine polymers and cellulase
Invention field
The present invention relates to contain the detergent composition of the cellulase and the polyamine of the water-soluble and/or water-dispersible modification with functionalized main chain, said composition provides the balling-up effect.Cellulase exists with the content that can make cellulose degradation.In addition, detergent composition weight is tensio-active agent at least about 0.1%.
Background of invention
Conventional detergent formulation often contains tensio-active agent, washing assistant and is used to promote other additive that dirt is removed.The technician of preparation detergent applications understands, and can be added in the conventional washing composition to improve the cleaning to fabric, tableware and other crust as the enzyme of a class particular protein.Enzyme is the material that the viable cell by the catalysis biological chemical reaction forms, and when being used for detergent formulation, their improve the cleansing power of washing composition.Equally, the technician in detergent for washing clothes field also knows, conventional when containing the enzyme detergent for washing clothes when using in washing process, tensio-active agent in the preparation and washing assistant have strengthened the effect of enzyme.The common enzyme that contains in the detergent for washing clothes of routine comprises: diastatic amylase, the proteolytic enzyme of catalytic decomposition proteins react, the lipase that lipid is worked, and cellulolytic cellulase.
Cellulase is considered to Mierocrystalline cellulose (β-1,4-dextran key) is hydrolyzed into the enzyme of glucose, cellobiose, Mierocrystalline cellulose oligose etc. in this area.The technician of washing composition formulation art thinks that cellulolytic enzyme is not only the reagent that improves the washing composition cleansing power, but also by softening and improving fabric feeling, as the reagent that fabric face is carried out modification.The repetitive scrubbing cotton-containing fabrics can make fabric produce coarse and undesirable stiff sense and cause balling-up.Balling-up is formed fiber tuftlet or " ball " assembling on cotton goods behind the repetitive scrubbing.The detergent for washing clothes preparation of use cellulase can reduce or get rid of the stiff sense and the harsh feeling of cotton-containing fabrics.In addition, cellulase also helps to reduce because the whiteness of balling-up that repetitive scrubbing causes and maintenance fabric.Moreover cellulase is used as spotting agent and uses in laundry detergent composition, and the gross impressions of the cleaning performance that the human consumer is felt are made contributions.
But the technician in washing composition zymetology field recognizes that cellulase preparation is complicated mixture, and just certain fraction wherein is effective as catalyzer in washing process.In addition, some cellulase can have a negative impact to the cotton clothes, and this is well-known in this field, and for example weight loss and tensile strength descend.These disadvantageous effects can be by selecting cellulase and helping to improve fabric face but do not have combined the reducing of specific detergent component of unfavorable effect.
Various loomage surface modification agent commercialization already is used in detergent composition and fabric softener/antistatic article and the composition at present.The example of surface-modifying agent is the decontamination polymkeric substance.The decontamination polymkeric substance contains an oligomeric or polymeric ester " main chain " usually, and is generally very effective to polyester textile or other synthetic textiles, and grease or similar hydrophobicity spot form coherent film on this kind fabric, are difficult for removing in the process of water laundry.The decontamination polymkeric substance is less to " blending " fabric effect that contains cotton and synthetic materials mixture, and then effect or effect are very not little to cotton products.
So far, still make us puzzled about the development of the effective loomage surface modification agent of cotton fabric.Some once attempted to utilize the example that successfully uses in polyester decontamination polymer arts, and the structure of decontamination polymkeric substance and fabric is complementary, but had been used for other loomage surface modification agent, during in particular for cotton fabric, are producing little effect.For example, use oligomeric unitary a kind of cotton polysaccharide-methylcellulose gum, confirm polyester comparison cotton more effective with modification.
Now be surprisingly found out that, can prepare the effective surface-modifying agent of textiles from the polyamine of some modification.The composition that this unpredictable consequence produced also can provide desirable surface modification effect, for example decontamination effect effectively not only to synthetic and synthetic-cotton blended fabric, and to cotton fabric.
Modified polyamine of the present invention is effective equally when disclosed laundry detergent composition is solid or liquid.The form of solid laundry washing composition can be particle, small pieces or laundry piece.Liquid washing agent can have very wide range of viscosities and can comprise the heavy-gravity enriched material, dumpable " ready-made " washing composition, or light dirty fabric pretreating agent.In addition, disclosed modified polyamine and other detergent for washing clothes additive and auxiliary consistency are good especially in the inventive method.
Therefore, although the disclosure of above-mentioned this area is arranged, but still need contain the cleansing power that can improve detergent for washing clothes and make the cotton goods softnessization and improve the detergent composition of the cellulase of feel.Also need a kind of detergent composition that removes stain removal.In addition, although the disclosed content in existing this area, but still a kind of cellulase of particular combinations and detergent composition of modified polyamine polymers of containing of needs, they can provide the enhanced cleanup action, softness turn into and go the balling-up effect, but cotton clothes generation weight loss and tensile strength are reduced.
Therefore, one of purpose of the present invention provides laundry detergent composition, and it contains a kind of effective cellulase and water-soluble and/or water-dispersible modified polyamine loomage surface modification of the present invention agent.This combination provides a kind of all fabrics is all effectively provided the surface modification effect, removes the laundry detergent composition of balling-up effect and cleanup action.
Another purpose of the present invention provides a kind of method that makes loomage surface modification during doing washing, and this method comprises makes fabric face contact with the aqueous solution of laundry detergent composition.
Background technology
The U.K.1 that announced on April 26th, 1973,314,897 mention and a kind ofly are used to prevent that the dirt that wets from depositing and improving the Vltra tears material that stain comes off again being washed on the fabric.The United States Patent (USP) 3,897,026 that is presented to Keamey discloses that hydroxylic moiety reaction by ethene-copolymer-maleic anhydride and cotton polymkeric substance obtains have improved decontamination and stain resistance can the cellulosic materials textile material.The United States Patent (USP) 3,912,681 that is presented to Dickson has been mentioned a kind of composition that is used for applying to cotton fabric the impermanency decontamination finishing composition that contains polycarboxylate polymer.Be presented to the United States Patent (USP) 3,948,838 of Hinton etc. and described high molecular (500,000 to 1,500, the 000) acrylic acid polymer that is used for decontamination.The United States Patent (USP) 4,559,056 of Leigh etc. discloses a kind of usefulness and has contained the compositions-treated cotton fabric of organopolysiloxane elastomerics, organo-siloxane oxyalkylene copolymers linking agent and siloxanes curing catalysts or the method for synthetic textiles.Also see United States Patent (USP) 4,579,681 and 4,614,519.These patent disclosures ethene hexanolactam material, its effectiveness is limited to the blending product of polyester textile, cotton and polyester and has hydrophobic cotton fabric by finishing composition.
The example of alkoxylate polyamine and quaternized alkoxylate polyamine is disclosed in european patent application 206,513, it is said that being suitable as dirt dispersant uses, may be as the application of loomage surface modification agent but do not mention them.In addition, these materials do not contain the N-oxide compound, and this is to be a kind of component that improves bleach stability to a key improvements of this invention polyamine and disclosed compound exhibits.
Except technology above-mentioned, following patent disclosure various decontamination polymkeric substance or modified polyamine: United States Patent (USP) 4,548,744, Connor, on October 22nd, 1985 issued; United States Patent (USP) 4,597,898, Vander Meer, on July 1st, 1986 issued; United States Patent (USP) 4,877,896, Maldonado etc., on October 31st, 1989 issued; United States Patent (USP) 4,891,160, Vander Meer, issue January 2 nineteen ninety; United States Patent (USP) 4,976,879, Maldonado etc., December 11 nineteen ninety, song was sent out; United States Patent (USP) 5,415,807, Gosselink, issue May 16 nineteen ninety-five; United States Patent (USP) 4,235,735, Marco etc., on November 25th, 1980 issued; English Patent 1,537 was announced on December 29th, 288,1978; English Patent 1,498 was announced on January 18th, 520,1978; WO 95/32272, announces November 30 nineteen ninety-five; German patent DE 28 29 022 was announced on January 10th, 1980; Japanese Patent JP announced on April 27th, 06313271,1994.
Following patent and publication disclose the detergent composition of cellulase: Bjork etc., United States Patent (USP) 5,120,463 (Genentech Intemational, Inc.); Boyer etc., WO93/11215 (The Procter ﹠amp; Gamble Company); Convents etc., United States Patent (USP) 5,443,750 (The Procter ﹠amp; Gamble Company); Suzuki etc., United States Patent (USP) 4,822,516 (Kao Corporation); Suzuki etc., United States Patent (USP) 4,978,470 (Kao Corporation).Following patent disclosure cellulase preparation: Bar-besgaard etc., United States Patent (USP) 4,435,307 (Novo Industri A/S); Rasmussen etc., EP 0,531,372 (Novo Nordisk A/S).
Brief summary of the invention
The present invention relates to detergent composition, wherein contain:
A) at least about a kind of detersive surfactant of 0.1% weight;
B) at least about the cellulase of 0.001% weight; With
C) at least about 0.05%, preferably about 0.5-10%, the more preferably from about a kind of water-soluble or water-dispersible, the polyamine loomage surface modification agent of modification of 1-7% weight, this reagent contains the polyamine main chain corresponding to following chemical formula:
Figure A9719610600111
Has modified polyamine chemical formula V (n+1)W mY nZ, or contain polyamine main chain corresponding to following chemical formula:
Figure A9719610600112
Has modified polyamine chemical formula V (n-k+l)W mY nY ' kZ, wherein k is less than or equal to n, and the molecular weight of this polyamine main chain before modification is greater than about 200 dalton, wherein
ⅰ) the V unit is the terminal units of following chemical formula:
Figure A9719610600113
ⅱ) the W unit is the backbone units of following chemical formula:
Figure A9719610600121
ⅲ) the Y unit is a chain unit of following chemical formula:
Figure A9719610600122
ⅳ) the Z unit is the terminal units of following chemical formula:
Figure A9719610600123
Wherein main chain linking group R is selected from C 2-C 12Alkylidene group, C 4-C 12Alkylene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy, C 8-C 12The dialkyl group arylidene ,-(R 1O) xR 1-,-(R 1O) xR 5(OR 1) x-,-(CH 2CH (OR 2) CH 2O)-(R 1O) yR 1O (CH 2CH (OR 2) CH 2) w-,-C (O) (R 4) rC (O)-,-CH 2CH (OR 2) CH 2-, and their mixture; R wherein 1Be C 2-C 6Alkylidene group and composition thereof; R 2Be hydrogen ,-(R 1O) xB and composition thereof; R 3Be C 1-C 18Alkyl, C 7-C 12Aralkyl, C 7-C 12The aryl that alkyl replaces, C 6-C 12Aryl and composition thereof; R 4Be C 1-C 12Alkylidene group, C 4-C 12Alkylene group, C 8-C 12Aryl alkylene, C 6-C 10Arylidene and their mixture; R 5Be C 1-C 12Alkylidene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy, C 8-C 12The dialkyl group arylidene ,-C (O)-,-C (O) NHR 6NHC (O)-,-C (O) (R 4) rC (O)-,-CH 2CH (OH) CH 2O (R 1O) yR 1O-CH 2CH (OH) CH 2-, and their mixture; R 6Be C 2-C 12Alkylidene group or C 6-C 12Arylidene; The E unit is selected from hydrogen, C 1-C 22Alkyl, C 3-C 22Alkenyl, C 7-C 22Aralkyl, C 2-C 22Hydroxyalkyl ,-(CH 2) p-CO 2M ,-(CH 2) qSO 3M ,-CH (CH 2CO 2M)-CO 2M ,-(CH 2) pPO 3M ,-(R 1O) xB ,-C (O) R 3With their mixture; Condition is, when any E unit of nitrogen-atoms was hydrogen, this nitrogen neither the N-oxide compound; B is a hydrogen, C 1-C 6Alkyl ,-(CH 2) qSO 3M ,-(CH 2) pCO 2M ,-(CH 2) qCH (SO 3M) CH 2SO 3M ,-(CH 2) qCH (SO 2M) CH 2SO 3M ,-(CH 2) pPO 3M ,-PO 3M and their mixture; M is the water-soluble cationic that hydrogen or quantity are enough to satisfy charge balance; X is a water soluble anion; The value of m is 4 to about 400; The value of n is 0 to about 200; The value of p is 1-6; The value of q is 0-6; The value of r is 0 or 1; The value of w is 0 or 1; The value of x is 1 to 100; The value of y is 0-100; The value of z is 0 or 1.
Detergent composition also randomly but preferably contain the auxiliary of effective quantity is selected from enzyme, enzyme activator, suds suppressor, dyestuff, spices, tinting material, filling salt, hydrotropic agent and their mixture of washing assistant, white dyes, SYNTHETIC OPTICAL WHITNER, bleach boosters, bleach-activating agent, non-cellulose enzyme.
Except as otherwise noted, all herein percentage ratio, ratio and ratio all refer to weight.Unless otherwise indicated, all temperature be degree centigrade (℃).
All quote as a reference in this article at all documents that relevant portion is mentioned.
Detailed Description Of The Invention
The present invention includes the detergent composition that is particularly suitable for cotton, non-cotton or cotton and non-cotton blended fabric.The present invention includes following preparation.
A kind of preferred liquid laundry detergent compositions that the fabric-modifying effect is provided, wherein contain:
A), be selected from anionic and non-ionic type detersive surfactant at least about the detersive surfactant of 10% weight;
B) cellulase of about 0.05-2% weight; With
C) the polyamine loomage surface modification agent of the water-soluble or water-dispersible modification of about 0.5-10% weight, this reagent contains the polyamine main chain corresponding to following chemical formula:
Figure A9719610600131
Has modified polyamine chemical formula V (n+1)W mY nZ, or contain polyamine main chain corresponding to following chemical formula:
Figure A9719610600141
Has modified polyamine chemical formula V (n-k+l)W mY nY ' kZ, wherein k is less than or equal to n, and the molecular weight of this polyamine main chain before modification is greater than about 200 dalton, wherein
ⅰ) the V unit is the terminal units of following chemical formula:
ⅱ) the W unit is the backbone units of following chemical formula:
Figure A9719610600143
ⅲ) the Y unit is a chain unit of following chemical formula:
Figure A9719610600144
ⅳ) the Z unit is the terminal units of following chemical formula:
Figure A9719610600145
Wherein main chain connector element R is selected from C 2-C 12Alkylidene group, C 4-C 12Alkylene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy, C 8-C 12The dialkyl group arylidene ,-(R 1O) xR 1-,-(R 1O) xR 5(OR 1) x-,-(CH 2CH (OR 2) CH 2O) z-(R 1O) yR 1(OCH 2CH (OR 2) CH 2) w-,-C (O) (R 4) rC (O)-,-CH 2CH (OR 2) CH 2-, and their mixture; R wherein 1Be C 2-C 6Alkylidene group and composition thereof; R 2Be hydrogen ,-(R 1O) xB and composition thereof; R 3Be C 1-C 18Alkyl, C 7-C 12Aralkyl, C 7-C 12The aryl that alkyl replaces, C 6-C 12Aryl and their mixture; R 4Be C 1-C 12Alkylidene group, C 4-C 12Alkylene group, C 8-C 12Aryl alkylene, C 6-C 10Arylidene and their mixture; R 5Be C 1-C 12Alkylidene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy, C 8-C 12The dialkyl group arylidene ,-C (O)-,-C (O) NHR 6NHC (O)-,-R 1(OR 1)-,-C (O) (R 4) rC (O)-,-CH 2CH (OH) CH 2-,-CH 2CH (OH) CH 2O (R 1O) yR 1OCH 2CH (OH) CH 2-and their mixture; R 6Be C 2-C 12Alkylidene group or C 6-C 12Arylidene; The E unit is selected from hydrogen, C 1-C 22Alkyl, C 3-C 22Alkenyl, C 7-C 22Aralkyl, C 2-C 22Hydroxyalkyl ,-(CH 2) pCO 2M ,-(CH 2) qSO 3M ,-CH (CH 2CO 2M)-CO 2M ,-(CH 2) pPO 3M ,-(R 1O) xB ,-C (O) R 3And their mixture; Condition is that when any E unit of nitrogen was hydrogen, this nitrogen was not the N-oxide compound simultaneously; B is a hydrogen, C 1-C 6Alkyl ,-(CH 2) q-SO 3M ,-(CH 2) pCO 2M ,-(CH 2) q(CHSO 3M) CH 2SO 3M ,-(CH 2) q-(CHSO 2M) CH 2SO 3M ,-(CH 2) pPO 3M ,-PO 3M and their mixture; M is the water-soluble cationic that hydrogen or quantity are enough to satisfy charge balance; X is a water soluble anion; The value of m is 4 to about 400; The value of n is 0 to about 200; The value of p is 1-6; The value of q is 0-6; The value of r is 0 or 1; The value of W is 0 or 1; The value of x is 1-100; The value of y is 0-100; The value of z is 0 or 1; With
D) alkaline matter, its quantity are enough to make composition when by 10% determination of aqueous solution, and pH is about 7-9.5.
The present invention also comprises a kind of method that makes fabric face modification in laundry processes, and this method comprises makes fabric face contact with the laundry detergent composition aqueous solution of the present invention.
Moreover the present invention also comprises and a kind ofly is used for washing and goes ball to contain balling-up fabric method, and this method comprises that the fabric that makes balling-up contacts with water lotion with the detergent composition formation of the present invention of effective quantity.
Laundry detergent composition of the present invention contains following composition.
Cellulase laundry detergent composition of the present invention contains at least 0.001% weight, preferably at least about 0.01% cellulase.But for using in laundry detergent composition as herein described, effectively the cellulase of quantity is enough." effectively quantity " speech be meant to dirt-carrying body such as fabric, tableware etc. can produce cleaning, except that spot, decontamination, brighten, deodorizing or become any amount of new improvement effect.The present composition contains about 0.05-2%, the preferred commercial enzyme preparation of about 0.1-1.5% weight usually.The content of cellulase of the present invention in the commodity preparation is enough to provide the activity of every gram composition 0.005-0.1 Anson unit (AU) usually.Preferably, the best pH that contains enzyme composition is about 7-9.5.
United States Patent (USP) 4,435,307 (Barbesgard etc., on March 6th, 1984 issued) disclose by unusual rotten cellulase of planting mould preparation.The example of the cellulase that other is suitable comprises by unusual rottenly plants that trichoderma strain, grey corruption are planted the cellulase of mould thermoidea mutation preparation and by the cellulase of genus bacillus or Aeromonas preparation.Other available cellulase is the cellulase by the hepatopancreas extraction of sea mollusk Dolabella Auricula Solander.Suitable cellulase: GB 2,075 is also disclosed in following patent, 028A (Novo Industri A/S); GB 2,095, and 275A (Kao Soap Co., Ltd.); United States Patent (USP) 3,844,890 (Rikagaku Kenkyusho) with Horikoshi etc.In addition, narrated suitable cellulase and preparation method thereof among the PCT international publishing WO 91/17243 of the Novo Nordisk A/S that announces on November 14th, 1991.
Cellulase is known in the art, can be obtained by supplier by following trade name: Celluzyme , Endolase And Carezyme
For the industrial production of cellulase among the present invention, preferably utilize recombinant DNA technology.But also can use other technology that relates to the fermentation of regulating related microorganism or sudden change produces with the excess that guarantees desired enzymatic activity.These methods and technology are well known in the prior art, are undertaken by those skilled in the art easily.
Modified polyamine polymers loomage surface modification agent of the present invention is water-soluble or the water-dispersible modified polyamine.These polyamine contain or straight chain or annular main chain.The polyamine main chain also can contain polyamine side chain more or less.Generally, described herein polyamine main chain is modified in some way, make each nitrogen-atoms of polyamine chain be called as hereinafter one be substituted, quaternized, oxidation or the combined unit of these modes.
For the present invention, " modification " speech is defined as with an E unit and replaces a main chain-NH hydrogen atom (replacement), makes main chain nitrogen quaternized (quaternized) or main chain nitrogen is oxidized to N-oxide compound (oxidation).When mentioning the process of the hydrogen atom that is connected with main chain nitrogen with the replacement of E unit, term " modification " is used interchangeably with " replacement ".Quaternization or oxygenizement can take place under no metalepsy in some cases, but metalepsy then preferably is accompanied by the oxidation of at least one main chain nitrogen or quaternized.
The straight chain or the acyclic polyamine main chain that constitute loomage surface modification agent of the present invention have following logical
Figure A9719610600171
This main chain before modification subsequently, contain by R " connection " unit connect primary, the second month in a season and tertiary amine nitrogen atom.The annular polyamine main chain that constitutes reagent of the present invention has following general formula:
Figure A9719610600172
This main chain before modification subsequently, contain by R " connection " unit connect primary, the second month in a season and tertiary amine nitrogen atom.
For the present invention, in a single day the primary amine nitrogen of formation main chain or side chain be modified and just be defined as V or Z " end " unit.For example, when being positioned at the polyamine main chain or the side chain end has structure H 2N-R]-primary amine part when being modified according to the present invention, then be called as V " end " unit afterwards, or be called for short the V unit.But, for purposes of the invention, some or all in the primary amine part through hereinafter further specifying restriction and can keep not being modified.These unmodified primary amine parts are owing to their positions in main chain remain " end " unit.Equally, be-NH when the structure that is positioned at main polyamine main chain end 2Primary amine part during according to modification of the present invention, it is called as Z " end " unit afterwards or is called for short the Z unit.This element can be through hereinafter further specifying restriction and keep not being modified.
In a comparable manner, the secondary amine nitrogen of formation main chain or side chain is known as W " main chain " unit after modification.For example, when secondary amine part with following structure as main chain of the present invention and side chain main component
Figure A9719610600173
When being modified according to the present invention, it is called as W " main chain " unit afterwards, or is called for short the W unit.But for purposes of the invention, some or all secondary amine parts may keep not being modified.These unmodified secondary amine parts are owing to their positions in main chain are still " main chain " unit.
Still by similar mode, the tertiary amine nitrogen that constitutes main chain or side chain is called Y " side chain " unit in addition after modification.For example, when tertiary amine part with following structure as the chain component point of polyamine main chain or other side chain or ring
Figure A9719610600181
After according to modification of the present invention, hereinafter be called as Y " side chain " unit, or be called for short the Y unit.But for purposes of the invention, some or all tertiary amine parts can keep not being modified.These unmodified tertiary amine parts are owing to their positions in main chain are still " side chain " unit.The R unit that is connected the effect of polyamine nitrogen that plays that links to each other with the unitary nitrogen of V, W and Y illustrates below.
Therefore, the polyamine structure of final modification of the present invention, can represent with following general formula for the straight-chain polyamine polymkeric substance:
V (n+1)W mY nZ can represent with following general formula for annular polyamine polymer
V (n-k+1)W mY nY ' kZ is for the polyamine that contains ring, and the Y ' unit of following chemical formula plays tapping point to main chain or supporting ring For each Y ' unit, the Y unit of a following chemical formula is arranged all It forms the tie point of ring and main polymer chain or side chain.At main chain is the special case of a complete ring, and the chemical formula of polyamine main chain is
Figure A9719610600191
Therefore do not contain the Z terminal units, chemical formula is
V N-kW mY nY ' kWherein k becomes to encircle the unitary number of side chain.Polyamine main chain of the present invention does not preferably contain ring.
In the situation of acyclic polyamine, index n is relevant with relative degree of branching with the ratio of m.Of the present invention fully not the straight chain modified polyamine of branching have following chemical formula
VW mZ promptly, n equals 0.The value of n big more (m is more little with the ratio of n), then the degree of branching of molecule is big more.Usually the m value be from minimum value 4 to about 400, but bigger m value, especially very low or near 0 the time as index n, also be preferred.
Each polyamine nitrogen no matter be primary, the second month in a season or tertiary N atom, all is defined as one of following three classes: simple that replace, quaternised or oxidation again after the modification according to the present invention.The polyamine nitrogen unit that those are not modified then according to they be primary, the second month in a season or uncle's nitrogen classifies as V, W, Y or Z unit.That is, for purposes of the invention, unmodified primary amine nitrogen is V or Z unit, and unmodified secondary amine nitrogen is the W unit, and unmodified tertiary amine nitrogen is the Y unit.
The primary amine of modification partly is defined as V " end " unit of one of following three kinds of forms:
A) the simple replacement unit of following structure:
Figure A9719610600192
B) the quaternized unit of following structure:
Figure A9719610600201
Wherein X provides the suitable gegenion of charge balance; With
C) oxidation unit of following structure:
Figure A9719610600202
The secondary amine of modification partly is defined as W " main chain " unit of one of following three kinds of forms:
A) the simple replacement unit of following structure:
Figure A9719610600203
B) the quaternized unit of following structure:
Figure A9719610600204
Wherein X provides the suitable gegenion of charge balance; With
C) oxidation unit of following structure:
The tertiary amine of modification partly is defined as Y " side chain " unit of one of following three kinds of forms:
A) the unmodified unit of following structure:
Figure A9719610600211
B) the quaternized unit of following structure: Wherein X provides the suitable gegenion of charge balance; With
C) oxidation unit of following structure:
Figure A9719610600213
The primary amine of some modification partly is defined as Z " not end " unit of one of following three kinds of forms:
A) the simple replacement unit of following structure:
Figure A9719610600214
B) the quaternized unit of following structure:
Figure A9719610600215
Wherein X provides the suitable gegenion of charge balance; And c) oxidation unit of following structure:
Figure A9719610600221
On any position of nitrogen, be not substituted when not being modified, then should understand hydrogen and will replace E.For example, the unitary primary amine of the E unit that contains a hydroxyethyl form is that chemical formula is (HOCH 2CH 2) the V terminal units of HN-.
For the purpose of the present invention, two class chain end unit: V and Z unit are arranged.Z " end " unit by structure is-NH 2The formation of deriving of terminal primary amino.Acyclic polyamine main chain according to the present invention only contains a Z unit, and annular polyamine can not contain the Z unit.Formed outside the situation of N-oxide compound except when the Z unit is modified, Z " end " unit can replace with any E unit that hereinafter will further specify.Be oxidized under the situation of N-oxide compound at Z unit nitrogen, nitrogen must be modified, so E can not be a hydrogen.
Polyamine of the present invention contains main chain R " connection " unit, and they play a part to connect the main chain nitrogen-atoms.The R unit comprises in the present invention and is known as " alkyl R " unit and " oxygen base R " unitary unit." alkyl " R unit is C 2-C 12Alkylidene group; C 4-C 12Alkylene group; C 3-C 12Hydroxy alkylidene, wherein hydroxylic moiety can on the R cellular chain except with the direct-connected carbon atom of polyamine main chain nitrogen any position on; C 4-C 12Alkyl sub-dihydroxy, wherein hydroxylic moiety can occupy on the R cellular chain except with direct-connected those carbon atoms of polyamine main chain nitrogen any two carbon atoms on; C 8-C 12The dialkyl group arylidene, for the present invention, they are that the arylene group of two alkyl substituents as the part connection chain arranged.For example, a kind of dialkyl group arylene units has following chemical formula
Figure A9719610600222
But this unit needs not to be 1, and 4-replaces, and also can be 1,2 or 1,3 C that replaces 2-C 12Alkylidene group, preferred ethylidene, propylene and their mixture, more preferably ethylidene." oxygen base " R unit comprises-(R 1O) xR 5(OR 1) x-,-(CH 2CH (OR 2) CH 2O) z-(R 1O) yR 1(OCH 2CH (OR 2) CH 2) w-,-CH 2CH (OR 2) CH 2-,-(R 1O) xR 1-, and their mixture.Preferred R unit is C 2-C 12Alkylidene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy, C 8-C 12The dialkyl group arylidene ,-(R 1O) xR 1,-CH 2CH (OR 2) CH 2-,-(CH 2CH (OH) CH 2O) z(R 1O) yR 1(OCH 2CH-(OH) CH 2) w-,-(R 1O) xR 5(OR 1) x-, preferred R unit is C 2-C 12Alkylidene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy ,-(R 1O) xR 1-,-(R 1O) xR 5(OR 1) x-,-(CH 2CH (OH) CH 2O) z(R 1O) yR 1(OCH 2CH-(OH) CH 2) w-reaching their mixture, further preferred R unit is C 2-C 12Alkylidene group, C 3Hydroxy alkylidene and their mixture, most preferably C 2-C 6Alkylidene group.It is the R unit of ethylidene that most preferred main chain of the present invention comprises at least 50%.
R 1The unit is C 2-C 6Alkylidene group and composition thereof, preferred ethylidene.
R 2Be hydrogen and-(R 1O) xB is preferably hydrogen.
R 3Be C 1-C 18Alkyl, C 7-C 12Aryl alkylene, C 7-C 12Aryl, C that alkyl replaces 6-C 12Aryl and their mixture, preferred C 1-C 12Alkyl, C 7-C 12Aryl alkylene, more preferably C 1-C 12Alkyl, most preferable.R 3The unit conduct unitary part of E hereinafter described.
R 4Be C 1-C 12Alkylidene group, C 4-C 12Alkylene group, C 8-C 12Aryl alkylene, C 6-C 10Arylidene, preferred C 1-C 10Alkylidene group, C 8-C 12Aryl alkylene, more preferably C 2-C 8Alkylidene group, most preferably ethylidene or butylidene.
R 5Be C 1-C 12Alkylidene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy, C 8-C 12The dialkyl group arylidene ,-C (O)-,-C (O) NHR 6NHC (O)-,-C (O) (R 4) rC (O)-,-R 1(OR 1)-,-CH 2CH (OH) CH 2O (R 1O) yR 1OCH 2CH (OH) CH 2-,-C (O) (R 4) rC (O)-,-CH 2CH (OH) CH 2-, R 5Preferably ethylidene ,-C (O)-,-C (O) NHR 6NHC (O)-,-R 1(OR 1)-,-CH 2CH (OH) CH 2-,-CH 2CH (OH) CH 2O (R 1O) yR 1OCH 2CH-(OH) CH 2-, more preferably-CH 2CH (OH) CH 2-
R 6Be C 2-C 12Alkylidene group or C 6-C 12Arylidene.
Preferably " oxygen base " R unit is also further according to R 1, R 2And R 5The unit definition.Preferably " oxygen base " R unit comprises preferred R 1, R 2And R 5The unit.It is the R of ethylidene that preferred surface-modifying agent of the present invention comprises at least 50% 1The unit.Preferred R 1, R 2And R 5The unit combines with " oxygen base " R unit, forms preferred " oxygen base " R unit in the following manner.
ⅰ) use preferred R 5Replace to go into-(CH 2CH 2O) xR 5(OCH 2CH 2) x-, formation-(CH 2CH 2O) xCH 2CHOHCH 2(OCH 2CH 2) x-.
ⅱ) use preferred R 1And R 2Replace to go into-(CH 2CH (OR 2) CH 2O) z-(R 1O) yR 1O (CH 2CH (OR 2) CH 2) w-, formation-(CH 2CH (OH) CH 2O) z-(CH 2CH 2O) yCH 2CH 2O (CH 2CH (OH) CH 2) w-.
ⅲ) use preferred R 2Replace to go into-CH 2CH (OR 2) CH 2-, formation-CH 2CH (OH) CH 2-.
The E unit is to be selected from hydrogen, C 1-C 22Alkyl, C 3-C 22Alkenyl, C 7-C 22Aralkyl, C 2-C 22Hydroxyalkyl ,-(CH 2) pCO 2M ,-(CH 2) qSO 3M ,-CH (CH 2CO 2M) CO 2M ,-(CH 2) pPO 3M ,-(R 1O) mB ,-C (O) R 3, preferred hydrogen, C 2-C 22Hydroxy alkylidene, benzyl, C 1-C 22Alkylidene group ,-(R 1O) mB ,-C (O) R 3,-(CH 2) qCO 2M ,-(CH 2) qSO 3M ,-CH (CH 2CO 2M) CO 2M, more preferably C 1-C 22Alkylidene group ,-(R 1O) xB ,-C (O) R 3,-(CH 2) pCO 2M ,-(CH 2) qSO 3M ,-CH (CH 2CO 2M) CO 2M, most preferably C 1-C 22Alkylidene group ,-(R 1O) xB and-C (O) R 3No modification or when replacing, then hydrogen atom will keep the part that E is represented in conduct on nitrogen-atoms.
When V, W or Z unit were oxidized, promptly when nitrogen was the N-oxide compound, the E unit is hydrogen atoms not.For example, main chain or side chain do not contain the unit of following structure:
Figure A9719610600241
In addition, when V, W or Z unit are oxidized, that is, when nitrogen was the N-oxide compound, the E unit did not contain the carbonyl moiety with the nitrogen-atoms Direct Bonding.According to the present invention, E unit-C (O) R 3Part not with the modification nitrogen bonding of N-oxide compound, that is, do not have N-oxide compound acid amides with following structure
Figure A9719610600242
Or its mixture.
B is hydrogen, C 1-C 6Alkyl ,-(CH 2) qSO 3M ,-(CH 2) pCO 2M ,-(CH 2) q(CHSO 3M) CH 2SO 3M ,-(CH 2) q(CHSO 2M) CH 2SO 3M ,-(CH 2) pPO 3M ,-PO 3M, preferred hydrogen ,-(CH 2) qSO 3M ,-(CH 2) q(CHSO 3M) CH 2SO 3M ,-(CH 2) q(CHSO 2M) CH 2SO 3M, more preferably hydrogen or-(CH 2) qSO 3M.
M is the water-soluble cationic that hydrogen or quantity are enough to satisfy charge balance.For example, a sodium cation similarly satisfies-(CH 2) pCO 2M and-(CH 2) qSO 3M, thereby formation-(CH 2) pCO 2Na and-(CH 2) qSO 3The Na group.Can be in conjunction with more than one monovalent cation (sodium, potassium etc.) to satisfy desired chemical charge balance.But more than one anionic group can perhaps may be needed the electric charge needs that more than one monovalent cation satisfies the multivalent anions group by a divalent cation charge balance.For example, by the Na atom replace-(CH 2) pPO 3The chemical formula of M group is-(CH 2) pPO 3Na 3Divalent cation such as calcium (Ca 2+) or magnesium (Mg 2+) can replace other suitable univalent water-soluble cationic or with its combination.Preferred cation is sodium and potassium, more preferably sodium.
X is for example chlorine (CL of water soluble anion -), bromine (Br -) and iodine (I -), perhaps X can be any electronegative group, for example sulfate radical (SO 4 2-) and methylsulfate (CH 3SO 3 -).
It is 1-6 that the chemical formula subscript has following numerical value: p, and q is 0-6, and r is 0 or 1, and W is 0 or 1, and x is 1-100, and y is 0-100, and z is 0 or 1, and m is 4 to about 400, and n is 0 to about 200, and m+n is at least 5.
Constitute the unitary R group of " oxygen base " R in the polyamine main chain that preferred modified polyamine surface-modifying agent of the present invention contains and be less than approximately 50%, preferably be less than approximately 20%, more preferably less than 5%, preferably the R unit does not contain " oxygen base " R unit.
Most preferred not containing in the polyamine main chain that the unitary reagent of " oxygen base " R contains, be less than 50% R group and contain 3 more than the carbon atom.For example, ethylidene, propylene and trimethylene contain 3 or carbon atom still less, are preferred " alkyl " R unit.That is, when main chain R unit be C 2-C 12During alkylidene group, C preferably 2-C 3Alkylidene group most preferably is an ethylidene.
Surface-modifying agent of the present invention contains all even uneven polyamine main chain of modification, wherein 100% or few slightly-NH unit be modified.For the present invention, term " polyamine main chain uniformly " is defined as the polyamine main chain of identical R unit (being ethylidene entirely).But the definition of this homogeny is not got rid of main chain in the polyamine and is contained other and add the unit, and these unitary existence are to be caused by the chemical synthesis process people who selects.For example, the known thanomin that can use in the synthesizing polyethylene imines of those skilled in the art is as " initiator ", therefore, contain the polymine sample of a hydroxyethyl groups that causes because of polymerization " initiator ", will be considered to constitute uniform polyamine main chain for purposes of the invention.The R unit that contains is ethylidene and not have the unitary polyamine main chain of side chain Y be uniform main chain entirely.All the R unit are that the polyamine main chain of ethylidene is uniform main chain, no matter the degree of branching of existing annular side chain or number are how.
For the present invention, term " uneven main polymer chain " is meant that the polyamine main chain is the R unit mixture of various different lengthss and type.For example, the R unit that contains of a kind of uneven main chain is the mixture of ethylidene and propylene.For the present invention, " alkyl " and the unitary mixture of " oxygen base " R not necessarily form uneven main chain.Suitably controlling these " R unit chain lengths " makes the makers-up can regulate the solubleness and the fabric affinity of polyamine reagent of the present invention.
Preferred polymers of the present invention contains uniform polyamine main chain, and these main chains are completely or partially replaced by polyethyleneoxy, and is completely or partially quaternized, and its nitrogen completely or partially is oxidized to the N-oxide compound, or the combination of these modifications.But, be not the nitrogen modification in the same way of all main chain amine, the selection of modification mode is determined according to concrete needs by formulator.The degree of ethoxylation is also determined by the concrete needs of formulator.
The preferred polyamine that contains the The compounds of this invention main chain generally is polyalkylene amine (PAA), polyalkyleneimine (PAI), preferably polyethylene amine (PEA), polymine (PEI) are perhaps by having PEA or the PEI that the unitary group of the R longer than parent PAA, PAI, PEA or PEI connects.A kind of common polyalkylene amine (PAA) is four butylidenes, five amine.PEA carries out fractionation by the reaction that relates to ammonia and Ethylene Dichloride to obtain subsequently.The common PEA that obtains is Triethylenetetramine (TETA) (TETA) and tetren (TEPA).On five amine, that is, hexamine, seven amine, eight amine and possibility nine amine, symbiotic mixture be it seems and can not be passed through fractionation by distillation, may contain other material such as cyclammonium, particularly piperazine.Also have with side chain in the cyclammonium of nitrogen-atoms appears.Referring to the United States Patent (USP) 2,792,372 that is presented to Dickinson May 14 nineteen fifty-seven, this patents state the preparation of PEA.
Preferred amine polymer main chain contains promising C 2The R unit of alkylidene group (ethylidene) is also referred to as polymine (PEI).Preferred PEI has the branching of moderate at least, that is, the ratio of m and n is less than 4: 1, but the ratio of m and n is that about 2: 1 PEI is most preferred.Preferred main chain general formula before modification is:
Figure A9719610600261
Wherein m and n are with defined above identical.The preferred molecular weight of PEI before modification is greater than about 200 dalton.
In the polyamine main chain primary, the second month in a season and the unitary relative proportion of tertiary amine, particularly, will become with preparation method in the situation of PEI.Each hydrogen atom of being connected with each nitrogen-atoms of polyamine main chain has been represented the possible position of replacement subsequently, quaternized or oxidation.
These polyamine can be by for example preparing the ethylene imine polymerization in the presence of catalyzer (as carbonic acid gas, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetate etc.).The concrete grammar for preparing these polyamine main chains is disclosed in United States Patent (USP) 2,182,306 (Ulrich etc., issue December 5 nineteen thirty-nine), United States Patent (USP) 3,033,746 (Mayle etc., on May 8th, 1962 issued), United States Patent (USP) 2,208,095 (Esselmann etc., on July 16th, 1940 issued), United States Patent (USP) 2,806,839 (Crowther, issue September 17 nineteen fifty-seven) and United States Patent (USP)s 2,553,696 (Wilson, issue May 21 nineteen fifty-one), above-mentioned patent is all quoted as a reference in this article.
The polymer-modified example of the PEI of containing of the present invention is shown in formula I-IV:
The formula I has been described the polymkeric substance that contains the PEI main chain, and wherein all commutable nitrogen are all by using polyoxy alkylidene oxygen base unit-(CH 2CH 2O) 7H replaces hydrogen and carries out modification, and its chemical formula is:
Figure A9719610600271
This is the examples of polymer with the complete modification of a kind of type group.
The formula II has been described a kind of polymkeric substance of the PEI of containing main chain, and wherein all commutable primary amine nitrogen are all by using polyoxy alkylidene oxygen base unit-(CH 2CH 2O) 7H replaces hydrogen and carries out modification, and this molecule carries out modification by all oxidable uncle's nitrogen and secondary nitrogen are oxidized to the N-oxide compound subsequently again, and the chemical formula of this reagent is:
The formula III has been described a kind of polymkeric substance of the PEI of containing main chain, and wherein all main chain hydrogen atoms all are substituted, and some main chain amine units are by quaternized.Substituting group is polyoxy alkylidene oxygen base unit-(CH 2CH 2O) 7H, or methyl.PEI polymkeric substance after the modification has following structure
Figure A9719610600282
The formula IV has been described the polymkeric substance that contains the PEI main chain, and wherein main chain nitrogen is by replacing (that is usefulness-(CH, 2CH 2O) 7H or methyl), combination quaternized, that be oxidized to N-oxide compound or several modes is modified.The chemical formula of formed polymkeric substance is:
Figure A9719610600291
In above example, be not that all nitrogen in the unit all carries out same modification.The present invention allows the makers-up to make the ethoxylation of a part of secondary amine nitrogen, and makes other secondary amine nitrogen be oxidized to the N-oxide compound.This also is applicable to the primary amine nitrogen-atoms, at this moment the makers-up can be chosen in oxidation or quaternized before make all or part of primary amine nitrogen modification with one or more substituting groups.Except restriction above-mentioned, any possible combination of E group all can be substituted on uncle or the secondary amine nitrogen atom.
Detersive surfactant is suitable for other detersive surfactant of the present invention and is hereinafter cationic, amphoteric, amphoteric ion type and their mixture of further narration except above-mentioned preferred anionic surfactants type and non-ionic type detersive surfactant.
The anionic detersive surfactant present composition contains at least about 0.1%, preferred at least 1%, more preferably at least 10%, the anionic detersive surfactant of about 5-80% weight preferably.The alkyl sulfate surfactant of uncle's type or secondary type all is to be used for the important aniorfic surfactant of the present invention.The general formula of alkyl-sulphate is ROSO 3M, wherein R is preferably C 10-C 24Alkyl, straight or branched alkyl preferably, or contain C 10-C 20The hydroxyalkyl of alkyl component, more preferably C 12-C 18Alkyl or hydroxyalkyl; And M is hydrogen or water-soluble cationic, alkali metal cation (as sodium, potassium, lithium) for example, replace or unsubstituted ammonium cation, for example first ammonium, dimethylammonium and TMA (TriMethylAmine) and quaternary ammonium cation, for example tetramethylammonium and lupetidine, and by alkanolamine thanomin, diethanolamine, trolamine and composition thereof positively charged ion that forms etc. of deriving for example.Usually, for lower wash temperature (for example being lower than about 50 ℃), preferred C 12-C 16The then preferred C of alkyl chain, higher wash temperature (for example about 50 ℃) 16-C 18Alkyl chain.
Alkoxylated alkyl group vitriol is another kind of preferred anionic surfactants type tensio-active agent.These tensio-active agents are water miscible salt or acid, and its chemical formula is generally RO (A) mSO 3M, wherein R is unsubstituted C 10-C 24Alkyl or contain C 10-C 24The hydroxyalkyl of alkyl component is preferably C 12-C 20Alkyl or hydroxyalkyl, more preferably C 12-C 18Alkyl or hydroxyalkyl.A is oxyethyl group or propoxy-unit, and m is greater than 0, usually between about 0.5 and about 6, and more preferably about 0.5-3; M is hydrogen or water-soluble cationic, for example the ammonium cation of metallic cation (as sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replacement.The alkyl-sulphate of ethoxylation and propenoxylated alkyl-sulphate are the objects that the present invention considers.The specific examples of the ammonium cation that replaces comprises methyl, dimethyl, trimethyl ammonium and quaternary ammonium cation, for example tetramethylammonium, lupetidine and the positively charged ion of being derived and being formed by alkanolamine such as monoethanolamine, diethanolamine and trolamine and composition thereof.Specifiable tensio-active agent has C 12-C 18Alkyl polyethoxye (1.0) vitriol, C 12-C 18Alkyl polyethoxye (2.25) vitriol, C 12-C 18Alkyl polyethoxye (3.0) vitriol and C 12-C 18Alkyl polyethoxye (4.0) vitriol, wherein M should be selected from sodium and potassium.
Non-ionic type surfactant for washing-present composition can contain at least about 0.1%, preferred at least 1%, more preferably at least about 10%, a kind of non-ionic type detersive surfactant of about 5-80% weight preferably.Preferred nonionic surfactants, for example C 12-C 18Alkylethoxylate (" AE ") comprises so-called narrow distribution alkylethoxylate and C 6-C 12Alkyl phenolic alkoxy thing (especially ethoxylate and blended oxyethyl group/propoxylated glycerine), C 6-C 12The oxyalkylene block condensates of alkylphenol, C 8-C 22The oxyalkylene condenses of alkanol and ethylene oxide/propylene oxide block polymer (Pluronic TM, BASF Corp.), and semi-polar nonionogenic tenside (for example amine oxide and phosphine oxide) can be used for the present composition.Authorize the extensive introduction that has in the United States Patent (USP) 3,929,678 of Laughlin etc. these type list surface-active agents on December 30th, 1975, this content is quoted as a reference in the present invention.
Such as at United States Patent (USP) 4,565, disclosed alkyl polysaccharide also is a preferred nonionic surfactants in the present composition among 647 (Llenado, the present invention quotes as a reference).
Another kind of preferred nonionic is the following polyhydroxy fatty acid amide of chemical formula: R wherein 7Be C 5-C 31Alkyl, preferred straight chain C 7-C 19Alkyl or alkenyl, more preferably straight chain C 9-C 17Alkyl or alkenyl, most preferably straight chain C 11-C 15Alkyl or alkenyl, or their mixture; R 8Be selected from hydrogen, C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, preferable methyl or ethyl, more preferably methyl.Q is the polyhydroxy alkyl part with linear alkyl chain, at least directly connects 3 hydroxyls on this chain, and perhaps Q is the alkoxy derivative of above-mentioned group; Preferred alkoxyl group is oxyethyl group or propoxy-and composition thereof.Preferred Q is derived in the reductive amination reaction by reducing sugar and forms.More preferably Q is a sugar alcohol base section.Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.As starting material, high glucose maize treacle, high-fructose corn syrup and high malt sugar maize treacle are the same with the single syrup of listing above can be used.These maize treacle can be formed for the mixture of the sugar component of Q.Should be clear, this plans to get rid of other proper raw material anything but.Q more preferably is selected from-CH 2(CHOH) nCH 2OH ,-CH (CH 2OH) (CHOH) N-1CH 2OH ,-CH 2(CHOH) 2-(CHOR ') be CH (CHOH) 2OH, and their oxyalkylated derivative, wherein n is the integer of 3-5, comprises 3 and 5, R ' is hydrogen or annular or aliphatic monose.The most preferred substituting group of Q part is that wherein n is 4 sugar alcohol base, particularly-and CH 2(CHOH) 4CH 2OH.
R 7CO-N＜can be is coconut oleoyl amine, stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitic amide, butter acid amides etc. for example.
R 8Can be for example methyl, ethyl, propyl group, sec.-propyl, butyl, 2-hydroxyethyl or 2-hydroxypropyl.
Q can be a 1-deoxy-glucose base, 2-deoxidation fructosyl, 1-deoxidation malt-base, 1-deoxidation lactose base, 1-deoxy-galactose base, 1-deoxymannose base, 1-deoxidation maltotriose glycosyl etc.
For in the present composition, using, it is desirable to alkyl-N-methyl glucose amide in this class tensio-active agent especially, it is following formula compound, wherein R 7Be alkyl (preferred C 11-C 13), R 8Be methyl, Q is a 1-deoxy-glucose base.
Other sugared deutero-tensio-active agent comprises N-alkoxyl group polyhydroxy fatty acid amide, for example C 10-C 18N-(3-methoxy-propyl) glucamide.The N-propyl group is to N-hexyl C 12-C 18Glucamide can be used for low bubble washing.C 10-C 20Conventional soap also can use.If wish high foam, can use side chain C 10-C 16Soap.In standard textbook, show other tensio-active agent commonly used.
For the present invention, other detersive surfactant of narrating below can be used in the laundry detergent composition.
The consumption that can be used for the limiting examples of other tensio-active agent of the present invention is generally about 1-55% weight, and this comprises conventional C 11-C 18Alkylbenzene sulfonate (" LAS "); Chemical formula is CH 3(CH 2) x(CHOSO 3 -M +) CH 3And CH 3(CH 2) y(CHOSO 3 -M +) CH 2CH 3C 10-C 18Secondary (2,3) alkyl-sulphate, wherein x and (y+1) be that M is a water-soluble cationic, especially sodium at least about 7, preferably at least about 9 integer; Undersaturated vitriol such as oleyl sulfate; C 10-C 18Alkyl alkoxy carboxylate salt (EO especially 1-5Ethoxy carboxylate); C 10-C 18Glyceryl ether; C 10-C 18Alkyl poly glucoside and corresponding sulfation glycan glycosides thereof; And C 12-C 18α-sulfonated fatty acid ester.If desired, in composition, can also comprise conventional non-ionic type and amphoteric surfactant, for example C 12-C 18Alkylethoxylate (" AE ") comprises so-called narrow distribution alkylethoxylate and C 6-C 12Alkyl phenolic alkoxy thing (especially ethoxylate and blended oxyethyl group/propoxylated glycerine), C 12-C 18Betaines and sulfonation betaines (" sultaine "), C 10-C 18Amine oxide etc.C 10-C 18N-alkyl polyhydroxy fatty acid amide also can use.Typical example comprises C 12-C 18The N-methyl glucose amide.Referring to WO 9,206,154.Other sugared deutero-tensio-active agent comprises N-alkoxyl group polyhydroxy fatty acid amide, for example C 10-C 18N-(3-methoxy-propyl) glucamide.C 10-C 20Conventional soap also can use.If wish high bubble, can use the C of side chain 10-C 16Soap.The mixture of negatively charged ion and nonionic surface active agent is especially suitable.In standard textbook, show the conventional surfactant that other is suitable for.
Other anion surfactant that is applicable to decontamination also can be included in the present composition.This comprise soap salt (ammonium salt of sodium, potassium, ammonium and replacement for example, for example one, two and triethanolamine salt), C 9-C 20Linear alkylbenzene sulfonate, C 8-C 22Uncle or secondary alkyl sulfonate, C 8-C 24Olefin sulfonate, sulfonation poly carboxylic acid, alkyl glycerol sulfonate; the aliphatic acyl glycerol sulfonate; aliphatic oil base glycerol vitriol, alkyl phenol epoxy ethane ether salt, sulfonated alkane; alkylphosphonic; isethionate is the acyl group isethionate for example, N-acyl taurine salt, the fatty acid amide of N-methyltaurine; succinic diamide acid alkyl ester and sulfosuccinate alkyl ester, sulfosuccinic acid monoesters (especially saturated and undersaturated C 12-C 18Monoesters), sulfosuccinate diester (especially saturated and undersaturated C 6-C 14Diester), the N-acyl sarcosinate, the vitriol of alkyl polysaccharide such as the vitriol of alkyl polyglucoside, chain primary alkyl sulfate, alkyl polyethoxye carboxylate salt such as chemical formula are RO (CH 2CH 2O) kCH 2COO -M +Those salt (wherein R is C 8-C 22Alkyl, k are the integers of 0-10, and M is the positively charged ion that forms soluble salt), and with hydroxyethylsulfonic acid esterification and usefulness sodium hydroxide neutral lipid acid.Other example visible surface promoting agent and washing composition (Surface Active Agents and Detergents) I and II volume, Schwartz, Perry and Berch work.
Laundry detergent composition of the present invention contains auxiliary component and carrier, auxiliary component is selected from enzyme, enzyme activator, suds suppressor, dyestuff, spices, tinting material, filling salt, hydrotropic agent and their mixture of washing assistant, white dyes, SYNTHETIC OPTICAL WHITNER, bleach boosters, bleach-activating agent, non-cellulose enzyme, but this list is not to have covered all, does not get rid of the makers-up and uses any other suitable material.
Auxiliary component
Non-cotton soil release agent can randomly use known polymkeric substance soil release agent in detergent composition of the present invention, be referred to as " SRA " later on.If use, SRA generally accounts for the 0.01-10.0% of composition weight, normally 0.1-5%, preferably 0.2-3.0%.Preferably SRA is above-mentioned those.
The SRA that is fit to the present composition has the hydrophilic segment of the surface hydrophilic that makes hydrophobic fibre (as polyester and nylon) usually, with the hydrophobic chain segment that is deposited on the hydrophobic fibre and keeps adhering with it in whole washing and rinse cycle, therefore hydrophobic chain segment plays a part anchor to hydrophilic segment.This makes easier being washed off in the stain washing step afterwards of generation after handling with SRA.
SRA can comprise many charged (for example anionic even cationic kind are seen the United States Patent (USP) 4,956,447 of authorizing September 11 nineteen ninety such as Gosselink etc.) and uncharged unit, and their structure can be straight chain, side chain or star structure.They can be included in the control molecular weight or change physics or the effective especially end-blocking part in surface-active property aspect.Can project organization with charge distribution to be used for different fibers or type of textiles and to be used for different washing composition or the detergent additives product.
SRA comprises oligomeric terephthalate class, and they with the method preparation that relates to a kind of transesterify/Oligomerisation at least, often use metal catalyst, for example titanium (IV) alkoxide usually.These esters can make with other monomer, these monomers can via one, two, three, four or more position be attached in the ester structure, and do not form fine and close crosslinked one-piece construction.
Suitable SRA comprises for example United States Patent (USP) 4; 968; the sulfonated products of the ester oligomer of the straight chain basically described in 451 (the authorizing J.J.Scheibel and E.P.Gosselink November 6 nineteen ninety), it contain the multiple unitary oligomer ester main chain of terephthaloyl and oxyalkylene oxygen basic weight and with main chain covalently bound by allyl group deutero-sulfonation terminal portions.This ester oligomer can prepare with following method: (a) with the vinyl carbinol ethoxylation; (b) make product and dimethyl terephthalate (DMT) (" DMT ") and 1 of (a), 2-propylene glycol (" PG ") is according to the transesterify/oligomerization step reaction in two steps; The product of (b) is reacted with Sodium Pyrosulfite in water.Other SRA comprises United States Patent (USP) 4,711,730 (on December 8th, 1987, Gosselink etc.) non-ionic type in end capped 1,2-propylidene/polyoxyethylene terephthalic polyester, for example ester that makes by the transesterify/oligomerization that gathers (ethylene glycol) methyl ether, DMT, PG and poly-(ethylene glycol) (" PEG ").Other SRA example comprises: part and the complete end capped oligomer ester of negatively charged ion (United States Patent (USP) 4,721,580, on January 26th, 1988, Gosselink), for example by ethylene glycol (" EG "), PG, DMT and 3, the oligopolymer that the hot sodium sulfonate of 6-two oxa-s-8-hydroxyl obtains; The end capped block polyester oligomeric compound (United States Patent (USP) 4 of nonionic, 702,857, on October 27th, 1987, Gosselink), for example by DMT, the end capped PEG of methyl (Me) and EG with and/or PG, or by DMT, EG and/or the end capped PEG of PG, Me and oligomeric compound that dimethyl-combination of 5-sulfonation m-phthalic acid sodium makes; And negatively charged ion; the end capped terephthalate of sulphur aroyl (United States Patent (USP) 4 particularly; 877; on October 31st, 896,1989, Maldonado, Gosselink etc.); the latter is the typical SRA that all is suitable in laundry and textile finishing product; an example is the ester composition of being made by a sulfosalicylic acid-sodium salt, PG and DMT, randomly but preferably also contain the PEG of adding, and PEG3400 for example.
SRA also comprises: the simple segmented copolymer of ethylene glycol terephthalate or propylene glycol ester terephthalate and polyoxyethylene or polyoxypropylene terephthalate, see and authorized the United States Patent (USP) 3 of Hays on May 25th, 1976,959, authorized the United States Patent (USP) 3 of Basadur on July 8th, 230 and 1975,893,929; Derivatived cellulose is the hydroxy ethers cellulose polymer compound sold with the METHOCEL title of Dow company for example; C 1-C 4Alkylcellulose and C 4Hydroxy alkyl cellulose is seen the United States Patent (USP) 4,000,093 of authorizing Nicol etc. on December 28th, 1976; And methyl cellulose ether, the average substitution degree of each dehydration glucose unit (methyl) is about 1.6-2.3, is about 80-120 centipoise 20 ℃ of 2% viscosity in aqueous solution that record.These materials are sold as METOLOSESM 100 and METOLOSE SM 200, and this is the trade name of the methyl cellulose ether of Shin-etsu Kagaku Kogyo KK manufacturing.
The suitable SRA that is feature with poly-(vinyl ester) hydrophobic segment comprises poly-(vinyl ester), for example C 1-C 6Vinyl ester, preferred poly-(vinyl-acetic ester) graft copolymer on the polyoxyalkylene main chain.See the european patent application 0 219 048 (Kud etc.) that on April 22nd, 1987 announced.The example of commercial goods comprises the SOKALAN SRA that can be obtained by BASF (Germany), for example SOKALAN HP-22.Other SRA contains 10-15% weight ethylene glycol terephthalate and the 80-90% weight polyester by the polyoxyethylene glycol deutero-polyoxyethylene terephthalate of molecular-weight average 300-5000 in the repeating unit.Commercial examples comprises the ZELON 5126 of Dupont company and the MILEASE of ICI company.
Another kind of SRA is that empirical formula is (CAP) 2(EG/PG) 5(T) 5(SIP) 1Oligopolymer; it contains terephthaloyl (T), sulfonation isophthaloyl base (SIP), oxygen inferior ethoxyl and Oxy-1; 2-propylidene (EG/PG) unit; and preferably use END CAPPED GROUP (CAP) end-blocking; preferably use the hydroxyethylsulfonic acid base end-blocking of modification; as in an oligopolymer, containing a sulfonation isophthaloyl base unit, 5 terephthaloyl unit, a certain proportion of oxygen inferior ethoxyl unit and oxygen-1, the inferior propoxy-unit (being preferably about 0.5: 1 to about 10: 1) of 2-and by two end-blocking unit of 2-(2-hydroxyl-oxethyl) ethyl sulfonic acid sodium deutero-.This SRA preferably also contains a kind of stablizer that reduces degree of crystallinity that accounts for oligopolymer weight 0.5%-20%, anion surfactant for example, as the Sodium dodecylbenzene sulfonate of straight chain or be selected from a kind of compound of dimethylbenzene, isopropyl benzene and tosylate or their mixture, these stablizers or conditioning agent are to be added in the synthesising container, fully as authorizing the United States Patent (USP) 5 of Gosselink, Pan, Kallett and Hall May 16 nineteen ninety-five, described in 415,807.The suitable monomers of above-mentioned SRA comprises 2-(2-hydroxyl-oxethyl) ethyl sulfonic acid sodium, DMT, dimethyl-5-sulfoisophthalic acid sodium, EG and PG.
The SRA of other type comprises: (I) uses the vulcabond coupling agent to connect the non-ionic type terephthalate that the polymeric ester structure forms, and sees United States Patent (USP) 4,201,804 (Violland etc.) and United States Patent (USP) 4,240,918 (Lagasse etc.); (II) has the SRA of carboxylicesters end group, and this carboxylicesters end group forms so that terminal hydroxyl is changed into trimellitate by add trimellitic acid 1,2-anhydride in known SRA.By selecting catalyst suitably, trimellitic acid 1,2-anhydride forms the chain link with polymer ends by its isolated acid esters rather than by opening anhydride bond.No matter be that non-ionic type or anionic SRA all can be used as the raw material use, but as long as they have the hydroxyl end groups of esterification.See United States Patent (USP) 4,525,524 (Tung etc.).Other type comprises: the SRA based on the anionic terephthalate of (III) urethanum connecting-type, see United States Patent (USP) 4,201,824 (Violland etc.); (IV) poly-(caprolactam) and with such as monomeric related copolymers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate, comprise non-ionic type and cation type polymer, see United States Patent (USP) 4,579,681 (Ruppert etc.); (V) is except the SOKALAN type of BASF AG, by the acrylic monomer graft copolymer that grafting forms on the sulfonated polyester.These SRA it is said to have the decontamination similar with known ether of cellulose and prevent sedimentary activity again, see EP279 in 1988,134A (Rhone-Poulenc Chemie).Several in addition classes comprise: (VI) vinyl monomer such as vinylformic acid and the vinyl-acetic ester grafts on protein such as casein, see EP 457,205A (BASF, 1991); The polyester-polyamide SRA that (VII) made by hexanodioic acid, hexanolactam and polyoxyethylene glycol condensation, it is used in particular for handling polyamide fabric, sees Beven etc., and DE 2,335,044 (Unilever N.V., 1974).At United States Patent (USP) 4,240, narrated other SRA that is suitable in 918,4,787,989 and 4,525,524.
Bleaching compounds---SYNTHETIC OPTICAL WHITNER and bleach-activating agent
Detergent composition of the present invention can randomly contain SYNTHETIC OPTICAL WHITNER or SYNTHETIC OPTICAL WHITNER wherein be arranged and the bleaching composition of one or more bleach-activating agents.When containing SYNTHETIC OPTICAL WHITNER, its content is about 0.05-30% of detergent composition, 1-30% more preferably from about, and preferably about 5-20% is especially for laundry operations.If contain bleach-activating agent, then its content in the bleaching composition that comprises SYNTHETIC OPTICAL WHITNER and bleach-activating agent is generally about 0.1-60%, more commonly about 0.5-40%.
The SYNTHETIC OPTICAL WHITNER of using among the present invention can be any SYNTHETIC OPTICAL WHITNER that is applicable to the detergent composition that uses in textiles cleaning, hard surface cleaning or known now or known other cleaning use that becomes.This comprises oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.Perborate bleach, for example Sodium peroxoborate (as one or tetrahydrate) can be used for the present invention.
Another kind of SYNTHETIC OPTICAL WHITNER that can unrestricted use comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The suitable example of this type of SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, the magnesium salts of metachloroperbenzoic acid, 4-nonyl amino-4-oxo Perbutyric Acid and diperoxy dodecanedioic acid.These SYNTHETIC OPTICAL WHITNER are disclosed in United States Patent (USP) 4,483,781 (Hartman, on November 20th, 1984), U.S. Patent application 740,446 (Burns etc., on June 3rd, 1985 submitted to), european patent application 0,133,354 (Banks etc., announced on February 20th, 1985) and United States Patent (USP) 4,412,934 (Chung etc., November 1 nineteen eighty-three).Highly preferred SYNTHETIC OPTICAL WHITNER for example comprises also that at United States Patent (USP) 4,634,6-nonyl amino-6-oxo of mentioning in 551 (Burns etc., on January 6th, 1987) is crossed oxy hexanoic acid.
Peroxygen bleach also can use.Suitable peroxy bleaching compound comprises yellow soda ash peroxyhydrate and suitable " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.Persulphate SYNTHETIC OPTICAL WHITNER (for example commodity OXONE of E.I.Du Pont Company's manufacturing) also can be used.
A kind of preferred percarbonate bleach contains average particle size and is the dried particle of about 500-1000 micron, in this particle less than about 200 microns about 10% weight that is no more than, greater than about 1250 microns about 10% weight that is no more than.This percarbonate can randomly use silicate, borate or water soluble surfactant active to coat.Percarbonate can obtain from various commercial source such as FMC, Solvay and Tokai Denka.
Also can use the mixture of SYNTHETIC OPTICAL WHITNER.
Perborate, peroxygen bleachs such as percarbonate are preferably combined with bleach-activating agent, and this activator can (that is, in washing process) produce and the corresponding peroxy acid of bleach-activating agent in the aqueous solution on the spot.At United States Patent (USP) 4,915, the various limiting examples of activator are disclosed in 854 (Mao etc., April 10 nineteen ninety) and the United States Patent (USP) 4,412,934.Typical example has nonanoly acyloxy benzene sulfonate (NOBS) and tetra acetyl ethylene diamine (TAED) activator, also can use their mixture.About being applicable to other typical SYNTHETIC OPTICAL WHITNER and activator of the present invention, also can be referring to United States Patent (USP) 4,634,551.
Extremely preferred amido deutero-bleach-activating agent is the compound of following chemical formula:
R 1N (R 5) C (O) R 2C (O) L or R 1C (O) N (R 5) R 2C (O) L is R wherein 1Be the alkyl that contains about 6-12 carbon atom, R 2Be the alkylidene group that contains about 1-6 carbon atom, R 5Be H or alkyl, aryl or the alkaryl that contains about 1-10 carbon atom, L is any suitable leavings group.Leavings group is owing to crossing the hydrolysis negatively charged ion breaks away from bleach-activating agent to the nucleophillic attack of bleach-activating agent any group.A kind of preferred leavings group is the phenylbenzimidazole sulfonic acid base.
The preferred embodiment of following formula bleach-activating agent comprises (the amino hexanoyl of 6-decoyl) oxygen base benzene sulfonate, (the amino hexanoyl of 6-nonanoyl) oxygen base benzene sulfonate, (the amino hexanoyl of 6-caprinoyl) oxygen base benzene sulfonate and composition thereof, as United States Patent (USP) 4,634,551 is described, and this patent is quoted as a reference in the present invention.
Another kind of bleach-activating agent comprises disclosed benzoxazine type activator in the United States Patent (USP) 4,966,723 that is presented to October 30 nineteen ninety such as Hodge etc., and this patent is quoted as a reference in the present invention.A kind of highly preferred benzoxazine type activator is,
Figure A9719610600371
The preferred bleach-activating agent of another class comprises the acyl lactam activator, the acyl caprolactam of especially following chemical formula and acyl group Valerolactim:
Figure A9719610600381
R wherein 6Be H or contain 1 alkyl, aryl, alkoxy aryl or alkaryl to about 12 carbon atoms.Highly preferred lactan activator comprises benzoyl caprolactam, decoyl hexanolactam, 3,5,5-trimethyl acetyl hexanolactam, nonanoyl hexanolactam, caprinoyl hexanolactam, undecylene acyl hexanolactam, benzoyl Valerolactim, decoyl Valerolactim, caprinoyl Valerolactim, undecylene acyl Valerolactim, nonanoyl Valerolactim, 3,5,5-trimethyl acetyl Valerolactim and their mixture.Other sees United States Patent (USP) 4,545, and 784 (on October 8th, 1985, Sanderson), this patent is quoted as a reference in this article, wherein discloses the acyl caprolactam that is adsorbed onto among the Sodium peroxoborate, comprises benzoyl caprolactam.
SYNTHETIC OPTICAL WHITNER outside the oxygen bleaching agent also is known in the art, can be used for the present invention.The non-oxygen bleaching agent of one class particularly important comprises the SYNTHETIC OPTICAL WHITNER of photoactivation, for example sulfonated Phthalocyanine Zinc and/or aluminium.See the United States Patent (USP) 4,033,718 that was presented to Holcombe etc. on July 5th, 1977.If use, contain this class SYNTHETIC OPTICAL WHITNER, especially the phthalocyanine sulfonic acid zinc of about 0.025-1.25% weight in the detergent composition usually.
If desired, bleaching compounds can be used manganic compound catalysis.This compounds is known in the art, for example comprises at United States Patent (USP) 5,246 621,5,244,594,5,194,416,5,114,606 and european patent application 549,271A1,549, disclosed manganese-based catalyst among 272A1,544,440 A2 and 544,490 A1; The preferred embodiment of these catalyzer comprises M n IV 2(u-O) 3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(PF 6) 2, M n III 2(u-O) 1(u-OAc) 2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(ClO 4) 2, M n IV 4(u-O) 6(1,4, the 7-7-triazacyclononane) 4(ClO 4) 4, M n IIIM n IV 4(u-O) 1(u-OAc) 2-(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(ClO 4) 3, M n IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)-(OCH 3) 3(PF 6) and their mixture.Other metal matrix bleaching catalyst is included in United States Patent (USP) 4,430,243 and United States Patent (USP) 5,114,611 in those disclosed.Reported also that in following United States Patent (USP) use manganese and various complex compound part are to strengthen bleaching action: 4,728,455,5,284,944,5,246,612,5,256,779,5,280,117,5,274,147,5,153,161 and 5,227,084.
In fact, but not, can regulate composition of the present invention and method,, be preferably formed about 0.1-700ppm, more preferably from about the catalyzer of 1-500ppm to form at least ten million/a active bleaching catalyst of having an appointment in the wash water solution as restriction.
In the present composition, can contain a variety of other components that are used in the detergent composition, comprise other active ingredient, carrier, hydrotropic agent, processing aid, dyestuff or pigment, the solvent that liquid preparation is used, the solid packing that bar composition is used etc.If wish high foam, then foaming booster can be mixed in composition, as C 10-C 16Alkanolamide, content is 1-10% usually.C 10-C 14Monoethanolamine and diglycollic amide are typical case's representatives of this class A foam A synergistic agent.It also is favourable that this class A foam A synergistic agent uses with height bubble cosurfactant such as above-mentioned amine oxide, trimethyl-glycine and sultaine.If desired, can add solubility magnesium salts such as the MgCl that consumption is generally 0.1-2% 2, MgSO 4Deng, remove the grease performance extra forming process to be provided and to strengthen.
The various decontamination components of using in the present composition can be randomly coat this carrier with hydrophobic coating then on the porous hydrophobic carrier and further stablize by this component is adsorbed on.Preferably, the decontamination component is mixed with a kind of tensio-active agent, and then be adsorbed onto in the porous support.In use, the decontamination component is discharged into from carrier in the wash water solution, plays the soil-removing action of expection therein.
For describing this technology in detail, (trade name SIPERNAT D10 is DeGussa) with the C that contains 3-5% with a kind of porous water drain silica 13-15The proteolysis enzyme solution of ethoxylated alcohol (EO7) nonionogenic tenside mixes.Usually, the weight of enzyme/surfactant soln is 2.5 times of silicon-dioxide.Formed powder utilizes dispersed with stirring (can use the various silicone oil of range of viscosities as 500-12500) in silicone oil.With the silicone oil dispersion emulsification that forms or add in to the end the detergent base.Utilize this method; can be " protected " so that be used in the washing composition such as components such as above-mentioned enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, light activating agent, dyestuff, white dyes, fabric conditioner and hydrolyzable tensio-active agents, comprise liquid laundry detergent compositions.
Liquid detergent composition can be moisture and other solvent as carrier.Low-molecular-weight primary alconol or secondary alcohol, for example methyl alcohol, ethanol, propyl alcohol and Virahol are suitable for.For solubilizing surfactant, preferred monohydroxy-alcohol, but polyvalent alcohol also can use to about 6 carbon atoms and 2 alcohol to about 6 hydroxyls (for example 1, ammediol, ethylene glycol, glycerol and 1,2-propylene glycol) as containing 2.Can contain 5%-90%, this class carrier of 10%-50% normally in the composition.
The pH that detergent composition of the present invention preferably is mixed with at washing operating period washing water is about 6.5-11, is preferably about 7.5-10.5.Liquid wash up product formulation pH is preferably about 6.8-9.0.The common pH of laundry product is 9-11.The technology that pH is controlled on the usage level of being advised comprises use buffer reagent, alkali, acid or the like, and this is well-known to those skilled in the art.
Other enzyme can comprise other enzyme of non-cellulose enzyme to be used for various purposes in detergent composition of the present invention, comprise the stain of removing protein-based, carbohydrate-based or triglyceride level base from the surface of for example textiles or tableware, prevent the dye transfer (for example in laundry) that comes off, and restore for fabric.Other suitable enzyme comprises proteolytic enzyme, amylase, lipase, peroxidase and composition thereof, and they are for example plant, animal, bacterium, fungi and yeast sources of any suitable source.Preferred select to be subjected to pH-activity for example and/or optimal stability value, thermostability and to the influence of the factors such as stability of activated detergent, washing assistant etc.Preferred bacterium enzyme or fungal enzyme, for example granulose bacterium and proteolytic enzyme in this respect.
" detergency enzymes " is meant any enzyme that has cleaning in laundry, hard surface cleaning or personal care detergent composition, remove stain or other advantageous effect in the present invention.Preferred detergency enzymes is a lytic enzyme, for example proteolytic enzyme, amylase and lipase.The preferred enzyme that is used to do washing includes but not limited to proteolytic enzyme, lipase and peroxidase.
Enzyme is usually to be enough to the providing content of " cleaning effective quantity " to be spiked in washing composition or the detergent additives composition.Term " cleans effective quantity " and is meant can be to generations such as dirt-carrying body such as fabric, tableware cleaning, go spot, scrubbing, brighten, deodorizing or become any amount of new role.In fact, for present commodity preparation, typical quantity is that every gram detergent composition is used up to about 5 milligrams more commonly about 0.01-3 milligram organized enzyme.In other words, the present composition contains the commercial enzyme preparation of about 0.001%-5%, preferred 0.01%-1% weight usually.In this class commercial enzyme preparation, proteolytic enzyme is enough to provide the active quantities of every gram composition 0.005-0.1 Anson unit (AU) to exist usually.In highly spissated detergent formulations, may need higher active quantities.
Be fit to amylase of the present invention and for example comprise at GB 1,296 α-Dian Fenmei of describing among 839 (Novo), International Bio-Synthetics, the RAPIDASE of Inc TERMAMYL with Novo company The FUNGAMYL of Novo company Particularly suitable.Be used for improving stability, the enzyme engineering of for example improving oxidative stability is known.For example see journal of biological chemistry (J.Biological Chem.), the 260th 11 phases of volume, in June, 1985,6518-6521 page or leaf.Some embodiment preferred of the present composition can be utilized the amylase of stability improvement in washing composition such as automatic bowl type washing composition, especially with 1993 the listing TERMAMYL The improved amylase of oxidative stability that records as the reference benchmark.These preferred amylase all have " stability-enhanced " diastatic characteristics, it is characterized in that having following one or more detectable improvement at least: oxidative stability with respect to above-mentioned reference data amylase, for example, to the oxidation of hydrogen peroxide/tetra acetyl ethylene diamine in the damping fluid of pH9-10; Thermostability, for example, 60 ℃ according to appointment of common wash temperatures; Or alkaline stability, for example, at the about 8-11 of pH.Stability can be measured with the disclosed any engineering test of prior art.For example see the reference of mentioning among the WO 9402597.Stability-enhanced enzyme can be obtained by Novo or Genencor International.The extremely preferred amylase of a class of the present invention has the site-directed mutagenesis of utilization from one or more bacillus amylase, especially bacillus α-Dian Fenmei deutero-general character, no matter its direct precursor is a kind of, two kinds or multiple amylase strain.Oxidative stability is preferably used than the above-mentioned amylase that improves with reference to amylase, in particular for bleaching, more preferably be used for the detergent composition of the present invention of the oxygen bleaching different with chlorine bleaching.The preferred amylase of this class comprises the WO 9402597 (Novo that (a) preamble is quoted, on February 3rd, 1994) amylase, further example is to replace bacillus licheniformis alpha-amylase (being called TERMAMYL) or be positioned at a kind of mutant that 197 methionine residue obtains with the similar parent amylase (as bacillus amyloliquefaciens, subtilis or bacillus stearothermophilus amylase) of source position variation with L-Ala or Threonine (preferred Threonine); (b) the stability-enhanced amylase described in the article " oxidation resistant α-Dian Fenmei " of the Genencor International that in the 207th American Chemical Society's annual meeting holding 13-17 day in March, 1994, reads out by C.Mitchinson.The SYNTHETIC OPTICAL WHITNER of wherein mentioning in the automatic dishwasher washing composition makes the α-Dian Fenmei inactivation, but Genencor company has made the amylase that oxidative stability improves by Bacillus licheniformis NCIB 8061.It is the group that most probable is modified that methionine(Met) (Met) is confirmed to be.8,15,197,256,304,366 and 438 places replace Met one at a time and cause forming special mutant in the position, particularly importantly M197L and M197T, and wherein the M197T variant is the mutant of stably express.Stability is at CASCADE And SUNLIGHT Middle mensuration; (c) the particularly preferred amylase of the present invention is included in the amylase variant that other modification is arranged in the intermediate parent body, and described in WO 9510603A, they can be by transferee Novo company as DURAMYL Buy.The amylase that other particularly preferred oxidative stability improves is included in those described in WO 9418314 (Genencor International) and the WO 9402597 (Novo).The amylase that any other oxidative stability improves all can use, for example the amylase of being derived and forming through site-directed mutagenesis by commercially available diastatic known chimeric, hybridization or simple mutant parent form.Other preferred enzyme-modified can be accomplished, sees WO 9509909 (Novo).
The lipase that is suitable for washing composition comprises by pseudomonas microbial, and the lipase that makes as Pseudomonas stutzeri ATCC 19.154 is for example at GB 1,372, disclosed in 034.Also can be referring to the lipase in the Japanese patent application 53,20487 (on February 24th, 1978 is open).This kind lipase can be buied trade name Lipase P " Amano ", or " Amano-P " by Amano Pharmaceutical Co Ltd. (Nagoya, Japan).Other suitable commercial lipases comprises Amano-CES, derive from thickness look bacillus for example thickness look bacillus separate the lipase of fat mutation NRRLB3673, Japanese Toyo Jozo Co. company (Tagata) produces; The thickness look bacillus lipase of U.S.Biochemical Corp (U.S.) and Disoynth Co. (Holland), and the lipase that derives from the gladiolus pseudomonas.Plant the mould LIPOLASE that derives and form by the fetal hair corruption Enzyme can obtain (also seeing EP 341,947) from Novo company, and it is to be used for preferred enzyme of the present invention.In WO 9414951 A (Novo), narrated peroxidase stable lipase and amylase variant.Also see WO 9205249 and RD 94349044.
Be suitable at of the present invention and in WO 8809367A (Genencor), explanation arranged.
Peroxidase can be used in combination with oxygen source (as percarbonate, perborate, hydrogen peroxide etc.), be used for " solution bleaching " or prevent from during washing to remove from the dirt-carrying body under dyestuff or pigment transfer to other dirt-carrying body that washings exists.Known peroxidase comprises horseradish peroxidase, ligninase and halo peroxidase, for example chloro or bromoperoxidase.In WO 89099813A (authorizing Novo on October 19th, 1989) and WO 8909813 (Novo), introduced the detergent composition that contains peroxidase.
At WO 9307263A and WO 9307260A (Genencor International) WO8908694A (Novo) and United States Patent (USP) 3, also narrated various enzymes in 553,139 (the authorizing McCarty etc. on January 5th, 1971) and it has been incorporated into method in the synthetic detergent composition.At United States Patent (USP) 4,101, in 457 (Place etc., on July 18th, 1978) and the United States Patent (USP) 4,507,219 (Hughes, on March 26th, 1985) various enzymes are disclosed also.At United States Patent (USP) 4,261, introduce the enzyme material that can be used in the liquid detergent preparation 868 (Hora etc., on April 14th, 1981) and it has been mixed method in this class preparation.The enzyme that is used for washing composition can in all sorts of ways stable.At United States Patent (USP) 3,600,319 (on August 17th, 1971, Gedge etc.), EP 199,405 and EP 200,586 are (on October 29th, 1986, open and enumerated the enzyme stabilising method in Venegas).For example also narrating the enzyme stabilising system in the United States Patent (USP) 3,519,570.In WO 9401532 (Novo), introduced a kind of useful genus bacillus AC13 that forms proteolytic enzyme, zytase and cellulase.
The suitable example of proteolytic enzyme is the subtilisin that the specific bacterial strain by subtilis and Bacillus licheniformis obtains.A kind of suitable proteolytic enzyme is that the bacterial strain by genus bacillus obtains, and maximum activity is all arranged in the entire area of pH 8-12, and it is by Novo Industries A/S (being called " Novo " later on) development of Denmark and with ESPERASE Title sell.The preparation of this kind enzyme and similar enzyme has explanation at GB 1,243 among 784 (Novo).Other useful proteases comprises the ALCALASE of Novo company And SAVINASE And Dutch Intemational Bio-Synthetics, the MAXATASE of Inc. And at EP 130, the disclosed Protease A of 756A (on January 9th, 1985), at EP 303,761A (on April 28th, 1987) and EP130, the disclosed Protease B of 756A (on January 9th, 1985).Also referring to a kind of high pH proteolytic enzyme that obtains by genus bacillus NCIMB 40338 of narration in WO 9318140A (Novo).In WO 9203529 A (Novo), narrated the enzyme-containing detergent that contains proteolytic enzyme, one or more other enzymes and a kind of reversible proteinase inhibitor.Other preferred proteolytic enzyme comprises WO 9510591 A (Procter ﹠amp; Gamble) those enzymes in.If desired, can buy as at WO 9507791 (Procter ﹠amp; Gamble) proteolytic enzyme that absorption minimizing described in and hydrolysis increase.In WO 9425583 (Novo), narrated a kind of proteolytic enzyme of recombinant trypsin formula of suitable washing composition of the present invention.
In more detail, the particularly preferred proteolytic enzyme of a kind of being called " Protease D " is the carbonylic hydrolase with the undiscovered aminoacid sequence of occurring in nature, as A.Baeck etc. at the U.S. Patent application 08/322 that is entitled as " cleaning combination that contains proteolytic enzyme ", 676 and C.Ghosh etc. be entitled as the U.S. Patent application 08/322 of " bleaching composition that contains proteolytic enzyme ", described in 677 (the two is all submitted on October 13rd, 1994), this enzyme is to be replaced with a kind of different amino acid by the precursor carbonylic hydrolase being equivalent in this carbonylic hydrolase+76 places, and preferably also have according to bacillus amyloliquefaciens subtilisin coding be equivalent to+99, + 101, + 103, + 104, + 107, + 123, + 27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, + 204, + 206, + 210, + 216, + 217, + 218, + 222, + 260, + 265, and/or+a plurality of amino-acid residues on one or more amino-acid residues position of 274 derive and form.
Preferred laundry detergent composition of the present invention can randomly contain the proteolytic enzyme of a kind of being called " Protease D ", it is a kind of carbonylic hydrolase variant with aminoacid sequence of non-natural existence, as A.Baeck etc. at the U.S. Patent application 08/322 that is entitled as " cleaning combination that contains proteolytic enzyme ", 676 and C.Ghosh etc. at the U.S. Patent application 08/322 that is entitled as " bleaching composition that contains proteolytic enzyme ", described in 677 (the two is all submitted on October 13rd, 1994), this enzyme be by the precursor carbonylic hydrolase be equivalent in a kind of different this carbonylic hydrolase of aminoacid replacement+on 76, and preferably also have according to bacillus amyloliquefaciens subtilisin coding be equivalent to+99, + 101, + 103, + 104, + 107, + 123, + 27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, + 204, + 206, + 210, + 216, + 217, + 218, + 222, + 260, + 265, and/or+a plurality of amino-acid residues on one or more amino-acid residues position of 274 derive and form.
Preferred proteolytic enzymes also comprises the bacterial serine proteolytic enzyme of modification, for example at european patent application 87 303, and the enzyme that 761.8 (on April 28th, 1987 submitted to, particularly the 17th, 24 and 98 page) are described, this paper is referred to as " Protease B "; The bacterial serine proteolytic ferment of the modification of mentioning in the european patent application 199,404 (Venegas announced on October 29th, 1986) above is referred to as " Protease A "; Disclosed Protease A and EP 303,761 A (on April 28th, 1987) and EP130 among EP 130,756 A (on January 9th, 1985), the disclosed Protease B of 756A (on January 9th, 1985).
Preferred proteolytic enzyme also comprises subtilisin, particularly undergos mutation by making to each nucleotide sequence of this enzyme coding, thus the aminoacid sequence of regulatory enzyme and the BPN ' that is modified.The subtilisin of these modifications is compared with the wild-type subtilisin, has reduced the absorption on insoluble substrate, has increased the hydrolysis of insoluble substrate.The gene mutation body of suitable also promising this BPN ' variant coding.
Preferred BPN ' variant comprises the wild-type amino acid sequence, and wherein the wild-type amino acid sequence is substituted in following one or more positions: 199,200,201,202,203,204,205,206,207,208,209,210,211,212,213,214,215,216,218,219 or 220; BPN ' compares with the wild-type subtilisin, and this BPN ' variant has reduced the absorption on insoluble substrate, has increased the hydrolysis of insoluble substrate.Amino acid whose optimum seeking site with replacement is 199,200,201,202,205,207,208,209,210,211,212 or 215; More preferably 200,201,202,205 or 207.
For being used for the present invention, preferred proteolytic enzyme also comprises subtilisin 309 variants.These proteolytic enzyme comprise a few subtilisin-like protease 309 variants.
A. ring district 6 replaces the aminoacid sequence that these subtilisin 309 variants of variant have the improvement of subtilisin 309 wild-type amino acid sequences, and wherein Gai Liang aminoacid sequence is included on one or several position of 193,194,195,196,197,199,200,201,202,203,204,205,206,207,208,209,210,211,212,213 or 214 and replaces; Thereby subtilisin 309 variants are compared with wild-type subtilisin 309, and the absorption on insoluble substrate reduces and has increased the hydrolysis of insoluble substrate.These proteolytic enzyme preferably carry out aminoacid replacement at 193,194,195,196,199,201,202,203,204,205,206 or 209 places, more preferably 194,195,196,199 or 200.
B. the Duo Huan district replaces the improvement aminoacid sequence that these subtilisin 309 variants of variant also can have subtilisin 309 wild-type amino acid sequences, wherein Gai Liang aminoacid sequence be included in first, second, third, fourth or the five rings district in one or more rings district in one or more positions on replace, thereby subtilisin 309 variants are compared with wild-type subtilisin 309, reduced the absorption of insoluble substrate and increased the hydrolysis of insoluble substrate.
C. replace in addition at place, acyclic district, one of wild-type subtilisin 309 replaces or polysubstituted can the generation position outside Huan Qu, and for example the position 74.If only 74 pairs of subtilisins 309 carry out additional replacement in the position, then preferably replace, preferably His or Asp with Asn, Asp, Glu, Gly, His, Lys, Phe or Pro.But also can on one or more rings position, modifying outside 74, for example on residue 97,99,101,102,105 or 121.
Further specifying of pair subtilisin BPN ' variant and subtilisin 309 variants arranged in WO 95/29979, WO 95/30010 and WO 95/30011, above-mentioned patent is all announced in November 9 nineteen ninety-five, is quoted as a reference in the present invention entirely.
The enzyme stabilising system is of the present invention to be contained enzyme (including but not limited to) liquid composition and can contain about 0.001-10%, preferably about 0.005-8%, most preferably from about the enzyme stabilising system of 0.01-6% weight.The enzyme stabilising system can be any stabilising system compatible with detergency enzymes.This stabilising system can be inherently provided by other actives of preparation, or adds in addition, is for example added by the makers-up or is added by the producer of washing composition alternation enzyme.This stabilising system can contain for example calcium ion, boric acid, propylene glycol, short chain carboxy acid, alkylboronic acids and their mixture, and designs to solve different stabilization problem with physical form according to the type of detergent composition.
A kind of stabilising method are to use water-soluble calcium and/or magnesium ion source so that provide these ions to enzyme in final product composition having.Calcium ion is more effective than magnesium ion usually, if only use one type of positively charged ion, then preferably uses calcium.Typical detergent composition, particularly liquid composition contain about 1-30, preferably about 2-20, the calcium ion of 8-12 mmole more preferably from about, but can change with various factors in every liter of finished product, comprise multiplicity, type and the consumption of the enzyme that is added.Preferred water-soluble calcium or the magnesium salts of using comprises for example calcium chloride, calcium hydroxide, calcium formiate, calcium malate, calcium maleate and lime acetate; More generally, can use calcium sulfate or with the corresponding magnesium salts of cited calcium salt.Further improve the content of calcium and/or magnesium yes useful, for example can promote the dissolving grease effect of some type list surface-active agent.
Another kind of stabilising method are to use borate.United States Patent (USP) 4,537,706 referring to Severson.When using the borate stablizer, its consumption the most nearly composition weight 10% or more, but more commonly, content is up to the boric acid of about 3% weight or other borate compound (as borax or ortho-borate) and is fit to liquid washing agent and uses.The boric acid that can use replacement for example phenyl-boron dihydroxide, butane boric acid, bromophenyl boric acid etc. is replaced boric acid, and can reduce total boron content in the detergent composition by the boron derivative that uses these replacements.
The stabilising system of some cleaning combination can also contain from 0 to about 10%, the preferred chlorine bleach scavenging agent of about 0.01-6% weight, attacks enzyme and makes its inactivation to prevent the chlorine bleaching material in a lot of water sources, especially under alkaline condition.Though the cl content in the water may be very little, be generally about 0.5-1.75ppm, at for example wash up or the chlorine that exists in the total volume of water that contacts with enzyme during washing fabric may be quite big; Therefore, enzyme is a problem sometimes to the stability of chlorine in use.Because perborate or percarbonate can react with chlorine bleach, and in some instant compositions its content can with the stabilising system separate computations, so may be no longer must use the stablizer of anti-chlorine in addition, but by using them then may make effect improved in most of situations.Suitable chlorine scavenger negatively charged ion is generally understood and is obtained easily, if use, can be the sulphite that contains ammonium cation, hydrosulphite, thiosulfite, thiosulphate, iodide salt etc.Antioxidant such as carbaminate, ascorbate salt etc., organic amine such as ethylenediamine tetraacetic acid (EDTA) (EDTA) or its an alkali metal salt, monoethanolamine (MEA) and their mixture can use equally.And, can mix special enzyme inhibition system so that different enzymes has maximum consistency.If desired, can use other conventional scavenging agent, for example hydrosulfate, nitrate, muriate, hydrogen peroxide cource such as sodium perborate tetrahydrate, Sodium peroxoborate monohydrate and SPC-D, and phosphoric acid salt, condensed phosphate, acetate, benzoate, Citrate trianion, formate, lactic acid salt, malate, tartrate, salicylate etc. and their mixture.In general, because the chlorine scavenger function can be finished by other component (for example hydrogen peroxide cource) that is listed in addition under the function name that more is known, so not necessarily need to add in addition chlorine scavenger, unless do not exist in the enzyme embodiment the compound of this function performance to the degree of wanting in of the present invention containing; Even at latter event, the adding of scavenging agent is also only for reaching best effect.In addition, the makers-up meets the tendency with chemist's common skill, to avoid using when preparing and the inconsistent basically any enzyme scavenging agent of other active ingredient or the stablizer that may use.As for the use of ammonium salt, this salt can mix with detergent composition simply, but when storing its easy planar water and/or emit ammonia.Therefore, if this class material exists,, be protected in the particle described in 392 (Baginski etc.) preferably as United States Patent (USP) 4,652.
Washing assistant can randomly comprise detergent builders with control mineral substance hardness in the present composition.Can use inorganic or organic washing-assisting detergent.Washing assistant is used in the laundry composition usually to help to remove the particulate state dirt.
The content of washing assistant can be with the end-use of composition and desired physical form thereof and great changes have taken place.If exist, composition contains the washing assistant at least about 1% usually.Liquid preparation generally contains about 5-50%, the washing assistant of about 5-30% weight more commonly.Granular preparation generally contains about 10-80%, the washing assistant of about 15-50% weight more commonly.But do not get rid of the washing assistant that uses higher or lower content.
Inorganic or phosphorated washing assistant includes but not limited to an alkali metal salt, ammonium salt or alkanol ammonium salts (example has tri-polyphosphate, pyrophosphate salt and glassy polymeric metaphosphate), phosphonate, phytinic acid, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and the aluminosilicate of Tripyrophosphoric acid.But, need nonphosphate builders in some occasion.Importantly, even the present composition is at so-called " weak " washing assistant (comparing with phosphoric acid salt) for example in the presence of the Citrate trianion, or under the situation that contingent what is called " helps and washes deficiency " with zeolite or layered silicate washing assistant the time, usefulness is also good astoundingly.
The example of silicate-like builder is an alkalimetal silicate, particularly SiO 2: Na 2The O ratio is 1.6: 1 to 3.2: 1 silicate and a lamellated silicate, for example at United States Patent (USP) 4,664, and lamina sodium silicate described in 839 (the authorizing H.P.Rieck on May 12nd, 1987).NaSKS-6 is the trade mark (being abbreviated as " SKS-6 " herein usually) of a kind of crystalline state layered silicate of Hoechst sale.Different with zeolite builders, the NaSKS-6 silicate-like builder does not contain aluminium.NaSKS-6 has δ-Na 2SiO 5The layered silicate pattern.Its available for example DE-A-3,417,649 and DE-A-3, the method preparation described in 742,043.SKS-6 is used for highly preferred layered silicate of the present invention, but also can use other layered silicate, and for example general formula is NaMSi xO 2x+1YH 2The layered silicate of O, wherein M is sodium or hydrogen, and x is the numerical value of 1.9-4, is preferably 2, and y is the numerical value of 0-20, is preferably 0.The various layered silicates of other of Hoechst company comprise NaSKS-5, NaSKS-7 and the NaSKS-11 as α, β and γ form.As mentioned above, for application of the present invention, δ-Na 2SiO 5(NaSKS-6 form) is most preferred.Other silicate also may be suitable for, Magnesium Silicate q-agent for example, and it can be used as very crisp in the granular preparation, the component of the stablizer of oxygen bleaching agent and foam control system.
The example of carbonate builders is as German patent application 2,321, disclosed alkaline-earth metal and alkaline carbonate in 001 (announcement on November 15th, 1973).
The aluminosilicate washing assistant can be used for the present invention.The aluminosilicate washing assistant has important application in the heavy dirty granular detergent composition of at present commercially available great majority, and also can be important builder component in liquid detergent preparation.The aluminosilicate washing assistant comprises the compound that empirical formula is following:
[M z(zAlO 2) y] xH 2O wherein z and y is at least 6 integer, and the mol ratio of z and y is 1.0 to about 0.5, and x is the integer of about 15-264.
The aluminosilicate ion exchange material that is suitable for has the commercially available prod.The structure of these aluminosilicates can be a crystalline state or amorphous, can be naturally occurring aluminosilicate or synthetic product.Authorize on October 12nd, 1976 in the United States Patent (USP) 3,985,669 of Krummel and narrated a kind of method for preparing aluminosilicate ion exchange material.Be applicable to the synthetic aluminosilicate ion exchange material of preferred crystalline state of the present invention can Zeolite A, the title of Zeolite P (B), Zeolite MAP and ZeoliteX buys.In particularly preferred embodiments, the crystalline aluminosilicate ion-exchange material has following chemical formula: Na 12[(AlO 2) 12(SiO 2) 12] xH 2O wherein x is about 20-30, especially about 27.This material is called as Zeolite A.The zeolite of dehydration (x=0-10) also can be used for the present invention.The size of particles of aluminosilicate is preferably the about 0.1-10 micron of diameter.
Be applicable to that organic washing auxiliary detergent of the present invention includes but not limited to a very big class multi-carboxylate compound.As used in this article, " multi-carboxylate " is meant many carboxyls, preferably has the compound of at least 3 carboxyls.The multi-carboxy acid salt washing agent generally can sour form join in the composition, but also can add with the form of neutral salt.Add in form with salt fashionable, preferred as alkali salt (as sodium, potassium and lithium salts) or alkanol ammonium salts.
Comprise the material that many kinds are suitable among the multi-carboxy acid salt washing agent.The important multi-carboxy acid salt washing agent of one class for example comprises that at United States Patent (USP) 3,128, the ether multi-carboxylate described in 287 (Berg, on April 7th, 1964) and the United States Patent (USP) 3,635,830 (Lamberti etc., on January 1st 8,1972) comprises oxygen di-succinate.Also can be referring to " TMS/TDS " washing assistant of the United States Patent (USP) 4,663,071 of authorizing Bush etc. on May 5th, 1987.Suitable ether multi-carboxylate also comprises annular compound, and alicyclic compound especially for example at United States Patent (USP) 3,923, is mentioned in 679,3,835,163,4,158,635,4,120,874 and 4,102,903.
Other washing assistant that is suitable for comprises ether hydroxypolycarboxylic acid salt.The multipolymer of maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, carboxymethyl oxosuccinic acid, various an alkali metal salts, ammonium salt and the substituted ammonium salt of polyacetic acid such as ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA), and multi-carboxylate, for example mellitic acid, succsinic acid, oxo disuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyl oxosuccinic acid and soluble salt thereof.
The Citrate trianion washing assistant, for example citric acid and salt thereof (particularly sodium salt) are because they can be by can the regenerated resource obtaining and have biodegradable, so be the multi-carboxy acid salt washing agent of particularly important for the heavy duty liquid laundry detergent preparation.Citrate trianion also can be used in the granular composition, especially is used in combination with zeolite and/or layered silicate washing assistant.Oxygen di-succsinic acid also is specially adapted in this based composition and the mixture.
What be fit to detergent composition of the present invention also has at United States Patent (USP) 4,566,984 (on January 28th, 1986, disclosed 3 in Buch), 3-dicarboxyl-4-oxa--1,6-adipate and relevant compound.The succsinic acid washing assistant that is suitable for comprises C 5-C 20Alkyl and alkenyl succinic and salt thereof.Particularly preferably be the dodecenyl succinic succsinic acid in this compounds.The specific examples of succinate washing assistant comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates etc.The lauryl succinate is that this class washing assistant is preferred, at european patent application 86200690,5/0,200, in 263 (announcements on November 5th, 1986) explanation is arranged.
At United States Patent (USP) 4,144, openly send out the multi-carboxylate that other is suitable in 226 (Crutchfield etc., on March 13rd, 1979) and the United States Patent (USP) 3,308,067 (Diehl, on March 7th, 1967).Also referring to the United States Patent (USP) 3,723,322 of Diehl.
Lipid acid, for example C 12-C 18Monocarboxylic acid also can be individually or with above-mentioned washing assistant particularly Citrate trianion and/or succinate washing assistant, is spiked in the composition so that extra washing assistant activity to be provided.This application of lipid acid generally can cause to bubble and reduce, and the makers-up should consider this point.
In the situation that can use phosphorus base washing assistant, especially, can use various alkali metal phosphates, the tripoly phosphate sodium STPP of for example knowing, trisodium phosphate and sodium orthophosphate in the piece agent that is used for hand-washing operation.Also can use the phosphonate washing assistant, for example ethane-1-hydroxyl-1,1-diphosphonate and other known phosphonate (for example seeing United States Patent (USP) 3,159,581,3,213,030,3,422,021,3,400,148 and 3,422,137).
Sequestrant detergent composition of the present invention also can randomly contain one or more iron and/or manganese sequestrant.This class sequestrant can be selected from aminocarboxylate, amino phosphonates do, the aromatic chelating agent of multiple functional radical replacement and their mixture, complete same definition hereinafter.Do not plan to do theoretical discussion, but believe that the advantageous effect of these materials partly is because they are by forming the soluble chelating thing removes de-iron and mn ion from washings uncommon ability.
The aminocarboxylate that is suitable as optional sequestrant comprises edetate, N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, their basic metal, ammonium and substituted ammonium salt and their mixture.
Allow in detergent composition when the total phosphorus content of low levels exists at least, amino phosphonates do also is adapted at using as sequestrant in the present composition, and this comprises the ethylenediamine tetraacetic (methylene phosphonic acid salt) that is called DEQUEST.Preferably these amino phosphonates do do not contain alkyl or the alkenyl that surpasses about 6 carbon atoms.
The aromatic chelating agent that multiple functional radical replaces also can be used for the present composition.See the United States Patent (USP) 3,812,044 of authorizing Connor etc. on May 21st, 1974.The compound of preferred this class acid form is a dihydroxyl disulfobenzene class, for example 1, and 2-dihydroxyl-3,5-disulfobenzene.
It is a kind of that to be preferred for biodegradable cheating agent of the present invention be quadrol two succinates (" EDDS "), especially as United States Patent (USP) 4,704, and [S, the S] isomer described in 233 (Hartman and Perkins, on November 3rd, 1987).
If use, these sequestrants generally account for about 0.1-10% of detergent composition weight.More preferably, if use, the consumption of these sequestrants is about 0.1-3.0% of composition weight.
Native dirt removing/anti-deposition agent present composition more also can randomly contain to have removes native dirt and the anti-water-soluble ethoxylated amine of deposit properties again.The granular detergent composition that contains these compounds contains the water-soluble ethoxylated amine of about 0.01%-10.0% weight usually; Liquid detergent composition generally contains about 0.01%-5%.
Most preferred scale removal and anti-deposition agent again are the tetrens of ethoxylation.Authorize on July 1st, 1986 in the United States Patent (USP) 4,597,898 of Vander Meer and further narrated exemplary ethoxylated amine.The another kind of soil dirt/anti-deposition agent again that preferably goes is a disclosed cationic compound in european patent application 111,965 (Oh and Gosselink announced on June 27th, 1984).Operable other goes soil dirt/anti-deposition agent again to be included in the disclosed ethoxylated amine polymer of european patent application 111984 (Gosselink announced on June 27th, 1984); Disclosed amphoteric ion type polymkeric substance in the european patent application 112,592 (Gosselink announced on July 4th, 1984); With United States Patent (USP) 4,548, disclosed oxidation amine in 744 (Connor, on October 22nd, 1985).Known in the art other goes soil dirt and/or anti-deposition agent more also can be used for the present composition.Another kind of preferred anti-deposition agent again comprises carboxymethyl cellulose (CMC) material.These materials are known in the art.
Polymeric dispersant can advantageously use the polymeric dispersant of about 0.1-7% weight in the present composition, especially in the presence of zeolite and/or layered silicate washing assistant.The suitable polymers dispersion agent comprises polymeric polycarboxylate and polyoxyethylene glycol, but other dispersion agent known in the art also can use.Though do not think bound by theory, but believe that polymeric dispersant is with other washing assistant (comprising low-molecular-weight polycarboxylate) when using, by suppressing crystal growth, granular dirt come off peptization and anti-resedimentation, strengthened the usefulness of whole detergent builders.
Polymeric poly carboxylic acid material can be by suitable unsaturated monomer (preferably with its sour form) polymerization or copolymerization.The unsaturated monomer acid that can polymerization forms suitable polymeric multi-carboxylate comprises vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.Having the monomer that does not contain the carboxylic acid group in polymeric multi-carboxylate of the present invention is suitable as segments such as methoxy ethylene, vinylbenzene, ethene, as long as these segments are no more than about 40% weight.
Specially suitable polymeric multi-carboxylate can be derived by vinylformic acid and form.The water-soluble salt that to can be used for this class acrylic acid based polymer of the present invention be polymeric acrylic acid.The molecular weight of the polymkeric substance of this sour form is preferably about 2000-10000,4000-7000 more preferably from about, preferably about 4000-5000.The water-soluble salt of this acrylate copolymer can comprise for example ammonium salt of an alkali metal salt, ammonium salt and replacement.This type of soluble polymer is a known substance.Authorize on March 7th, 1967 in the United States Patent (USP) 3,308,067 of Diehl and disclose this application of class polyacrylate in detergent composition.
The preferred ingredient that vinylformic acid/maleic copolymer also can be used as dispersion/anti-deposition agent again uses.This class material comprises the water-soluble salt of the multipolymer of vinylformic acid and toxilic acid.The molecular-weight average of the sour form of this multipolymer is preferably about 2000-100000, and more preferably about 5000-75000 most preferably is about 7000-65000.The ratio of acrylic and maleic segment was generally about 30: 1 to about 1: 1 in the multipolymer, more preferably about 10: 1 to 2: 1.The water-soluble salt of this vinylformic acid/maleic acid can comprise for example ammonium salt of an alkali metal salt, ammonium salt and replacement.Solubility vinylformic acid/the maleic acid of this class is a known substance, at european patent application 66915 (announcement on December 15 nineteen eighty-two) and EP 193, in 360 (announcements on September 3rd, 1986) explanation is arranged, back one patent has also been mentioned this base polymer that contains hydroxypropyl acrylate.Another kind of available dispersion agent comprises toxilic acid/vinylformic acid/vinyl alcohol terpolymer.In EP 193,360, also disclose this class material, comprised that ratio for example is the terpolymer of vinylformic acid/toxilic acid/vinyl alcohol of 45/45/10.
Another polymkeric substance that can be included is polyoxyethylene glycol (PEG).PEG can demonstrate dispersion agent usefulness and work the soil dirt/anti-deposition agent effect again that removes.The typical molecular weight that is used for these purposes is about 500-100000, preferably about 1000-50000, more preferably from about 1500-10000.
Polyaspartic acid salts and polyglutamic acid dipersant also can use, and especially use with zeolite builders.The molecular-weight average of dispersion agent such as polyaspartic acid salts is preferably about 10000.
Whitening agent any white dyes known in the art or other increase gorgeous or whitening agent all can be incorporated in the detergent composition of the present invention, and its content is generally about 0.05%-1.2% weight.Be applicable to that commodity white dyes of the present invention can be divided into following a few class, including but not limited to: the derivative of stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanine, dibenzothiophene-5,5-dioxide, pyroles, 5 and 6 yuan of heterocycles and other miscellaneous agents.The example of these whitening agent is at " manufacturing of glimmering calcofluor white and application " (The Productionand Application of Fluorescent Brightening Agents) of a M Zahradnik book (JohnWiley ﹠amp; Sons, New York, 1982) in explanation is arranged.
The specific examples that can be used for the glimmering calcofluor white of the present composition is at United States Patent (USP) 4,790,856 (on December 13rd, 1988, Wixon) middle those that confirm.These whitening agent comprise the PHORWHITE series whitening agent of Verona company.Disclosed other whitening agent comprises in the document: Tinopal UNPA, Tinopal CBS and Tinopal 5BM can be obtained by Ciba-Geigy company; Artic White CC and Artic White CWD can be obtained by Hilton-Davis (Italy); 2-(4-styryl phenyl)-2H-naphthols is [1,2-d] triazole also; 4,4 '-two (1,2,3-triazoles-2-yl) stilbene; 4,4 '-two (styryl) biphenyl and aminocoumarin.The specific examples of these whitening agent comprises 4-methyl-7-diethyl amino coumarin, 1, two (the ethene, 1 of benzimidazolyl-2 radicals-yl) of 2-, 3-diphenylpyrazoline class, 2, the two (benzoxazoles of 5--2-yl) thiophene, 2-styryl naphtho-[1,2-d] oxazole, and 2-(stilbene-4-yl)-2H-naphtho-[1,2-d] triazole.Also see and authorized the United States Patent (USP) 3,646,015 of Hamilton on February 29th, 1972.Preferred anionic type whitening agent of the present invention.
Suds suppressor is used for reducing or suppresses the compound that foam forms can be spiked into the present composition.Suppress foam at for example United States Patent (USP) 4,489,455 and 4,489, possible particularly important in the what is called described in 574 " high density washing out method " and the European plan washing machine of feeding previously.
A variety of materials can be used as suds suppressor and use, and suds suppressor is well-known to those skilled in the art.For example see chemical encyclopedia (the Kirk OthmerEncyclopedia of Chemical Technology) third edition the 7th volume of KirlOthmer, 430-477 page or leaf (John Wiley ﹠amp; Sons, Inc., 1979).One class suds suppressor of particularly important comprises mono carboxylic lipid acid and soluble salt thereof.Referring to United States Patent (USP) 2,954,347 (September 27 nineteen sixty, Wayne St.John).The hydrocarbyl chain that mono carboxylic lipid acid that uses as suds suppressor and salt thereof have about 24 carbon atoms of 10-, preferred 12-18 carbon atom usually.Suitable salt comprises an alkali metal salt, for example sodium, potassium and lithium salts, and ammonium salt and alkanol ammonium salts.
Detergent composition of the present invention can also contain the nonsurfactant suds suppressor.This for example comprises: high-molecular weight hydro carbons such as paraffin, fatty acid ester (as fatty acid triglycercide), the fatty acid ester of monovalent alcohol, aliphatic C 18-C 40Ketone (as stearone) etc.Other suds suppressor comprises the alkylating aminotriazine of N-, for example contain three to six alkyl melamines or two that the reaction product of the uncle of 1-24 carbon atom or secondary amine forms to tetraalkyl diamines chlorination triazine as cyanuric chloride and two or three moles, propylene oxide, and phosphoric acid one stearyl ester is as a stearyl alcohol phosphoric acid ester and a stearyl two basic metal (as K, Na and Li) phosphoric acid salt and phosphoric acid ester.Hydro carbons such as paraffinic hydrocarbons or halogenation paraffinic hydrocarbons can use by liquid form.Liquid hydrocarbon is liquid under room temperature and normal pressure, and its pour point is being made an appointment with-40 ℃ to about 50 ℃ scope, and minimum boiling point is not less than about 110 ℃ (normal atmosphere).The also known waxy hydrocarbon that uses, preferred fusing point is lower than about 100 ℃.Hydro carbons constitutes the preferred detergent use suds suppressor of a class.The hydro carbons suds suppressor is authorized on May 5th, 1981 in the United States Patent (USP) 4,256,779 of Gandolfo etc. explanation.For example, these hydro carbons comprise the hydrocarbon of aliphatic series, alicyclic, aromatics and the saturated or undersaturated 12-70 of having an appointment the carbon atom of heterocyclic.It is to comprise the real paraffinic hydrocarbons and the mixture of cyclic hydrocarbon that " paraffinic hydrocarbons " speech looks like in about this discussion of suds suppressor.
Another kind of preferred on-surface-active formulation suds suppressor comprises the polysiloxane suds suppressor.Comprise in this class and use organopolysiloxane oil (for example polydimethylsiloxane), the dispersion of organopolysiloxane oil or resin or milk sap, and the two molectron of on silica dioxide granule, forming of organopolysiloxane chemisorption or fusion.The polysiloxane suds suppressor is well known in the art, in for example United States Patent (USP) 4,265,779 (Gandolfo etc., on May 5th, 1981) and european patent application 89307851.9 (Starch, M.S.1990 announced February 7) explanation is arranged.
United States Patent (USP) 3,455 has been mentioned other polysiloxane suds suppressor in 839, and this patent relates to and add composition and the method that a small amount of polydimethylsiloxane fluid comes froth breaking in the aqueous solution.
In German patent application DOS 2,124,526 for example, mentioned the mixture of the silicon-dioxide of polysiloxane and silanization.At United States Patent (USP) 3,933,672 (Bartolotta etc.) and United States Patent (USP) 4,652,392 disclose polysiloxane defoamers and the Foam Control in granular detergent composition in (Baginski etc., on March 24th, 1987).
A kind of example that is used for polysiloxane group suds suppressor of the present invention is the Foam Control that presses down bubble quantity, and it mainly contains:
Viscosity under (1) 25 ℃ is about the polydimethylsiloxane fluid of 20-1500 centipoise;
(2) (1) of per 100 weight parts silicone resin of having an appointment 5-50 part, this resin by ratio be about 0.6: 1 to about 1.2: 1 (CH 3) 3SiO 1/2Unit and SiO 2The unit is formed; With
(3) (1) of per 100 weight parts solid silicone of having an appointment 1-20 part.
In the preferred polysiloxane suds suppressor that the present invention uses, the solvent of external phase is made up of some polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers or its mixture (preferably) or polypropylene glycol.Main polysiloxane suds suppressor is a side chain/crosslinked, preferably is not straight chain.
For further specifying this point, have the typical liquid laundry detergent compositions of controlled foamy and randomly contain the 0.001-1% that has an appointment, preferred about 0.01-0 7%, the polysiloxane suds suppressor of 0.05-0.5% weight most preferably from about, the non-water emulsion that wherein contains (1) main defoamer, it is the mixture of following material: (a) a kind of organopolysiloxane, (b) polysiloxane compound of a kind of resinousness siloxanes or generation polyorganosiloxane resin, (c) finely divided filler, (d) a kind of catalyzer is so that promote component of mixture (a), (b) and (c) reaction forms silanol; (2) at least a non-ionic type polysiloxane surfactant; (3) under polyoxyethylene glycol or the room temperature in the water solubleness surpass the polyethylene/polypropylene glycol multipolymer of about 2% weight; Do not contain polypropylene glycol.In granular composition, gel etc., can use similar quantity.Also referring to United States Patent (USP) 4,978,471 (Starch, December 18 nineteen ninety) and 4,983,316 (Starch, on January 8th, 1991), 5,288,431 (Huber etc., on February 22nd, 1994) and United States Patent (USP) 4,639,489 and 4,749,740 (Aizawa etc.) walk to the 4th hurdle 35 row from first hurdle 46.
Polysiloxane suds suppressor of the present invention preferably contains polyoxyethylene glycol and polyethylene/polypropylene glycol multipolymer, and its molecular-weight average all less than about 1000, is preferably about 100-800.Among the present invention polyoxyethylene glycol and polyethylene/polypropylene glycol multipolymer at room temperature the solubleness in the water be preferably greater than about 5% weight greater than about 2% weight.
Preferred solvent is a molecular-weight average less than about 1000, more preferably about 100-800, the preferably polyoxyethylene glycol of 200-400, and polyethylene/polypropylene glycol multipolymer, preferably PPG200/PEG 300.Polyoxyethylene glycol: the weight ratio of polyethylene/polypropylene glycol multipolymer is preferably about 1: 1 to 1: 10, most preferably between 1: 3 and 1: 6.
The preferred polysiloxane suds suppressor that uses among the present invention does not contain polypropylene glycol, particularly the polypropylene glycol of molecular weight 4000.And preferably do not contain the segmented copolymer of oxyethane and propylene oxide, for example PLURONIC L 101.
Can be used for the mixture that other suds suppressor of the present invention comprises disclosed polysiloxane among secondary alcohol (as the 2-alkyl chain triacontanol) and it and silicone oil such as United States Patent (USP) 4,798,679,4,075,118 and the EP 150,872.This class secondary alcohol includes C 1-C 16The C of carbochain 6-C 16Alkyl alcohol.A kind of preferred alcohol is 2-butyl octanol, and it can be obtained by Condea company, and trade name ISOFOL 12.The secondary alcohol mixture can be obtained by Enichem, and trade name ISALCHEM 123.The mixed type suds suppressor contains the mixture that weight ratio is 1: 5 to 5: 1 a pure and mild polysiloxane usually.
For any detergent composition that will be used in the automatic washing machine, foam should not be formed into the degree that overflows washing machine.Suds suppressor in use, its consumption is preferably " inhibition bubble amt "." inhibition bubble amt " is meant that the makers-up of composition can select the quantity of this Foam Control, and this quantity is enough to control foam, is formed on the low foam detergent for washing clothes that uses in the automatic washing machine.
The present composition generally contains 0% to about 5% suds suppressor.When using as suds suppressor, the consumption of a carboxylic fatty acids and salt thereof generally reaches most about 5% of detergent composition weight.The preferred aliphatic monocarboxylate's suds suppressor that uses about 0.5%-3%.The consumption of polysiloxane suds suppressor mostly is the about 2% of detergent composition weight usually most, but also can use higher consumption.This upper limit is actually practicable, mainly is the efficient for consideration that reduces cost and the blistered lower amount of effective control.The preferred polysiloxane suds suppressor that uses about 0.01-1%, more preferably consumption is about 0.25-0.5%.These weight percent numerical value that use among the present invention comprise any silicon-dioxide that can be used in combination with organopolysiloxane, and any auxiliary that may use.The consumption of mono phosphoric acid ester stearyl ester suds suppressor is generally about 0.1-2% of composition weight.The consumption of hydro carbons suds suppressor is generally about 0.01-5%, but also can use higher consumption.The consumption of alcohols suds suppressor is generally the 0.2-3% of final product composition having weight.
The fabric softener that fabric softener various whens washing add, especially United States Patent (USP) 4,062,647 (Storm and Nirschl, on December 13rd, 1977) particle type terre verte and other softening agent clay known in the art, can be randomly use, so that the effect of fabric softener is provided when fabric cleans with the consumption of about 0.5-10% of being generally present composition weight.The clay softening agent can be as United States Patent (USP) 4,375, and 416 (Crisp etc., March 1 nineteen eighty-three) and United States Patent (USP) 4,291,071 (Harris etc., on September 22nd, 1981) are described, are used in combination with amine and cationic softener.
The dye transfer inhibitor present composition can also comprise for suppressing dyestuff transfers to effective one or more additional substancess on another fabric from a kind of fabric in cleaning process.In general, this class dye transfer inhibitor comprises polyvinyl pyrrolidone polymers, polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole multipolymer, manganese phthalocyanine, peroxidase and their mixture.If use, these reagent account for about 0.01-10% of composition weight usually, are preferably about 0.01-5%, more preferably about 0.05-2%.
More particularly, be preferred for the unit that polyamine N-oxide pllymers of the present invention includes following structural formula: R-A x-P; Wherein P is a polymerisable unit, and the N-O group can be connected or can constitute its part with it, and perhaps the N-O group can link with two unit; A is one of following structure :-NC (O)-,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; R is fat base, aromatic group, heterocyclic radical or the alicyclic radical of fat base, ethoxylation, or their any combination, and the nitrogen of N-O group can be connected with it or the N-O group is the part of these groups.R is a heterocyclic radical in the preferred polyamine N-oxide compound, for example pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines and derivative thereof.
The N-O base can be represented with following universal architecture formula:
Figure A9719610600561
R wherein 1, R 2And R 3Be aliphatic series, aromatics, heterocycle or alicyclic group, or their combination; X, y and z are 0 or 1; The nitrogen of N-O base can be connected or constitute its part with above-mentioned any group.The unitary pKa of the amine oxide of polyamine N-oxide＜10, preferred pKa＜7, more preferably pKa＜6.
Optional aggregation owner's chain all can utilize, as long as the amine oxide polymers that forms is water-soluble and have a performance that suppresses dye transfer.The example of suitable polymers main chain has polyethylene kind, polyalkenes hydro carbons, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and their mixture.These polymkeric substance comprise that wherein a class monomer is that amine n-oxide, another kind of monomer are the random or segmented copolymers of N-oxide compound.Common amine is 10: 1 to 1: 1000000 with the amine n-oxide ratio in the amine n-oxide polymkeric substance.But the number of the amine oxide group that exists in the polyamine oxide polymer can change by suitable copolymerization or suitable N-degree of oxidation.The polyamine oxide compound almost can obtain with any polymerization degree.Generally, molecular-weight average is 500-1,000,000, more preferably 1, and 000-500,000, most preferably be 5,000-100,000.The preferred material of this class can be described as " PVNO ".
The most preferred polyamine N-oxide that is suitable in the detergent composition of the present invention is poly-(4-vinylpridine-N-oxide compound), and its molecular-weight average is about 50,000, and amine is about 1: 4 with the ratio of amine n-oxide.
The multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole (being called " PVPVI " as a class) also is preferred for the present invention.The molecular-weight average of PVPVI is preferably 5,000-1, and 000,000, more preferably 5,000-200,000, most preferably be 10,000-20,000.(average molecular weight range is pressed Barth etc. and determine that with light scattering method the disclosed content of the document is quoted as a reference at this paper described in chemical analysis (Chemical Analysis) the 113rd volume " modernism of polymer characterization " (Modern Methods of Polymer Characterization)).The mol ratio of N-vinyl imidazole and N-vinyl pyrrolidone is generally 1: 1 to 0.2: 1 in the PVPVI multipolymer, more preferably 0.8: 1 to 0.3: 1, most preferably is 0.6: 1 to 0.4: 1.These multipolymers can be straight or brancheds.
The compounds of this invention can also use molecular-weight average to be about 5000-400, and 000, be preferably about 5000-200,000, the polyvinylpyrrolidone of about 5000-50000 (" PVP ") more preferably.PVP is that detergent applications is known to the skilled, for example sees EP-A-262,897 and EP-A-256,696, and they are all quoted as a reference at this paper.The composition that contains PVP also can contain molecular-weight average for about 500-100000, be preferably the polyoxyethylene glycol (" PEG ") of about 1000-10000.According to the ppm meter that discharges in washings, PEG is preferably about 2: 1 to about 50: 1, more preferably about 3: 1 to about 10: 1 with the ratio of PVP.
Detergent composition of the present invention can also contain the 0.005-5% weight of having an appointment some also have the inhibiting wetting ability white dyes of dye transfer.If use, the present composition preferably contains this white dyes of about 0.01-1% weight.
Can be used for wetting ability white dyes of the present invention and have following structural formula: R wherein 1Be selected from anilino, N-2-double hydroxyethyl and NH-2-hydroxyethyl; R 2Be selected from N-2-double hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chlorine and amino; M is salt-forming cation such as sodium or potassium.
R in above chemical formula 1Be anilino, R 2Be that N-2-double hydroxyethyl and M are positively charged ions for example during sodium, then whitening agent be 4,4 '-two ((4-anilino-6-(N-2-double hydroxyethyl)-S-triazine-2-yl) amino)-2,2 '-Stilbene disulfonic acid and disodium salt.This specific brightener species is by the trade name list marketing of Ciba-Geigy Corporation with Tinopal-UNPA-GX.Tinopal-UNPA-GX is the preferred wetting ability white dyes that can be used in the detergent composition of the present invention.
R in above chemical formula 1Be anilino, R 2Be that N-2-hydroxyethyl-N-2-methylamino-, M are positively charged ions for example during sodium, this whitening agent is 4,4 '-two ((4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-S-triazine 2-yl) amino) 2,2 '-the Stilbene disulfonic acid disodium salt.The specific brightener species of this kind is by the trade name list marketing of Ciba-Geigy Corporation with Tinopal 5BM-GX.
R in above chemical formula 1Be anilino, R 2Be morpholino, when M was positively charged ion such as sodium, this whitening agent was 4,4 '-two ((4-anilino-6-morpholino-S-triazine-2-yl) amino) 2,2 '-the Stilbene disulfonic acid, sodium salt.The specific brightener species of this kind is by the trade name list marketing of Ciba GeigyCorporation with Tinopal AMS-GX.
Selection is used for the present invention's the white dyes of these special kinds when being used in combination with selected aforementioned polymer dye transfer inhibitor, and providing especially effectively, dye transfer suppresses usefulness.This selected polymkeric substance (for example PVNO and/or PVPVI) is combined with selected white dyes (for example Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX), all obvious better dye transfer restraining effect when providing than any independent uses of these two kinds of detergent composition components in washing water liquid.Do not make deep theoretical discussion, but it is believed that this effect of these whitening agent is because they have high affinity to fabric in washings, therefore at a good pace be deposited on these fabrics.The degree that whitening agent is deposited in washings on the fabric can be with the parameter-definition that is referred to as " exhaustion coefficient ".Exhaust coefficient and generally be the whitening agent that is deposited on the fabric a) with washings in initial whitening agent concentration b) ratio.For the present invention, the whitening agent with higher exhaustion coefficient is optimum for suppressing dye transfer.
It will be appreciated, of course, that the compound that in the present composition, can randomly use conventional fluorescent brightening formulation so that the conventional fabric effect of " brightening " to be provided, rather than real dye transfer restraining effect.This purposes is that conventional purposes and washing composition formulation art are known.
Using method
Fabric and washings generally are to come in contact under stirring condition.Good for cleaning, stirring preferably is provided in washing machine.After the washing preferably in the clothes drying machine of routine with wet fabric drying.Liquid in the washing water liquid of washing machine or effective quantity of granular detergent composition are preferably about 500-7000ppm, more preferably from about 1000-3000ppm.
Embodiment I molecular-weight average is 1800 the ethoxylation that gathers (ethylenimine)
To one be equipped with the claisen head, with thermostat (Therm-O-Watch TM, I 2R) add poly-(ethylenimine) (Polysciences, 50.0 grams, 0.028 mole) of MW1800 in 250 of the thermometer of Xiang Lianing, spray tube and mechanical stirrer milliliters of 3 mouthfuls of flasks.Under argon atmospher and in about 140 ℃ of rapid down stirrings, add ethylene oxide gas (liquid Carbonics), up to weightening finish 52 grams (being equivalent to 1.2 ethoxy units) through scavenging duct.The material of a 50 this yellow gel shapes that restrain is preserved, added potassium hydroxide granule (Baker, 0.30 gram, 0.0053 mole) in the remaining material.After the potassium hydroxide dissolving, add oxyethane as described above, until weightening finish 60 grams (being equivalent to amount to 4.2 ethoxy units).This brown thick liquid of a 53 grams is preserved.In remaining material, add oxyethane as previously mentioned, reach 35.9 grams (being equivalent to amount to 7.1 ethoxy units), to obtain 94.9 gram Vandyke brown liquid until weightening finish.Potassium hydroxide in two duplicate samples of back is by adding the methylsulfonic acid neutralization of theoretical quantity.
Embodiment II PEI 1800 E 7Quaternized
In 500 milliliters of Erlenmeyer flasks that the magnetic splash bar is housed, add by ethoxylation to each nitrogen and have an appointment 7 inferior ethoxyls and advanced molecular weight 1800 polyethylene imine based of a modification (PEI 1800, E 7) (207.3 grams, 0.590 mole of nitrogen are pressed embodiment 1 preparation) and acetonitrile (120 gram).Under stirring fast, in solution, once add methyl-sulfate (28.3 grams, 0.224 mole), cover bottle, at room temperature stir and spend the night.Under about 60 ℃, remove acetonitrile with Rotary Evaporators, under about 80 ℃, further remove solvent with bulb formula distiller subsequently, obtain the quaternised material of the 220 desired parts of gram, be the Vandyke brown thick liquid.One duplicate samples of reaction product 13C-NMR (D 2O) stave bright～the 58ppm place does not exist and the corresponding carbon resonance of methyl-sulfate. 1HNMR (D 2O) the bright methylene radical adjacent of stave with not quaternised nitrogen in the resonance at about 2.5ppm place partial dislocation to about 3.0ppm.This nitrogen with about 38% takes place desired quaternized consistent.
Embodiment III PEI 1800 E 7The formation of hydrogenated amines
In 500 milliliters of Erlenmeyer flasks that the magnetic splash bar is housed, add molecular weight and be 1800 and ethoxylation to each nitrogen have an appointment polyethylene imine based (PEI-1800, the E of 7 oxyethyl groups 7) (209 grams, 0.595 mole of nitrogen are pressed embodiment 1 preparation) and hydrogen peroxide (120 grams, 30% weightaqueous solution, 1.06 moles).Bottle is built, after initial heat release, solution at room temperature stirred spend the night.The reaction mixture sample 1H-NMR (D 2O) stave is bright transforms fully.The resonance of the methene proton that cause links to each other with unoxidized nitrogen moves to about 3.5ppm by the original position of about 2.5ppm.In reaction soln, add the palladium/aluminum oxide granule of about 5 grams 0.5%, solution was at room temperature placed about 3 days.Check this solution, find the superoxide test paper is negative.The material that obtains like this should be stored as the aqueous solution of 51.1% actives.
Quaternized PEI 1800 E of embodiment IV 7The formation of amine oxide
In 500 milliliters of Erlenmeyer flasks that the magnetic splash bar is housed, add polyethylene imine based, hydrogen peroxide (48 grams, 30% weightaqueous solution, 0.423 mole) and water (～50 gram), this polyethylene imine based molecular weight is 1800, utilizes ethoxylation to each nitrogen 7 inferior ethoxyls of having an appointment to carry out modification (PEI 1800 E 7), use methyl-sulfate quaternized then again to about 38% further modification of quilt (preparation is with embodiment 1 for 130 grams ,～0.20 mole of oxidable nitrogen).Build flask, after initial heat release, solution at room temperature stirred and spend the night.Obtain by the sample of taking from reaction mixture 1H-NMR (D 2O) stave bright original in the 2.5-3.0ppm scope the observed resonance that belongs to methylene peak change into fully and have the material that chemical shift is about the methylene radical of 3.7ppm.In reaction soln, add about 5 gram 0.5%Pd/ oxidation aluminum shots, solution was at room temperature placed about 3 days.Check this solution, find the superoxide test paper is negative.38% the nitrogen of having obtained having an appointment is oxidized to the desired material of amine oxide by the nitrogen of quaternized and 62%, and it should be stored with the form of 44.9% the actives aqueous solution.
Quaternized PEI 1800 E of embodiment V 7Oxidation
Polyethylene imine based, the hydrogen peroxide (aqueous solution of 40 grams, 50% weight that in 500 milliliters of Erlenmeyer flasks that the magnetic splash bar is housed, add molecular weight 1800,0.588 mole) and water (109.4 restrain), this polyethylene imine basedly carries out modification (PEI 1800 E by ethoxylation to each nitrogen 7 inferior ethoxyls of having an appointment 7), use methyl-sulfate quaternized subsequently to about 4.7% (121.7 grams ,～0.32 mole of oxidable nitrogen).Build this flask, after initial heat release, solution at room temperature stirred spend the night.Obtain by a reaction mixture sample 1H-NMR (D 2O) methylene peak of spectrum indication at the 2.5-3.0ppm place moves to～3.5ppm.In reaction soln, add～5 gram 0.5%Pd/ oxidation aluminum shots, make solution at room temperature place～3 days.Check this solution, find the hydrogen peroxide test paper is negative.This has just obtained having～and 4.7% nitrogen is oxidized to the desired material of amine oxide by quaternized and nitrogen～95.3%, and it should be stored with the form of 46.5% aqueous solution.
Embodiment VI PEI 1800 E 7Quaternized
In 500 milliliters of Erlenmeyer flasks that the magnetic splash bar is housed, add molecular weight and be 1800 and ethoxylation degree be about polyethylene imine based (224 grams, 0.637 mole of nitrogen) and the acetonitrile (150 restrain 3.65 moles) of 7 modification.Once add methyl-sulfate (3.8 grams, 0.030 mole) under stirring fast, flask is built in solution, at room temperature stirred solution spends the night.Under about 60 ℃, remove acetonitrile with Rotary Evaporators.Further remove last trace solvent with the bulb distiller down at～80 ℃, obtain the desired material of about 220 grams, be the Vandyke brown thick liquid, wherein about 4.7% nitrogen is by quaternized. 13C-NMR (D 2O) there is not the resonance at about 58ppm place in the spectrum, shows that methyl-sulfate has consumed light. 1H-NMR (D 2O) resonance at the bright 2.5ppm of stave place (MU (methylene unit) that is connected with not quaternised nitrogen) partial dislocation to about 3.0ppm.
Below each table high density liquid detergent composition of the present invention has been described:
Embodiment VII-X
Weight %
Component VII VIII IX X
Poly-hydroxy coconut fatty acid acid amides ????3.65 ?3.50 ??????- ??????-
C 12-C 13Alcohol ethoxylate E 9 ????3.65 ?0.80 ??????- ??????-
C 12-C 15Alcohol sodium sulfate ????6.03 ?2.50 ??????- ??????-
C 12-C 15Alcohol ethoxylate (E 2.5) sodium sulfate ????9.29 ?15.10 ??????- ??????-
C 14-C 15Alcohol ethoxylate (E 2.25) sodium sulfate ?????- ???- ????18.00 ????18.00
Alkyl N-methyl glucose amide ?????- ???- ????4.50 ????4.50
C 10The amido propylamine ?????- ?1.30 ??????- ??????-
Citric acid ????2.44 ?3.00 ????3.00 ????3.00
Lipid acid (C 12-C 14) ????4.23 ?2.00 ????2.00 ????2.00
NEODOL23-9 1 ?????- ???- ????2.00 ????2.00
Ethanol ????3.00 ?2.81 ????3.40 ????3.40
Monoethanolamine ????1.50 ?0.75 ????1.00 ????1.00
Propylene glycol ????8.00 ?7.50 ????7.50 ????7.00
Boric acid ????3.50 ?3.50 ????3.50 ????3.50
Tetren ?????- ?1.18 ??????- ??????-
Toluenesulfonic acid sodium salt ????2.50 ?2.25 ????2.50 ????2.50
NaOH ????2.08 ?2.43 ????2.62 ????2.62
Subsidiary 2 ????1.60 ?1.30 ????0.27 ????0.27
The loomage surface modification polymkeric substance 3 ????0.50 ?0.50 ??????- ??????-
The loomage surface modification polymkeric substance 4 ?????- ???- ????2.00 ????1.00
Carezyme (5000 Cevu/g) enzyme ????0.05 ?0.05 ????0.05 ????0.05
Water 5 Surplus Surplus Surplus Surplus
1.E 9Ethoxylated alcohol is sold as Shell Oil Co..
2. subsidiary---comprise white dyes and enzyme (proteolytic enzyme, lipase, cellulase and amylase).
3. the polymkeric substance of embodiment 4.
4. the polymkeric substance of embodiment 1.
5. complement to 100%, for example can comprise subsidiary,, comprise CaCO as white dyes, spices, suds suppressor, dirt dispersant, proteolytic enzyme, lipase, sequestrant, dye transfer inhibitor, the water that adds in addition and filler 3, talcum, silicate etc.
Embodiment XI-X IV
Component XI XII X III X IV
C 14-C 15Alcohol ethoxylate (E 2.25) sodium sulfate ????13.00 ?????- ??- ????8.43
C 12-C 15Alcohol ethoxylate (E 2.5) sodium sulfate ?????- ????18.00 ?13.00 ?????-
C 12-C 13Linear alkylbenzene sulphonic acid ????9.86 ?????- ??- ????8.43
Lipid acid (C 12-C 14) ?????- ????2.00 ?2.00 ????2.95
C 12-C 13Alcohol ethoxylate ?????- ?????- ??- ????3.37
C 10The amido propylamine ?????- ?????- ?0.80 ?????-
NEODOL?23-9 1 ????2.22 ????2.00 ?1.60 ?????-
Alkyl N-methyl glucose amide ?????- ????5.00 ?2.50 ?????-
Citric acid ????7.10 ????3.00 ?3.00 ????3.37
Ethanol ????1.92 ????3.52 ?3.41 ????1.47
Monoethanolamine ????0.71 ????1.09 ?1.00 ????1.05
Propylene glycol ????4.86 ????8.00 ?6.51 ????6.00
Boric acid ????2.22 ????3.30 ?2.50 ?????-
The tetren of ethoxylation ????1.18 ????1.18 ??- ????1.48
The isopropyl benzene sodium sulfonate ????1.80 ????3.00 ??- ????3.00
Toluenesulfonic acid sodium salt ?????- ?????- ?2.50 ?????-
NaOH ????6.60 ????2.82 ?2.90 ????2.10
Dodecyltrimethyl ammonium chloride ?????- ?????- ??- ????0.51
List and disuccinic acid tartrate sodium salt ?????- ?????- ??- ????3.37
Sodium formiate ?????- ?????- ??- ????0.32
White dyes ????1.60 ????1.80 ?2.00 ????1.60
The fabric-modifying polymkeric substance 2 ????0.50 ????2.00 ??- ?????-
The fabric-modifying polymkeric substance 3 ????1.50 ?????- ?2.00 ????3.00
Endolase enzyme (5000 Cevu/g) ????0.1 ????0.1 ?0.5 ????0.2
The detergency polymkeric substance ?????- ????1.15 ??- ????1.50
Water 5 Surplus Surplus Surplus Surplus
1.E 9Ethoxylated alcohol is sold as Shell Oil Co..
2. the polymkeric substance of embodiment 4.
3. the polymkeric substance of embodiment 1.
4. complement to 100%, for example can comprise subsidiary,, comprise CaCO as spices, suds suppressor, dirt dispersant, proteolytic enzyme, lipase, amylase, sequestrant, dye transfer inhibitor, the water of adding and filler 3, talcum, silicate etc.
Embodiment X V-XI X
Component X V X VI X VII X VIII XI X
Poly-hydroxy coconut fatty acid acid amides 3.50 ?3.50 ?3.15 ?3.50 ?3.00
NEODOL?23-9 1 2.00 ?0.60 ?2.00 ?0.60 ?0.60
C 25Alkyl ethoxylate sulfate 19.00 ?19.40 ?19.00 ?17.40 ?14.00
C 25Alkyl-sulphate ?- ??- ??- ?2.85 ?2.30
C 10-amino propionic acid amide ?- ??- ??- ?0.75 ?0.50
Citric acid 3.00 ?3.00 ?3.00 ?3.00 ?3.00
Tallow fatty acid 2.00 ?2.00 ?2.00 ?2.00 ?2.00
Ethanol 3.41 ?3.47 ?3.34 ?3.59 ?2.93
Propylene glycol 6.22 ?6.35 ?6.21 ?6.56 ?5.75
Single carbinolamine 1.00 ?0.50 ?0.50 ?0.50 ?0.50
Sodium hydroxide 3.05 ?2.40 ?2.40 ?2.40 ?2.40
Paratoluenesulfonic acid sodium salt 2.50 ?2.25 ?2.25 ?2.25 ?2.25
Borax 2.50 ?2.50 ?2.50 ?2.50 ?2.50
Proteolytic enzyme 2 0.88 ?0.88 ?0.88 ?0.88 ?0.88
Lipase 3 0.04 ?0.12 ?0.12 ?0.12 ?0.12
Duramyl 4 0.10 ?0.10 ?0.10 ?0.10 ?0.40
The CAREZYME cellulase 0.053 ?0.053 ?0.053 ?0.053 ?0.053
White dyes 0.15 ?0.15 ?0.15 ?0.15 ?0.15
The agent of polyamine loomage surface modification 5 1.18 ?1.18 ?1.18 ?1.18 ?1.75
The silicon-dioxide of smoking 0.119 ?0.119 ?0.119 ?0.119 ?0.119
Subsidiary beautifies articles for use, water Surplus Surplus Surplus Surplus Surplus
1.C 12-C 13Alkyl E9 ethoxylate is sold as Shell Oil Co..
2. the bacillus amyloliquefaciens subtilisin that is entitled as the U.S. Patent application 08/322,676 of " cleaning combination that contains proteolytic enzyme " according to A.Baeck etc.
3. plant mould deriving by the fetal hair corruption and form, can buy by Novo.
4. be disclosed in WO 9510603A, can buy by Novo.
5. the polymkeric substance of embodiment 4.
Embodiment XX-XX III
Liquid laundry detergent compositions
Component XXX XI X XII XX III
C 12-C 15Alkyl-sulphate ?????- ?????- ?????- ?????-
C 12-C 15Alkyl ethoxylated sulfate ????18.0 ????16.0 ????18.0 ????16.0
C 12-C 14The N-methyl glucose amide ????4.5 ????3.1 ????4.5 ????3.1
C 12-C 14Fatty alcohol ethoxylate ????2.0 ????1.0 ????2.0 ????1.0
C 12-C 16Lipid acid ????2.0 ????2.0 ????2.0 ????2.0
Citric acid (anhydrous) ????3.0 ????2.5 ????3.0 ????2.5
Monoethanolamine ????0.0 ????0.75 ????0.0 ????0.75
Propylene glycol ????0.0 ????5.1 ????0.0 ????5.1
NaOH ????2.93 ????2.9 ????2.93 ????2.9
Ethanol ????3.52 ????2.88 ????3.52 ????2.88
Proteolytic enzyme, lipase, amylase ????1.25 ????0.7 ????1.25 ????0.7
The detergency polymkeric substance ????0.2 ????1.18 ????0.2 ????1.18
Sodium formiate ????0.093 ????0.058 ????0.093 ????0.058
Boric acid ????3.5 ????2.5 ????3.5 ????2.5
The polysiloxane suds suppressor ????0.119 ????0.085 ????0.119 ????0.085
Carezyme(5000?CEVU/g) ????0.05 ?????- ????1.0 ?????-
Endolase(5000?CEVU/g) ?????- ????0.2 ?????- ????0.1
PEI?1800?E7 1 ????2.0 ????2.0 ????2.0 ????2.0
The TinopalUNPA-GX whitening agent ????0.05 ?????- ????0.05 ?????-
Water and auxiliary Surplus Surplus Surplus Surplus
1. fabric face modifying agent.

Claims (17)

1. detergent composition, wherein contain:
A) a kind of detersive surfactant of at least 0.1% weight;
B) cellulase of at least 0.001% weight; With
C) the polyamine loomage surface modification agent of a kind of water-soluble or dispersible modification of water of at least 0.05% weight, this reagent contain one and the corresponding polyamine main chain of following chemical formula:
Figure A9719610600021
Polyamine chemical formula V with modification (n+1)W mY nZ, or contain one and the corresponding polyamine main chain of following chemical formula:
Figure A9719610600022
Polyamine chemical formula V with modification (n-k+l)W mY nY ' kZ, wherein k is less than or equal to n, and the molecular weight of described polyamine main chain before modification is greater than 200 dalton, wherein
ⅰ) the V unit is the following terminal units of chemical formula:
Figure A9719610600023
ⅱ) the W unit is the following backbone units of chemical formula:
Figure A9719610600024
ⅲ) the Y unit is the following chain unit of chemical formula:
Figure A9719610600031
ⅳ) the Z unit is the following terminal units of chemical formula:
Figure A9719610600032
Wherein main chain connector element R is selected from C 2-C 12Alkylidene group, C 4-C 12Alkylene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy, C 8-C 12The dialkyl group arylidene ,-(R 1O) xR 1-,-(R 1O) xR 5(OR 1) x-,-(CH 2CH (OR 2) CH 2O) z-(R 1O) yR 1(OCH 2CH (OR 2) CH 2) w-,-C (O) (R 4) rC (O)-,-CH 2CH (OR 2) CH 2-, and their mixture; R wherein 1Be C 2-C 6Alkylidene group and composition thereof; R 2Be hydrogen ,-(R 1O) xB and composition thereof; R 3Be C 1-C 18Alkyl, C 7-C 12Aralkyl, C 7-C 12The aryl that alkyl replaces, C 6-C 12Aryl, and their mixture; R 4Be C 1-C 12Alkylidene group, C 4-C 12Alkylene group, C 8-C 12Aryl alkylene, C 6-C 10Arylidene and their mixture; R 5Be C 1-C 12Alkylidene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy, C 8-C 12The dialkyl group arylidene ,-C (O)-,-C (O) NHR 6NHC (O)-,-R 1(OR 1)-,-C (O) (R 4) rC (O)-,-CH 2CH (OH) CH 2-,-CH 2CH (OH) CH 2O (R 1O) yR 1-OCH 2CH (OH) CH 2-, and their mixture; R 6Be C 2-C 12Alkylidene group or C 6-C 12Arylidene; The E unit is to be selected from hydrogen, C 1-C 22Alkyl, C 3-C 22Alkenyl, C 7-C 22Aralkyl, C 2-C 22Hydroxyalkyl ,-(CH 2) pCO 2M ,-(CH 2) qSO 3M ,-CH (CH 2CO 2M)-CO 2M ,-(CH 2) pPO 3M ,-(R 1O) xB ,-C (O) R 3And their mixture; Condition is that when any E unit of nitrogen-atoms was hydrogen, this nitrogen-atoms was not the N-oxide compound simultaneously; B is a hydrogen, C 1-C 6Alkyl ,-(CH 2) q-SO 3M ,-(CH 2) pCO 2M ,-(CH 2) q(CHSO 3M) CH 2SO 3M ,-(CH 2) q(CHSO 2M) CH 2SO 3M ,-(CH 2) pPO 3M ,-PO 3M, and their mixture; M is a kind of water-soluble cationic that hydrogen or quantity are enough to satisfy charge balance; X is a water soluble anion; The value of m is 4-400; The value of n is 0-200; The value of p is 1-6; The value of q is 0-6; The value of r is 0 or 1; W is 0 or 1; X is 1-100; Y is 0-100; Z is 0 or 1.
2. the composition of claim 1, wherein said composition also contains the auxiliary composition, is selected from washing assistant, white dyes, SYNTHETIC OPTICAL WHITNER, bleach boosters, bleach-activating agent, non-cellulose enzyme enzyme, enzyme activator, suds suppressor, dyestuff, spices, tinting material, filling salt, hydrotropic agent and their mixture.
3. the composition of claim 1, wherein R is C 2-C 12Alkylidene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy, C 8-C 12The dialkyl group arylidene ,-(R 1O) xR 1-,-(R 1O) xR 5(OR 1) x-,-(CH 2CH (OH) CH 2O) z(R 1O) yR 1-(OCH 2CH (OH) CH 2) w-,-CH 2CH (OR 2) CH 2-, and their mixture.
4. the composition of claim 3, wherein R is C 2-C 12Alkylidene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy ,-(R 1O) xR 1-,-(R 1O) xR 5(OR 1) x-,-(CH 2CH (OH) CH 2O) z(R 1O) yR 1(OCH 2CH (OH) CH 2) w-, and their mixture.
5. the composition of claim 4, wherein R is C 2-C 12Alkylidene group, C 3-hydroxy alkylidene and their mixture.
6. the composition of claim 5, wherein R is C 2-C 12Alkylidene group, preferred C 2-C 6Alkylidene group.
7. the composition of claim 1, wherein R 1At least 50% is ethylidene, R 2Be hydrogen.
8. the composition of claim 1, wherein R 3Be C 1-C 12Alkyl, C 7-C 12Alkyl arylene and their mixture.Preferred R 3Be C 1-C 12Alkyl and composition thereof, more preferably R 3Be C 1-C 6Alkyl and composition thereof.
9. the composition of claim 1, wherein R 4Be C 2-C 12Alkylidene group, C 8-C 12Aryl alkylene and their mixture, preferred R 4Be C 2-C 6Alkylidene group and composition thereof.
10. the composition of claim 1, wherein R 5Be ethylidene ,-C (O)-,-C (O) NHR 6NHC (O)-,-R 1(OR 1) y-,-(CH 2CH (OH) CH 2O) z(R 1O) yR 1-(OCH 2CH (OH) CH 2) w-,-CH 2CH (OH) CH 2-and their mixture, preferred R 5Be-CH 2CH (OH) CH 2-.
11. the composition of claim 1 wherein contains the polyamine loomage surface modification agent of modification, wherein the E unit is to be selected from hydrogen, C 3-C 22Hydroxyalkyl, benzyl, C 1-C 22Alkyl ,-(R 1O) xB ,-C (O) R 3,-(CH 2) pCO 2 -M +,-(CH 2) qSO 3 -M +,-CH (CH 2CO 2M) CO 2M and their mixture are preferably hydrogen, C 1-C 22Alkyl ,-(R 1O) xB ,-C (O) R 3With their mixture.
12. the composition of claim 11, wherein the B unit is hydrogen, C 1-C 6Alkyl ,-(CH 2) qSO 3M ,-(CH 2) q(CHSO 3M) CH 2SO 3M ,-(CH 2) q(CHSO 2M)-CH 2SO 3M, and their mixture, wherein q is 0-3; Preferred B be hydrogen ,-(CH 2) qSO 3M and their mixture, wherein q is 0-3.
13. the composition of claim 1, detersive surfactant wherein is a kind of aniorfic surfactant that is selected from alkyl alkoxy sulfate, alkyl-sulphate and their mixture, and preferably this detersive surfactant is a kind of nonionic surface active agent that is selected from the fatty acid amide and composition thereof of alkyl alkoxylates, following chemical formula:
Figure A9719610600051
R wherein 7Be C 7-C 22Alkyl, R 8Be independently selected from hydrogen, C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl ,-(C 2H 4O) jH and composition thereof, wherein j is 1-3.
Rottenly plant mould, grey corruption and plant the hepatopancreas of mould thermoidea mutation, genus bacillus, Aeromonas, sea mollusk DolabellaAuricula Solander and the cellulase that their mixture is derived and formed 14. the composition of claim 1, wherein said cellulase are selected from by unusual.
15. the liquid laundry detergent compositions with modified fabric effect wherein contains:
A) at least 10% weight is selected from a kind of detersive surfactant of anionic and non-ionic type detersive surfactant;
B) a kind of cellulase of 0.05-2% weight;
C) the polyamine loomage surface modification agent of the water-soluble or water-dispersible modification of 0.5-10% weight, this reagent contains the polyamine main chain corresponding to following chemical formula:
Figure A9719610600052
Has modified polyamine chemical formula V (n+1)W mY nZ, or contain polyamine main chain corresponding to following chemical formula:
Figure A9719610600053
Has modified polyamine chemical formula V (n-k+l)W mY nY ' kZ, wherein k is less than or equal to n, and the molecular weight of described polyamine main chain before modification is greater than 200 dalton, wherein
ⅰ) the V unit is the following terminal units of chemical formula:
ⅱ) the W unit is the following backbone units of chemical formula:
Figure A9719610600062
ⅲ) the Y unit is the following chain unit of chemical formula:
ⅳ) the Z unit is the following terminal units of chemical formula: Wherein main chain connector element R is selected from C 2-C 12Alkylidene group, C 4-C 12Alkylene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy, C 8-C 12The dialkyl group arylidene ,-(R 1O) xR 1-,-(R 1O) xR 5(OR 1) x-,-(CH 2CH (OR 2) CH 2O) z-(R 1O) yR 1(OCH 2CH (OR 2) CH 2) w-,-C (O) (R 4) rC (O)-,-CH 2CH (OR 2) CH 2-and their mixture; R wherein 1Be C 2-C 6Alkylidene group and composition thereof; R 2Be hydrogen ,-(R 1O) xB and their mixture; R 3Be C 1-C 18Alkyl, C 7-C 12Aralkyl, C 7-C 12The aryl that alkyl replaces, C 6-C 12Aryl, and their mixture; R 4Be C 1-C 12Alkylidene group, C 4-C 12Alkylene group, C 8-C 12Aryl alkylene, C 6-C 10Arylidene, and their mixture; R 5Be C 1-C 12Alkylidene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy, C 8-C 12The dialkyl group arylidene ,-C (O)-,-C (O) NHR 6NHC (O)-,-R 1(OR 1)-,-C (O) (R 4) rC (O)-,-CH 2CH (OH) CH 2-,-CH 2CH (OH) CH 2O (R 1O) yR 1-OCH 2CH (OH) CH 2-, and their mixture; R 6Be C 2-C 12Alkylidene group or C 6-C 12Arylidene; The E unit is to be selected from hydrogen, C 1-C 22Alkyl, C 3-C 22Alkenyl, C 7-C 22Arylalkyl, C 2-C 22Hydroxyalkyl ,-(CH 2) pCO 2M ,-(CH 2) qSO 3M ,-CH (CH 2CO 2M)-CO 2M ,-(CH 2) pPO 3M ,-(R 1O) xB ,-C (O) R 3, and their mixture; Condition is that if any E unit of certain nitrogen-atoms is a hydrogen, then this nitrogen is not the N-oxide compound simultaneously; B is a hydrogen, C 1-C 6Alkyl ,-(CH 2) q-SO 3M ,-(CH 2) pCO 2M ,-(CH 2) q(CHSO 3M) CH 2SO 3M ,-(CH 2) q-(CHSO 2M) CH 2SO 3M ,-(CH 2) pPO 3M ,-PO 3M, and their mixture; M is the water-soluble cationic that hydrogen or quantity are enough to satisfy charge balance; X is a water soluble anion; The value of m is 4-400; The value of n is 0-200; The value of p is 1-6; The value of q is 0-6; The value of r is 0 or 1; W is 0 or 1; The value of x is 1-100; The value of y is 0-100; Z is 0 or 1; With
D) enough alkaline matter, so that when composition is measured by 10% aqueous solution, pH is 7-9.5.
16. the method for an improvement fabric face during doing washing, this method comprises makes fabric face contact with the detergent for washing clothes aqueous solution of claim 1.
17. the washing of a fabric that is used to contain the balling-up fiber and go the method for balling-up, this method comprise that the wash water solution that the fabric that makes balling-up and detergent composition with the claim 1 of effective quantity form contacts.
CN 97196106 1996-05-03 1997-04-25 Detergent compositions comprising modified polyamine polymers and cellulase Pending CN1224456A (en)

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