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CN1104488C - Detergent compositions having suds suppressing properties - Google Patents

Detergent compositions having suds suppressing properties Download PDF

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Publication number
CN1104488C
CN1104488C CN95194695A CN95194695A CN1104488C CN 1104488 C CN1104488 C CN 1104488C CN 95194695 A CN95194695 A CN 95194695A CN 95194695 A CN95194695 A CN 95194695A CN 1104488 C CN1104488 C CN 1104488C
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acid
alkyl
suds suppressor
carbon atom
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CN1155899A (en
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R·T·哈茨霍恩
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Procter and Gamble Co
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Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides

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

Abstract

A detergent composition formulated with conventional detersive surfactants, optional builders, detergent adjuncts and a suds suppressor, wherein said suds suppressor is an amino acid of formula (I), or its alkali metal, alkaline earth metal salt or mixtures thereof, wherein R1 is an alkyl, aryl or alkaryl group containing from 1 to 14 carbon atoms, R2 is an alkylene, arylene or alkarylene group containing from 1 to 14 carbon atoms, R5 is H or an alkyl, aryl, or alkaryl group containing from 1 to 10 carbon atoms. The invention also relates to a detergent composition comprising a mixture of amidoacid and amidoperacid suds suppressors and to an aqueous wash liquor containing a detersive surfactant comprising a C10-C20 alkyl sulphate, optionally together with builders and detergent adjuncts and a suds suppressor compound wherein said suds suppressor is formed from a suds suppressor precursor.

Description

Detergent composition with suds suppressing properties
Invention field
The present invention relates to have the detergent composition of suds suppressing properties.More specifically, the present invention relates to novel suds suppressor compound.
Background of invention
Known the detergent composition that contains high level of surfactant in the art.For example negatively charged ion, nonionic or cats product help to get on except that the dirt suspension on grease and the maintenance fabric from fabric to require tensio-active agent.More specifically, need high-load anion surfactant to keep pure white.Yet when using some high-load tensio-active agents, when particularly using the big anion surfactant of gas release, the problem that is run into is that tensio-active agent produces a large amount of foamy characteristics; Particularly at high temperature, this problem is even more serious.
Traditionally, use high-load suds suppressor for example silicone, fatty acid and twin chain alcohols suds suppressor inhibition foam always.Yet the problem that this usage ran into is that their expense costliness does not but almost have cleaning function.
The precursor of also knowing peracid is used for bleaching more effective.Hydrophobicity bleach precursor nonanoyl phenolsulfonate (NOBS) for example especially effectively, it produces fatty acid by-products in washings.Yet under the high-temperature wash condition, be invalid with its control foam.
In US SN 08/064,563 and EP 0170386, narrated at another kind of hydrophobicity bleach precursor known in the art.US SN 08/064,563 have spoken of for example mixture of (6-decoylamide hexanoyl) phenolsulfonate, (6-pelargonamide hexanoyl) phenolsulfonate, (6-decyl amide hexanoyl) phenolsulfonate and they and enzyme compatibility of acid amides peralcohol and precursor thereof, and this kind of enzyme has bleaching detergent and enzymic detergency ability.It discloses the detergent composition that contains the nil-LAS tensio-active agent, and speaks of and can use for example TAED preparation acid amides peralcohol of wetting ability activator.EP 0170386 speaks of acid amides peralcohol and the precursor thereof in peroxide bleaching compositions, and they play effective bleaching action to textiles in very wide temperature range.
Have now found that, for example can also further strengthen suds suppressing properties at acid amides peralcohol described in US SN 08/064,563 and the EP 0170386 and precursor thereof.
Find that in addition the amido acid compounds has suds suppressing properties.
The purpose of this invention is to provide a kind of detergent composition, wherein comprise and be selected from the novel suds suppressor compound that amido acid and amido acid and acid amides are crossed acid mixture.
Another object of the present invention provides and contains detersive surfactant, wherein comprises C 10-C 20Alkyl sulfuric ester salt, optional washing assistant, the water-washing liquid of detergent additive and suds suppressor, wherein said suds suppressor is generated by the suds suppressor precursor.
Summary of the invention
The present invention includes the detergent composition of preparing with common detersive surfactant, optional washing assistant, detergent additive and suds suppressor, wherein said suds suppressor is that general formula is Amido acid or its basic metal, alkaline-earth metal salt or their mixture, R in the formula 1Be alkyl, aryl or the alkaryl that contains 1-14 carbon atom, R 2Be alkylidene group, arylidene or the alkyl arylene that contains 1-14 carbon atom, R 5Be H or alkyl, aryl or the alkaryl that contains 1-10 carbon atom.
Detailed Description Of The Invention
The object of the present invention is to provide detergent composition with suds suppressing properties.
Being used for main component of the present invention is the suds suppressor compound of detergent composition, said composition is to be prepared by common detersive surfactant, optional washing assistant, detergent additive, and wherein said suds suppressor is selected from the mixture of amido acid and amido acid and acid amides peracid.
The content of described tensio-active agent in detergent composition is generally the 1%-80% (weight) of detergent composition and the content of described suds suppressor is the 0.025%-20% (weight) of detergent composition.
Described compound, promptly the mixture of amido acid and amido acid and acid amides peracid demonstrates fabulous suds suppressing properties, and can be used as " decontamination active (detergent acfive) " suds suppressor or be used as collaborative suds suppressor.
So-called " decontamination is active " is meant except that the bubble of pressing down activity is arranged, and whether no matter have under the situation of SYNTHETIC OPTICAL WHITNER existence, the mixture of amido acid or amido acid and acid amides peracid all has bleaching activity.
When making collaborative suds suppressor with it, the detergent composition of being developed has two advantages: the first, strengthened the suds suppressing properties of detergent composition.The second, can use the expensive suds suppressor that is lower than general content, for example silicone, lipid acid, twin chain alcohol, thus reduced the cost of product.In addition; by the mixture deutero-organic peroxide acid SYNTHETIC OPTICAL WHITNER of perhydrate and precursor or ready-formed peracid for example in the presence of acid amides peracid or the diperacid; the detergent composition of being developed still keeps its suds suppressing properties, and wherein said precursor for example TEAD, NOBS, acyl lactam and cation precursor contains one or more N-acyl groups or O-acyl group.
Since the existence of this class peroxyacid bleach, the feasible bleaching action that might use the most widely spot.And, amido acid and amido acid use with tensio-active agent with the mixture of acid amides peracid, demonstrate good pressing down and steep activity, tensio-active agent is selected from negatively charged ion, positively charged ion, nonionic both sexes, (soda acid) both sexes and zwitterionics and composition thereof.Particularly preferred tensio-active agent is selected from negatively charged ion, nonionic, cats product and composition thereof.For a large amount of foams that produced by tensio-active agent that reduce, most preferred tensio-active agent is the nil-LAS tensio-active agent.
The main component that is used to produce suds suppressing properties is that general formula is Amido acid or its basic metal, alkaline-earth metal salt or its mixture, R in the formula 1Be alkyl, aryl or the alkaryl that contains 1-14 carbon atom, R 2Be alkylidene group, arylidene or the alkyl arylene that contains 1-14 carbon atom, R 5Be H or alkyl, aryl or the alkaryl that contains 1-10 carbon atom.
Being used for another kind of suds suppressor composition of the present invention is that above-mentioned amido acid and general formula is
Figure C9519469500082
Mixture or its basic metal, alkaline-earth metal salt or its mixture of acid amides peracid, R in the formula 1Be alkyl, aryl or the alkaryl that contains 1-14 carbon atom, R 2Be alkylidene group, arylidene or the alkyl arylene that contains 1-14 carbon atom, R 5Be H or alkyl, aryl or the alkaryl that contains 1-10 carbon atom.
Preferred suds suppressor, for example mentioned above, be R in the formula 1For containing the alkyl of 6-12 carbon atom, R 2Contain 1-8 carbon atom, and R 5Be some compounds of H or methyl.Particularly preferred suds suppressor is in the above-mentioned general formula, R 1Be the alkyl that contains 7-10 carbon atom, and R 2Be some compounds that contain 4-5 carbon atom.
The add-on of described suds suppressor in detergent composition is generally the 0.025%-20% (weight) of composition, is preferably 0.05%-15%, 0.06%-12% more preferably, and most preferably be 0.06%-7%.
Can adopt the detergent composition of described suds suppressor to comprise and be used to wash for example composition of fabric, fiber, crust, skin etc. of matrix; The for example detergent composition of the composition of washed hardened surface (containing or do not contain abrasive), laundry usefulness, the automatic and manual dish composition of washing. The suds suppressor precursor
Another aspect of the present invention comprises and contains detersive surfactant, wherein comprises C 10-C 20Alkyl sulfuric ester salt, the water-washing liquid of optional washing assistant, detergent additive and suds suppressor compound, wherein said suds suppressor are to be by general formula Suds suppressor precursor or its mixture generate R in the formula 1Be alkyl, aryl or the alkaryl that contains 1-14 carbon atom, R 2Be alkylidene group, arylidene or the alkyl arylene that contains 1-14 carbon atom, R 5Be that H or alkyl, aryl or the alkaryl that contains 1-10 carbon atom and L are leavings groups.
L can be arbitrary suitable leavings group basically.Leavings group is the arbitrary group that cements out from the suds suppressor precursor because the suds suppressor precursor is subjected to the anionic nucleophillic attack of hydrogen peroxide.This peroxidation hydrogenolysis (perhydrolysis) reaction causes the generation of percarboxylic acids suds suppressor.Also competing reaction, i.e. hydrolysis reaction may take place.This hydrolysis reaction causes the generation of carboxylic acid suds suppressor.Under the situation that does not have the hydrogen peroxide negatively charged ion to exist, nucleophillic attack is undertaken by hydroxide anion, and is identical with above-mentioned competing reaction, and what taken place is hydrolysis reaction.This causes the generation of carboxylic acid suds suppressor.For suitable leavings group, must have the effect that attracts electronics usually.It also should form a kind of stable compound, so that the speed of reversed reaction can be ignored.This helps the hydrogen peroxide negatively charged ion or hydroxide anion carries out nucleophillic attack.The L group must have enough activity to the reaction that takes place in the best time limit (for example wash(ing)cycle).Yet if L is too active, this precursor will be difficult to stablize in detergent composition.Usually utilize the pKa of leavings group conjugate acid to make these characteristics synchronous.Although known this convention also has exception.The leavings group that presents this behavior, normally conjugate acid pKa wherein is the group of 4-13, is preferably 6-11 and most preferably is 8-11.
Preferred suds suppressor precursor is the compound in the above-mentioned general formula, and the definition of R1, R2 and R5 and suds suppressor (amido acid and acid amides peracid) is identical in the formula, and L then is selected from: And composition thereof, R1 is alkyl, aryl or the alkaryl that contains 1-14 carbon atom in the formula, and R3 is the alkyl group that contains 1-8 carbon atom, and R4 is that H or R3 and Y are H or solubilizing group.
Preferred solubilizing group is-SO 3 -M +,-CO 2 -M +,-SO 4 -M +,-N +(R3) 4X -And O＜--N (R3) 3, and most preferably-SO 3 -M +With-CO 2 -M +, R3 is the alkyl group that contains 1-4 carbon atom in the formula, M is that the positively charged ion and the X that make the suds suppressor precursor have solubility make the suds suppressor precursor have the negatively charged ion of solubility.Preferred M is the positively charged ion of the ammonium of basic metal, ammonium or replacement, and most preferably sodium and potassium and preferred X are halogenide, oxyhydroxide, methylsulfuric acid ester salt or acetate negatively charged ion.Should be noted that dissolving, they are dispersed in the detergent composition well for the suds suppressor precursor that helps to have the leavings group that does not contain solubilizing group.Preferred suds suppressor precursor is the compound with above-mentioned general formula, and wherein L is selected from The definition of R3 is with above-mentioned identical in the formula, and Y is-and SO 3 -M +Or-CO 2 -M +, wherein the definition of M is with above-mentioned identical.Preferred L has following general formula:
Figure C9519469500112
The content of suds suppressor precursor defined above is at least 0.1% (weight) of detergent composition, is preferably 0.1%-50%, and more preferably 0.2%-30% most preferably is 0.5%-25%.
Another embodiment of the invention is to add other suds suppressor and/or detersive surfactant in detergent composition of the present invention.
With detergent composition of the present invention with additional suds suppressor hereinafter described ' silicone ' and anion surfactant when using for example, described anion surfactant is preferably at least 10 to 1 with the ratio of described silicone, and more preferably at least 15 to 1.In addition, if anion surfactant is an alkyl sulfuric ester salt, preferred described alkyl sulfuric ester salt is at least 20 to 1 with the ratio of described silicone. Additional phase infusion
Can adopt various material well-known to those skilled in the art as additional or collaborative suds suppressor.For example, see chemical technology encyclopaedia that Ke Keaosimo shows, the third edition the 7th volume, 430-447 page or leaf (John Wiley in 1979; Sons, Inc.).A significant especially class suds suppressor comprises monobasic aliphatic carboxylic acid and solubility salt wherein.See and be presented to Wei grace St. John's's United States Patent (USP) 2,954,347 September 27 nineteen sixty.As the monobasic aliphatic carboxylic acid of suds suppressor and the chain alkylene that its esters contains 10-24 carbon atom usually, preferably contain 12-18 carbon atom.Suitable salt comprises alkaline metal salt for example sodium, potassium and lithium salts class and ammonium and alkanol ammonium salt.
The detergent composition of this paper also can contain the nonsurfactant suds suppressor.They for example comprise high-molecular weight hydro carbons for example paraffinic hydrocarbons, fatty acid ester (for example, fatty acid triglyceride), the fatty acid ester of monovalent alcohol, C 18-C 40Aliphatic ketone (for example stearone) etc.Other suds suppressor comprises the alkylating aminotriazine of N-, for example three or six alkyl melamines or contain two-tetraalkyl diammonium chloride triazine, propylene oxide and a stearyl phosphoric acid salt that the product of the primary amine of 1-24 carbon atom or secondary amine generates for example stearyl alcohol phosphate ester salt, a stearyl two basic metal (for example K, Na and Li) phosphoric acid salt and phosphates as cyanuric chloride and 2-3 mole.Hydro carbons for example paraffinic hydrocarbons and halogenated paraffin can be used with liquid form.Liquefied hydrocarbon is in a liquid state under room temperature and normal atmosphere, and its pour point is-40 ℃-50 ℃, and minimum boiling point is not less than 110 ℃ (under atmospheric pressure).Also known use napalite, preferred fusing point is lower than 100 ℃ napalite.This class hydrocarbon constitutes the preferred detergent composition suds suppressor of a class.For example in being presented to people's such as sweet Dorr richness United States Patent (USP) 4,265,779 on May 5th, 1981, narrated the hydro carbons suds suppressor.This hydro carbons comprises aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbons and heterocycle stable hydrocarbon or the unsaturated hydrocarbons that contains 12-70 carbon atom.Be defined in the mixture that the term " paraffinic hydrocarbons " that is adopted in this suds suppressor discussion comprises straight-chain paraffin and cyclic hydrocarbon.
Preferred another kind of nonsurfactant suds suppressor comprises the silicone suds suppressor.This type of suds suppressor comprises use organopolysiloxane oils, for example polydimethylsiloxane; The dispersion agent of organopolysiloxane oils or resene or emulsifying agent; With the binding substances of organopolysiloxane and silicon dioxide granule, wherein organopolysiloxane is by chemisorption or merge on silicon-dioxide.The silicone suds suppressor is well known in the art, and open in the european patent application of announcing February 7 nineteen ninety 8930785.9 at the United States Patent (USP) 4,265,779 that for example was presented to people such as sweet Dorr richness on May 5th, 1981 and this Tacchinardi M.S..
At United States Patent (USP) 3,455, other silicone suds suppressor is disclosed in 839, this patent relates to and add some compositions and the method that a spot of polydimethylsiloxane fluid makes its froth breaking in the aqueous solution.
For example in German patent application DOS 2,124,526, narrated the mixture of the silicon-dioxide of silicone and silanization.Silicone defoamer and Foam Control in the granular detergent composition disclosed in people's such as crust holder Trotta United States Patent (USP) 3,933,672 and the United States Patent (USP) 4,652,392 the people such as Ba Jinsiji of issue on March 24th, 1987.
The representative silicone base suds suppressor of Shi Yonging is the Foam Control that suppresses foam volume in this article, and its essentially consist is as follows:
(i) polydimethylsiloxane fluid, its viscosity is 20cs-1 under 25 ℃, 500cs;
(ii) silicone resin is for the 5-50% (weight) of (i), by (CH 3) 3SiO 1/2Unit and SiO 2The unit is formed, (CH 3) 3SiO 1/2Unit and SiO 2The ratio of unit is 0.6: 1-1.2: 1; With
(iii) solid silicone is the 1-20% (weight) of (i).
In preferred silicone suds suppressor used herein, the external phase solvent is by multipolymer or its mixture (preferably) of some polyoxyethylene glycol or polyethylene glycol-propylene glycol, or the polypropylene glycol preparation.Main silicone suds suppressor is a side chain/crosslinked, and preferred non-straight chain.
In order to further specify this point, the typical liquid laundry of control foam is chosen the described silicone suds suppressor that contains 0.001-1% (weight) wantonly with detergent composition, preferably contain 0.01-0.7%, most preferably contain 0.05-0.5%, the silicone suds suppressor comprises: the non-aqueous emulsion of (1) main defoamer, it is (a), (b), (c), (d) mixture, (a) be organopolysiloxane, (b) be arborescens siloxanes or the silicone compounds of producing silicone resin, (c) be fine filler and (d) be to promote mixing element (a), (b) and (c) reaction generates the catalyzer of silanol; (2) at least a nonionic silicone surfactant; (3) multipolymer of polyoxyethylene glycol or polyethylene glycol-propylene glycol, its at room temperature the solubleness in water greater than 2% (weight); But do not contain polypropylene glycol.In granular composition, gel etc., can adopt same quantity.Also can be referring to the United States Patent (USP) 4 of this Tacchinardi of issuing December 18 nineteen ninety, 4,983 of this Tacchinardi of issue on January 8th, 978,471 and 1991,316, the Xiu Baidi people's of issue on February 22nd, 1994 5,288,431, and people's such as Ai Zhawa United States Patent (USP) 4,639,1 hurdle the 46th such as 489 and 4,749,740 grades walks to the 4th hurdle the 35th row.
The silicone suds suppressor of this paper preferably contains the multipolymer of polyoxyethylene glycol and polyethylene/polypropylene glycol, and their molecular-weight average is lower than 1,000, is preferably 100-800.The polyoxyethylene glycol of this paper and the polyethylene/polypropylene copolymers at room temperature solubleness in water are preferably greater than 5% (weight) greater than 2% (weight).
The preferred solvent of this paper is polyoxyethylene glycol and polyethylene/polypropylene glycol multipolymer, and the molecular-weight average of polyoxyethylene glycol is lower than 1,000, and more preferably 100-800 most preferably is 200-400 and polyethylene/polypropylene glycol multipolymer, preferred PPG 200/PEG 300.The weight ratio of preferred polyoxyethylene glycol and polyethylene glycol-propylene glycol copolymers is 1: 1-1: 10, most preferably be 1: 3-1: 6.
It is 4,000 polypropylene glycol that preferred silicone suds suppressor used herein does not contain polypropylene glycol, particularly molecular weight.The segmented copolymer of also preferred oxygen-free ethene and propylene oxide is as PLURONIC L101.
Other suds suppressor used herein comprises the mixture of secondary alcohol (for example, 2-alkyl alkanol) and this class alcohol and silicone oil, for example at United States Patent (USP) 4,798,679,4,075,118 and EP 150,872 in disclosed ketone.The secondary alcohol class comprises and contains C 1-C 16The C of carbochain 6-C 16Alkanols.Preferred alcohol is 2-butyl octanol, and this alcohol can have been bought from Conded, and trade mark is ISOFOL 12.The mixture of secondary alcohol class can have been bought from Enichem, and trade mark is ISALCHEM 123.It is 1 that the mixing suds suppressor generally contains weight ratio: 5-5: the mixture of alcohol+silicone of 1.
Narrated another kind of foam regulation system very preferably in WO 93/17772, this system is a kind of granular immobilising foaming regulator, and wherein carrier does not contain tensio-active agent.The composition of tensio-active agent is preferably the alkyl poly glucoside that contains the C12-C18 alkyl of C12-C22 alkyl sulfuric ester salt, especially glucosyl group and/or an alkali metal salt of C12-C22 lipid acid (first) ethyl ester sulfonated products.This system does not contain SiO 2, the not phosphorous hydrochlorate of carrier and be water miscible or water dispersible and paraffin at room temperature is solid-state, and be liquid up to 100% (weight) below 90 ℃.
So-called defoaming compounds is meant at this paper and particularly under the situation that stirs this solution, plays solution to detergent composition and to suppress foaming or the arbitrary compound of forming process and the mixture of compound.
The typical foaming regulator system that this paper adopts is the immobilising foaming regulator of granulous, wherein comprise: 1. the granular carrier that does not contain tensio-active agent, with the 2. uniform defoamer mixtures that are adsorbed, it is siloxane-containing copolymer and the tensio-active agent that plays emulsification or dissemination not, wherein comprises:
A) a kind of paraffin of 70-95% (weight) or mineral wax mixture and
B) bisamide that generates by the saturated carboxylic acid class of two amines of C2-C7 and C12-C22 of 30-5%.
Narrated another kind of froth breaking control agent very preferably in WO 94/00547, this froth breaking control agent is a Yelkin TTS, preferably soya lecithin.
The composition of this paper comprises the additional suds suppressor of 0%-5% usually.When adopting monobasic aliphatic carboxylic acid and its esters as suds suppressor, its amount generally is up to 5% (weight) of detergent composition.The preferred monobasic fat carboxylate suds suppressor that adopts 0.5%-3%.When adopting the silicone suds suppressor, its consumption generally is up to 2.0% (weight) of detergent composition, although can adopt higher amount.In fact this upper limit is practical, and for control foaming effectively, it mainly is related to makes cost keep minimum and effective level is reduced.The preferred silicone suds suppressor that adopts 0.01%-1% more preferably adopts 0.25%-0.5%.These weight percent rate scores used herein are fallen into a trap into any silicon-dioxide and the utilizable any additives material that can be used with organopolysiloxane.When adopting a stearyl phosphoric acid salt suds suppressor, its consumption is the 0.1%-2% (weight) of composition.When adopting the hydro carbons suds suppressor, its consumption is generally 0.01%-5.0%, although can use higher amount.When adopting the alcohols suds suppressor, its consumption is the 0.2%-3% (weight) of final product composition having. Detersive surfactant
The limiting examples (content of tensio-active agent is generally 1%-55% (weight)) that is applicable to the tensio-active agent of this paper comprises common C 11-C 18Alkylbenzene sulfonate (" LAS ") and have side chain and random C 10-C 20Primary alkyl sulfuric acid (" AS "), general formula are 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 sulfuric ester salt, x and (y+1) be to be at least 7 integer in the formula, preferably be at least 9 and M be water miscible positively charged ion, particularly sodium, unsaturated sulfuric acid is oil base sulfuric acid, C for example 10-C 18Alkyl alkoxy sulfuric ester salt (" AE xS "); The oxyethyl group sulfuric ester salt of EO1-7 particularly), C 10-C 18Alkyl alkoxy metal carboxylate (the particularly ethoxy carboxylate salt of EO1-5), C 10-C 18Glycerine ethers, C 10-C 18The alkyl polysaccharide glycoside and with the glycan glycoside of their corresponding sulfuric ester salinization, and C 12-C 18α-sulfonated fatty acid ester.
Preferred detergent composition be substantially free of the LAS tensio-active agent (be 1% (weight) that the content of LAS tensio-active agent is lower than composition, preferably be lower than 0.5% and most preferably do not contain the LAS tensio-active agent).
If desired, total composition also can contain common nonionogenic tenside and amphoterics, for example comprises so-called narrow peak alkylethoxylate and C 6-C 12The C of alkylphenol alcoxylates (particularly ethoxylate and blended oxyethyl group/propoxy-) 12-C 18Alkylethoxylate (" AE "), C 12-C 18Trimethyl-glycine and sultaine (" Sultaines "), C 12-C 18Amine oxide etc.
Amine oxide is a kind of detersive surfactant of the present invention that is applicable to because it with other detersive surfactant for example the oil base sarcosinate match and can produce very strong clean effect.If be used with other tensio-active agent, particularly preferably be the C14 amine oxide.Also can adopt C 10-C 18Many hydroxy fatty acids of N-alkyl acid amides.Typical example comprises C 12-C 18N-methyl glucoside acid amides.Referring to WO 92/06154.Comprise many hydroxy fatty acids of N-alkoxyl group amides, for example C by other tensio-active agent of sugared deutero- 10-C 18N-(3-methoxycarbonyl propyl) glucose amide.In order to reduce foaming effect, can adopt the N-propyl group to N-hexyl C 12-C 18Glucose amide.Also can use C 10-C 20Common soap.The mixture of negatively charged ion and nonionogenic tenside is effective especially.
In the detergent composition of this paper, also can use cats product.Being suitable for preferred cationic tensio-active agent of the present invention is coconut N-hydroxyethyl-N, N-dimethyl ammonium and cholinesterase.In general textbook, show other tensio-active agent commonly used. Additional decontamination composition
Detergent composition of the present invention can also contain additional decontamination composition.The physical aspect that the definite kind of these supplementary components and add-on thereof depend on composition and the decontamination character of operation of using these supplementary components.
For example composition of the present invention can be mixed with the detergent composition that is used to hand-wash with machine washing of clothes, comprising the laundry additive composition be applicable to the pretreated composition of dirty fabric, and the dishwasher composition.
Be applicable to the machine washing mode in preparation, when for example machine laundry and machine were washed the composition of dish, composition of the present invention preferably contained one or more additional decontamination compositions, and these compositions are selected from bleach-activating agent class and ready-formed peracid, SYNTHETIC OPTICAL WHITNER and composition thereof.When adopting the ready-formed peracid, they can be selected from acid amides peracid, diperacid and composition thereof. Bleach-activating agent
If bleach-activating agent is arranged in the detergent composition, its content is generally 0.1%-60%, 0.5-40% more commonly used.These activators contain one or more N-or O-acyl group, and can be selected from many types.Be presented to people's such as hair United States Patent (USP) 4,915,854 in April 10 nineteen ninety and at United States Patent (USP) 4,412, disclose the various limiting examples of some activators in 934.Nonanoyl phenolsulfonate (NOBS) and tetraacetyl ethylene diamine (TAET) activator are representational, and also can use its mixture.As bleach-activating agent, also comprise for example disclosed diphenylketone sulfocarbolate in EPA-0341947, and the cationic derivative of diphenylketone sulfocarbolate.For other typical SYNTHETIC OPTICAL WHITNER and activator used herein, be also shown in United States Patent (USP) 4,634,551.
Amide group suds suppressor precursor of the present invention also can play activator, is the useful bleach-activating agent of a class.In addition, these activators can also use with for example other activator as herein described (NOBS, TAED, benzoxazine activator, acyl lactam activator and cationic activation agent and composition thereof).
Another kind of bleach-activating agent comprises benzoxazine class activator, and is open in the United States Patent (USP) 4,966,723 of issue on October 30 nineteen ninety by people such as Huo Qi, is hereby incorporated by.Benzoxazine class activator very preferably is:
Figure C9519469500171
Also have the preferred bleach-activating agent of a class, this class comprises that acyl lactam activator, particularly general formula are
Figure C9519469500172
Acyl caprolactam class and acyl group Valerolactim class, R in the formula 6Be H or alkyl, aryl, alkoxy aromatic yl or the alkaryl that contains 1-12 carbon atom.Lactan activator very preferably comprises benzoyl hexanolactam, decoyl hexanolactam, 3,5,5-trimethyl acetyl hexanolactam, nonanoyl hexanolactam, caprinoyl hexanolactam, undecanoyl hexanolactam, benzoyl Valerolactim, decoyl Valerolactim, caprinoyl Valerolactim, undecanoyl Valerolactim, nonanoyl Valerolactim, 3,5,5-trimethyl acetyl Valerolactim and composition thereof.Also can be presented to the United States Patent (USP) 4,545,784 of SANDERSON Cael referring on October 8th, 1985, be hereby incorporated by, this patent disclosure comprise the acyl caprolactam of benzoyl hexanolactam, they are attracted in the Sodium peroxoborate.
Another kind of preferred bleach-activating agent comprises that its general formula is by the cationic bleach activators of Valerolactim and acyl caprolactam compound deriving: X is 0 or 1 in the formula, substituent R, R ' and R, and " each all is C 1-C 10Alkyl or C 2-C 4Hydroxyalkyl, formula [(C yH 2y) O] n-R , y=2-4 in the formula, n=1-20 and R are C 1-C 4Alkyl or hydrogen and X are negatively charged ion. SYNTHETIC OPTICAL WHITNER
The detergent composition of this paper can be chosen wantonly and contain SYNTHETIC OPTICAL WHITNER.When SYNTHETIC OPTICAL WHITNER existed, particularly for the washing of fabric, the content of SYNTHETIC OPTICAL WHITNER was generally the 1%-30% of detergent composition, 5%-20% more commonly used.
SYNTHETIC OPTICAL WHITNER used herein can be any SYNTHETIC OPTICAL WHITNER that is applicable in the detergent composition of textile washing, hard surface detergent or now known other washing occasion.These SYNTHETIC OPTICAL WHITNER comprise oxygen-bearing bleaching agent and other SYNTHETIC OPTICAL WHITNER.This paper can adopt the alkali metal perborate SYNTHETIC OPTICAL WHITNER, for example Sodium peroxoborate (for example monohydrate or tetrahydrate).
Also can use peroxygen bleach.Suitable peroxy bleaching compound comprises sodium percarbonate (Sodium Carbonate Peroxyhydrate) and " percarbonate " SYNTHETIC OPTICAL WHITNER, mistake trisodium phosphate, the plain superoxide of urea and sodium peroxide of equal value.Also can adopt persulphate SYNTHETIC OPTICAL WHITNER (for example, the OXONE of DuPont lot production).
Preferred percarbonate bleach contains the dried particle that mean particle size is 500 μ-1,000 μ, and described particle is no more than 10% (weight) and also is no more than 10% (weight) greater than 1,250 μ less than 200 μ's.Can choose wantonly with silicate, borate or water soluble surfactant active and coat percarbonate.Percarbonate can for example FMC, Solvay and Tokai Denka buy from various commercial source.Also can use the SYNTHETIC OPTICAL WHITNER mixture.
Another kind of SYNTHETIC OPTICAL WHITNER that can unrestricted use comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its esters.The example that this class SYNTHETIC OPTICAL WHITNER is suitable comprises that six water cross the magnesium salts of an oxygen phthalic acid magnesium, metachloroperbenzoic acid, 4-nonyl amine base-4-oxo Perbutyric Acid and cross the dioxy lauroleic acid.This class SYNTHETIC OPTICAL WHITNER is at the Hartmann's of on November 20th, 1984 issue United States Patent (USP) 4,483,781, the Berne of submitting on June 3rd, 1985 this etc. people's U.S. Patent application 740,446, the people's such as Ban Kesi that announced on February 20th, 1985 european patent application 0,133,354 and the people's such as clock of November 1 nineteen eighty-three issue United States Patent (USP) 4,412,934 in open.6-amino in the ninth of the ten Heavenly Stems-6-oxo that SYNTHETIC OPTICAL WHITNER very preferably also is included in the United States Patent (USP) 4,634,551 that was presented to this people such as grade of Berne on January 6th, 1987 narration cross oxy hexanoic acid and the ninth of the ten Heavenly Stems amino peroxide hexanodioic acid.
Also know non-oxygen bleaching agent in the art, and can use it for this paper.A significant especially class non-oxygen bleaching agent comprises light catalytic bleaching agent, for example sulfonated zinc and/or aluminium phthalocyanine class.See the United States Patent (USP) 4,033,718 that was presented to people such as Hall Kang Bu on July 5th, 1977.If use this class SYNTHETIC OPTICAL WHITNER, particularly sulfonated zinc phthalocyanine, detergent composition contains this class SYNTHETIC OPTICAL WHITNER of 0.025%-1.25% (weight) usually.
If desired, bleaching compounds can be used manganic compound catalysis.This compounds is well-known in this area, and they comprise for example at United States Patent (USP) 5,246,621,5,244,594,5,194,416,5,114,606 and european patent application 549,271 A1,549, disclosed manganese-based catalyst among 272 A1,544,440 A2 and 544,490 A1 (publication No.); These catalyzer preferred examples comprise Mn IV 2(u-O) 3(1,4,7-trimethylammonium-1,4,7-three azo-cycle nonanes) 2(PF 6) 2, Mn III 2(u-O) 1(u-OAc) 2(1,4,7-trimethylammonium-1,4,7-three azo-cycle nonanes) 2(C1O 4) 2, Mn IV 4(u-O) 6(1,4,7-three azo-cycle nonanes) 4(ClO 4) 4, Mn IIIMn IV 4(u-O) 1(u-OAc) 2-(1,4,7-trimethylammonium-1,4,7-three azo-cycle nonanes) 2(ClO 4) 3, Mn IV(1,4,7-trimethylammonium-1,4,7-three azo-cycle nonanes)-(OCH 3) 3(PF 6) and composition thereof.Other metal matrix bleaching catalyst comprises at United States Patent (USP) 4,430, those disclosed metal matrix SYNTHETIC OPTICAL WHITNER in 243 and 5,114,611.At following United States Patent (USP): reported also in 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 that use manganese and various complex compound ligand strengthen bleaching action.
As a practical problems and not as restriction, can adjust composition and the method for this paper, so that in water-washing liquid, keep active bleaching catalyst at least about 1/10000000th, and in washing liquid the preferred catalyzer that keeps 0.1ppm-700ppm, more preferably 1ppm-500ppm.
Additive component
The composition of this paper can randomly comprise one or more other detergent additives or other preparation, so that promote or strengthen scourability, be cleaned the processing of matrix or strengthen beautify (for example spices, tinting material, the dyestuff etc.) of detergent composition.Following is the illustrative example of this class additive material. Washing assistant
In the composition of this paper, can randomly comprise detergent builder compound, to help to control hardness of minerals.Can use inorganic and organic washing-assisting detergent.Washing assistant generally is used for fabric cleaning composition, to assist in removing the fine particle dirt.
The content of washing assistant can have very big variation, and this depends on the end-use of composition and the physical aspect of desired composition.When containing washing assistant, content is generally at least 1% of composition altogether.Liquid formulations contains the detergent builder compound of 5%-50% (weight) usually, more generally contains 5%-30%.Granular prescription contains the detergent builder compound of 10%-80% (weight) usually, more generally contains 15%-50%.Yet this does not also mean that the washing assistant content that eliminating is lower or higher.
Detergent builder compound inorganic or that contain P includes, but are not limited to polyphosphoric acid salt (is example with tri-polyphosphate, pyrophosphate salt and glassy polymer metaphosphate), phosphonates, phytic acid, silicates, carbonate (comprising bicarbonate salts and sesquicarbonate class), Sulfates and the aluminum silicate of basic metal, ammonium and alkanol ammonium salt.Yet, but need nonphosphate builders in some occasion.Importantly, even at so-called " weak " washing assistant (comparing) for example in the presence of the Citrate trianion with phosphoric acid salt, or under the situation that the what is called that adopts zeolite or layered silicate washing assistant to occur " helps and washes deficiency ", the composition of this paper also can play a part fabulous.
The example of silicate-like builder is the alkali metal silicate salt, particularly contains SiO 2With Na 2The ratio of O is 1.6: 1-3.2: 1 silicates and laminar silicic acid salt, for example be presented to the United States Patent (USP) 4,664 that restrains in the H.P., the lamina sodium silicate described in 839 on May 12nd, 1987.NaSKS-6 is the trade mark (this paper generally is abbreviated as it " SKS-6 ") of the crystalline layered silicate of Hoechst sale.Be different from zeolite builders, the NaSKS-6 silicate-like builder does not contain aluminium.NaSKS-6 has layered silicate 6-Na 2Si 2O 5Structural form.It can be with for example at German patent DE-A-3, and 417,649 and DE-A-3, those methods preparations described in 742,043.With regard to regard to the application of this paper, SKS-6 is a kind of layered silicate very preferably, but also can use other this class layered silicate at this paper, and for example general formula is NaMSi xO 2x+1YH 2The silicate of O, M is sodium or hydrogen in the formula, x is the number of 1.9-4, be preferably 2 and y be the number of 0-20, be preferably 0.The various layered silicates of other of Hoechst comprise NaSKS-5, NaSKS-7 and the NaSKS-11 of α, β and γ type.As mentioned above, with regard to this paper uses, 6-Na 2Si 2O 5(NaSKS-6 type) is most preferred.Other silicate for example Magnesium Silicate q-agent also is useful, can be used as the fluffy powder (crispening agent) of granular prescription, also can be used as the stablizer of oxygen bleaching agent, can also be as the composition of foam control system.
The example of carbonate builders is disclosed alkaline-earth metal and an alkaline carbonate in the German patent application of announcing on November 15th, 1,973 2,321,001.
The aluminosilicate washing assistant also is suitable in the present invention.The aluminosilicate washing assistant is very important in best-selling granular reinforcement detergent composition, and can also wash composition as important helping in the liquid detergent prescription.The aluminosilicate washing assistant comprises that empirical formula is Na z[(AlO 2) z(SiO 2) y] xH 2The aluminosilicate of O, z and y are at least 6 integer in the formula, and the mol ratio of z and y is that 1.0-0.5 and x are the integers of 15-264.
On market, can buy suitable aluminosilicate ion exchange material.The structure of these aluminosilicates can be a crystalline or unbodied, and they can be naturally occurring or by the synthetic aluminosilicate that obtains.A kind of method of producing aluminosilicate ion exchange material is disclosed in the people's such as Crewe Mel of on October 12nd, 1976 issue United States Patent (USP) 3,985,669.The preferred synthetic crystalline aluminosilicate ion exchange material that is applicable to this paper can have been bought with Zeolite A, Zeolite P (B), ZeoliteMAP and the Zeolite X name of an article.In particularly preferred embodiments, the general formula of crystalline aluminosilicate ion exchange material is:
Na 12[(AlO 2) 12(SiO 2) 12] xH 2X is 20-30 in the O formula, particularly 27.This material is known as Zeolite A.This paper also can use dehydration zeolite (x=0-10).The particle diameter of preferred aluminosilicate is 0.1-10 μ.
Be applicable to that organic detergent builder compound of the present invention includes, but are not limited to various polycarboxylic acid salt compounds." polycarboxylate " used herein is meant the compound that contains a plurality of carboxylate radicals, preferably is at least tribasic carboxylic acid salt.Usually can the polycarboxylate washing assistant be added in the composition with the form of acid, but also can add with the form of neutral salt.When using with the form of salt, the basic metal for example salt of sodium, potassium and lithium or alkanol ammonium all is preferred.
In polycarboxylic acid salt washing assistant, comprise multiple useful preparation.The important polycarboxylate washing assistant of one class comprises the polycarboxylic acid salt of ether, comprising at the people's such as Lan Baidi of the United States Patent (USP) issue on January 18th, 3,128,287 and 1972 of the Burger of on April 7th, 1964 issue United States Patent (USP) 3, disclosed hydroxy-butanedioic acid hydrogen salt in 635,830.Also can be presented to " TMS/TDS " washing assistant of people's such as Bush United States Patent (USP) 4,663,071 referring on May 5th, 1987.Suitable ether polycarboxylate also comprises ring compound, particularly alicyclic compound, for example at United States Patent (USP) 3,923, and 679,3,835,163,4,158,635,4,120,874 and 4,102, the compound described in 903.
Other detergent builder compound that is suitable for comprises hydroxyl polycarboxylic acid's salt, maleic anhydride and the ethene of ether or the multipolymer, 1 of vinyl methyl ether, 3,5-trihydroxybenzene-2,4,6-trisulfonic acid, carboxymethyl hydroxy-butanedioic acid and polyacetic acid be the salt and the polycarboxylic acid salt of the ammonium of various basic metal, ammonium and the replacement of ethylenediamine tetraacetic acid (EDTA) and nitrogen base nitrilotriacetic for example, for example benzene hexacarboxylic acid, Succinic Acid, hydroxyl two Succinic Acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyl hydroxy-butanedioic acid and soluble salt thereof.
The Citrate trianion washing assistant is citric acid and solubility salt (particularly sodium salt) thereof for example, because they can obtain from renewable source and their biodegradable, so for strengthening liquid detergent formula, they are polycarboxylate washing assistants of particularly important.In granular composition, when particularly being used, also can adopt Citrate trianion with zeolite and/or layered silicate washing assistant.In this based composition and binding substances, the hydroxy-butanedioic acid hydrogen salt also is useful especially.
Disclosed 3 in the Bush's of on January 28th, 1986 issue United States Patent (USP) 4,566,984,3-dicarboxyl-4-Evil-1,6-adipate and relevant compound also are applicable to detergent composition of the present invention.The Succinic Acid washing assistant that is suitable for comprises C 5-C 20Alkyl and alkenyl Succinic Acid and its esters.Particularly preferred this compounds is the dodecylene Succinic Acid.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 wherein preferred washing assistant, and in the european patent application of announcing on November 5th, 1,986 86200690.5/0,200,263 it is done narration.
Other suitable polycarboxylate is disclosed in the United States Patent (USP) 3,308,067 of the Deere of the people's such as Crutchfield of on March 13rd, 1979 issue United States Patent (USP) 4,144,226 and issue on March 7th, 1967.Also can be referring to the United States Patent (USP) 3,723,322 of Deere.
Also can be with fatty acid C for example 12-C 18The monocarboxylic acid class add in the composition separately, or be used, so that it plays the bigger effect of washing that helps with above-mentioned washing assistant, particularly Citrate trianion and/or succinate washing assistant.This usage of fatty acid can reduce foaming effect usually, and the detergent formulation Designers should take into account this.
Under the situation that can adopt phosphorus base washing assistant, and, can use various alkali metal phosphate classes, for example well-known tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate particularly at the strip prescription that is used for hand-washing operation.Also can use for example ethane-1-hydroxyl-1 of phosphonate washing assistant, 1-diphosphonate and other known phosphonates (for example, seeing United States Patent (USP) 3,159,581,3,213,030,3,422,021,3,400,148 and 3,422,137). SequestrantThe detergent composition of-this paper also can be chosen the sequestrant that contains one or more iron and/or manganese wantonly.This class sequestrant can be selected from aromatic chelating agent of aminocarboxylate class, aminophosphonic acid salt, polyfunctional group replacement and composition thereof, makes best explain hereinafter.Under the situation of bound by theory not, can think that the benefit of these preparations should remove the special ability of de-iron and mn ion to a certain extent owing to them by the inner complex that generates solubility from washing soln.
Aminocarboxylic acid salt as optional sequestrant comprises salt of edetate, N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid salt, ethylenediamine tetrapropionic acid(EDTP) salt, teiethylene tetramine-hexacetic acid salt, diethylenetriamine pentaacetic acid salt and ethanol Diglycocol, its basic metal, ammonium and replacement ammonium and composition thereof.
When having the total phosphorus of low levels at least in allowing detergent composition, amino phosphonates do also is suitable as the sequestrant in the present composition, and it comprises that ethylenediamine tetraacetic (methylene phosphonic acid salt) is as DEQUEST.Preferred amino phosphonates do does not contain the alkyl or the alkenyl of 6 above carbon atoms.
The aromatic chelating agent that polyfunctional group replaces also is applicable to the composition of this paper.See the United States Patent (USP) 3,812,044 that was presented to people such as Kang Na on May 21st, 1974.Preferred this class acid type compound is a dihydroxyl disulfonic acid base benzene class for example 1,2-dihydroxyl-3,5-disulfonic acid base benzene.
The preferred biodegradable cheating agent that is used for this paper was quadrol disuccinate (" EDDS "), particularly was presented to the United States Patent (USP) 4,704 of Hartmann and Perkins on November 3rd, 1987, [S, the S] isomer described in 233.
If adopt these sequestrants, its content is generally the 0.1%-10% (weight) of this paper detergent composition.If the employing sequestrant, more preferably its content is the 0.1%-3.0% (weight) of this based composition.Enzyme-can comprise enzyme in the prescription of this paper to be used for the washing of various fabrics, for example to comprise the spot of removing protein-based, carbohydrate-based or tri-glyceride base and is used to prevent the dye transfer of fading, and the recovery that is used for fabric.The enzyme that adds comprises proteinase, amylase, lipase, cellulase and peroxidase and composition thereof.The enzyme that also can comprise other type.They can result from any suitable source, for example vegetables, animal, bacterium, fungi and yeast source.But, their selection is to be subjected to multiple factor for example pH activity and/or optimal stabilityization, thermostability and to the Stability Control of activated detergent, washing assistant etc.In this respect, bacterium or fungal enzyme are preferably for example bacterial amylase and bacterium proteinase and fungal cellulase.
The enzyme amount that adds is enough to generally guarantee that every gram composition contains the organized enzyme that is up to the 5mg weight, is more typically 0.01mg-3mg.Explanation in addition, the composition of this paper generally contains the commercial enzyme preparation of 0.001%-5% (weight), preferably contains 0.01%-1%.In this class commercial enzyme preparation, the consumption of proteinase is enough to generally guarantee that every gram composition contains 0.005-0.1 Anson unit (AU) activity.
Suitable proteinase example is a subtilysin, and it is produced from B. withered grass and the lichen-forming special bacterial strain of B..Another kind of suitable proteinase is from there being the Bacillus strain of maximum activity to produce at pH8-12, and by Novo Industries A/S development with sell, registered trademark is ESPERASE.In the british patent specification 1,243,784 of Novo, narrated the preparation of this kind of enzyme and similar enzyme.On market, can buy the proteolytic enzyme that is fit to remove protein-based spot, that sell with ALCALASE and the SAVINASE name of an article comprising Novo Industries A/S (Denmark) and International Bio-Synthetics, the proteolytic enzyme that Inc. (Holland) sells with the MAXATASE name of an article.Other proteinase comprises that proteinase A (sees the european patent application 130 that on January 9th, 1985 announced, 756) and proteinase B (seeing the rich top grade people's of the european patent application 87303761.8 (sequence number (SN)) submitted on April 28th, 1987 and announcement on January 9th, 1985 european patent application 130,756).
Amylases comprises, for example in british patent specification 1,296, and α-Dian Fenmei, the International Bio-Synthetics of narration among 839 (Novo), the TERMAMYL of the RAPIDASE of Inc. and Novo Industries.FUNGAMYL is a particularly suitable.
The available cellulase comprises two kinds of bacteria cellulose enzyme or fungal cellulases in the present invention.Their optimum pH are preferably 5-9.5.United States Patent (USP) 4 the people such as this gold of BABEI of on March 6th, 1984 issue, 435, suitable Mierocrystalline cellulose enzyme is disclosed in 307, this patent disclosure the fungal cellulase produced from Humicola insolens and Humicala strain DSM 1800 or the mould of generation belong to the cellulase-212 of Aeromonas and the cellulase that from the liver pancreas of extra large mollush (Dolabella Auricula Solander), extracts.At Britain application GB-A-2, suitable cellulase is also disclosed in 075,028, GB-A-2,095,275 and German patent DE-OS-2,247,832.CAREZYME (Novo) is a particularly suitable.
The lipase that is suitable for washing usefulness comprises by the pseudomonas class, for example in English Patent 1,372, and the enzyme of disclosed pseudomonas Stutzeri ATCC 19.154 microorganisms in 034.Be also shown in and be the lipase in the disclosed Japanese patent application 53,20487 of public's examination on February 24th, 1978.This quasi-lipase can have been bought from the Amano Pharmaceutical Co.Ltd. of Japan Nagoya, and its commodity are called Lipase P " Amano ", hereinafter are called " Amano-P ".Other commodity lipase comprises Amano-CES, lipase from Chromo-bacter viscosum, the another kind of Chromobacter viscosum lipase that for example on market, can buy a kind of Chromobacter viscosum lipolytic enzyme NRRLB 3673 from the Toyo Jozo Co. of Japanese Tagata and can buy from the Disoynth Co. of the U.S.Biochemical Corp. of the U.S. and Holland, and from the lipase of Pseudomonas gladioli.From Humicola Lanuginosa deutero-and the LIPOLASE enzyme (visible EPO 341947) that can buy from Novo on market is a kind of preferred lipase that is used for this paper.
Can be with peroxidase and oxygen source, for example percarbonate, perborate, persulphate, hydrogen peroxide etc. are used.They are used to " solution bleaching ", promptly prevent during washing operation on the dyestuff taken off from matrix or pigment dye transfer other matrix to the washing soln.Peroxide enzyme is known in this area, and comprises for example horseradish peroxidase, lignoenzyme and halo peroxidase, for example chloro and bromoperoxidase.The detergent composition that contains peroxidase is open in the PCT International Application No. WO of announcing for example on October 19th, 1,989 89/099813 that is transferred Novo IndustriesA/S by O. Ke Ke.
Be presented to the very wide zymin of the scope that also discloses in people's such as Mai Kadi the United States Patent (USP) 3,553,139 on January 5th, 1971 and it is added method in synthetic detergent composition.Some enzymes are disclosed again in the Hughes's of the people's such as Price of on July 18th, 1978 issue United States Patent (USP) 4,101,457 and issue on March 26th, 1985 United States Patent (USP) 4,507,219.In the people's such as Huo Le of on April 14th, 1981 issue United States Patent (USP) 4,261,868, disclose the zymin that is applicable to the liquid detergent prescription and it has been added method in this class prescription.Can in all sorts of ways and make enzyme used in the washing composition stable.Be presented to the United States Patent (USP) 3 that lattice very wait the people on August 17th, 1971, open and for example clear stable method of enzyme that makes in the european patent application 0199405 (publication No.) of the Wei Neijiasi that on October 29th, 600,319 and 1986 announced, 86200586.5 (application numbers).For example, at United States Patent (USP) 3,519, the stable system of some enzymes has been described in 570. The removal of earth dirt/anti-sinking agent again-composition of the present invention also can be chosen the amine that contains water miscible ethoxylation wantonly, and they have the earth of removal dirt and anti-settled again performance.The granular detergent composition that contains these compounds generally contains the water-soluble ethoxylated amines of 0.01%-10.0% (weight); Liquid detergent compositions contains 0.01%-5% usually.
Most preferred dirt discharges and anti-sinking agent again is the tetraethylene-pentamine of ethoxylation.In the United States Patent (USP) 4,597,898 of the model Mahmut Demir of on July 1st, 1986 issue, further narrated the amine of typical ethoxylation.Another kind of preferred earth dirt removal-anti-sinking agent again is a disclosed cation compound in the european patent application 111,965 of Austria of announcement on June 27th, 1984 and Ge Silinke.Operable other earth dirt removes/and anti-sinking agent again comprises the amine polymer of disclosed ethoxylation in the european patent application 111,984 of the Ge Silinke that announces on June 27th, 1984; Disclosed amphoteric ion polymer in the european patent application 112,592 of the Ge Silinke that announces on July 4th, 1984; With disclosed amine oxide in the United States Patent (USP) 4,548,744 of the Kang Na of on October 22nd, 1985 issue.In the composition of this paper, also can utilize at other earth dirt known in the art and remove and/or anti-sinking agent again.Another kind of preferred anti-sinking agent again comprises carboxymethyl cellulose (CMC) preparation.These preparations are well known in the art. Polymeric dispersant-in the composition of this paper, particularly in the presence of zeolite and/or layered silicate washing assistant, can adopt content is that the polymeric dispersant of 0.1%-7% (weight) is useful.Suitable polymeric dispersant comprises polymerization polycarboxylic acid salt and polyethylene glycols, but also can use at other dispersion agent known in the art, under the situation of bound by theory not, can think with polymeric dispersant and other washing assistant (the polycarboxylic acid salt that comprises lower molecular weight) when being used, by suppressing peptization and the anti-settlement action again that crystalline is grown up, the fine particle dirt is removed, polymeric dispersant strengthens the over-all properties of detergent builder compound.
Can preferably adopt the suitable polymerization of unsaturated monomers or the copolymerization of acid type to prepare polymeric polycarboxylic acid salt pref.The unsaturated monomer acids that can aggregate into suitable polymerization polycarboxylate comprises vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, aconitic acid, methylfumaric acid, citraconic acid and methylenemalonic acid.Have existence such as for example vinyl methyl ether that do not contain carboxylate radical, vinylbenzene, ethene to suit in the polymerization polycarboxylate of this paper or monomer segment, condition is that these segments are no more than 40% (weight).
Shi Yi polymerization polycarboxylate can be produced by vinylformic acid especially.This class acrylic acid based polymer that is applicable to this paper is polyacrylic water-soluble salt.The molecular-weight average of this class acid-based polymer is preferably 2,000-10,000, more preferably 4,000-7,000 and most preferably be 4,000-5,000.The water soluble salt of this class acrylate copolymer can comprise for example ammonium salt of an alkali metal salt, ammonium salt and replacement.The polymkeric substance of this class solubility is known preparation.For example, in the United States Patent (USP) 3,308,067 of the Deere of on March 7th, 1967 issue this application of class polyacrylate in detergent composition is disclosed.
Also can be the multipolymer of vinylformic acid/maleic as disperseing/the anti-preferred component of sinking agent again.This class material comprises the water soluble salt of vinylformic acid and maleic acid.The molecular-weight average of this class acid type multipolymer is preferably 2,000-100, and 000, more preferably 5,000-75,000, most preferably be 7,000-65,000.In this analog copolymer, acrylate is generally 30 with the ratio of maleate segment: 1-1: 1, more preferably 10: 1-2: 1.The water soluble salt of this class vinylformic acid/maleic acid can comprise for example ammonium salt of an alkali metal salt, ammonium salt and replacement.Acrylate/the maleate copolymer of this class solubility is known material, at the european patent application 66915 of announcement on December 15 nineteen eighty-two and the EP 193 that announced on September 3rd, 1986, in 360 it is narrated, the latter also narrates this base polymer and comprises the hydroxypropyl acrylate.Other useful dispersion agent also comprises toxilic acid/vinylformic acid/vinyl alcohol trimer.Also disclosing this class material in EP 193,360, is 45/45/10 trimer comprising for example vinylformic acid/toxilic acid/vinyl alcohol.
The another kind of polymeric material that can comprise is polyoxyethylene glycol (PEG).PEG can present the performance of dispersion agent, can play the earth dirt again to remove-anti-sinking agent again.For its typical molecular weight of these purposes is 500-100,000, be preferably 1,000-50,000, more preferably 1,500-10,000.
Also can use polyaspartic acid salts and polyglutamic acid dipersant, particularly use with zeolite builders.This class dispersion agent is polyaspartic acid salts for example, and preferred molecular weight (on average) is 10,000. The polymeric soil releasing agent-in the compositions and methods of the invention, can choose wantonly and use any polymeric soil releasing agent well known by persons skilled in the art.The characteristics of polymeric soil releasing agent are to have hydrophilic and hydrophobic two kinds of segments, its hydrophilic segment makes for example surface hydrophilic of polyester and nylon of hydrophobic fiber, hydrophobic segment is then attached on the hydrophobic fiber, and in whole washing and rinse cycle, all keep sticking on the fiber, therefore, it plays a part anchor to hydrophilic segment.This can make the spot after handling with soil releasing agent, easier cleaning in the washing step afterwards.
The polymeric soil releasing agent that is applicable to this paper comprises that especially those contain (a) or (b), or not only contained (a) but also contained the soil releasing agent of (b): (a) one or more nonionic hydrophilic components, mainly contain: (i) polymerization degree is at least 2 polyoxyethylene segment, or (ii) the polymerization degree is propylene oxide or the polyoxypropylene segment of 2-10, wherein said hydrophilic segment does not comprise any propylene oxide unit, unless its each end all is bonded on the adjacent segment by ehter bond, or (iii) contain the oxidation alkene unit mixture of ethylene oxide unit and 1-30 propylene oxide unit, wherein said mixture contains the ethylene oxide unit of q.s, therefore hydrophilic component has very high wetting ability, when soil releasing agent attached to common polyethylene terephthalate surface on the time, be enough to increase these surperficial wetting abilities, described hydrophilic segment preferably contains at least 25% ethylene oxide unit, particularly, more preferably contain 50% ethylene oxide unit at least to having this composition of 20-30 propylene oxide unit; (b) one or more hydrophobic ingredients are comprising (i) C 3Oxidation alkene terephthalate segment, if described hydrophobic ingredient also comprises the ethylene oxide terephthalate, then wherein ethylene oxide terephthalate and C 3The ratio of oxidation alkene terephthalate unit is 2: 1 or lower, (ii) C 4-C 6Alkene or oxidation C 4-C 6Alkene segment or its mixture, (iii) poly-(vinyl acetate) segment, preferably polyethylene acetic ester), its polymerization degree is at least 2, or (iv) C 1-C 4Alkyl oxide or C 4Hydroxyalkyl ether substitution product, or its mixture, wherein said substitution product is with C 1-C 4Alkyl oxide or C 4The form of hydroxyalkyl ether derivatived cellulose or its mixture exist, and the plain derivative of this fibrid is amphoteric, thereby they contain the C of q.s 1-C 4Alkyl oxide and/or C 4The hydroxyalkyl ether unit when it adheres on this common synthon surface, has just increased the wetting ability of fiber surface attached on the common polyethylene terephthalate surface and keep enough hydroxyls.
Although can adopt the higher polymerization degree, in the ordinary course of things, (a) polymerization degree of (i) polyoxyethylene segment is 200, is preferably 3-150, more preferably 6-100.Suitable oxidation C 4-C 6The hydrophobic segment of alkene included, but are not limited to the end-blocking of polymeric soil releasing agent, for example was presented to disclosed MO in the United States Patent (USP) 4,721,580 of Ge Silinke on January 26th, 1988 3S (CH 2) nOCH 2CH 2O-, M is that sodium and n are the integer of 4-6 in the formula.
Be applicable to that polymeric soil releasing agent of the present invention also comprises derivatived cellulose, for example copolymerization block of hydroxy ethers cellulose polymer compound, ethylene terephthalate or propylene terephthalate and polyoxyethylene or polyoxypropylene terephthalate etc.This class reagent can have been bought on market, and comprising cellulosic hydroxyl ethers, for example METHOCEL (Dow).The Mierocrystalline cellulose soil releasing agent that is used for this paper comprises that also those are selected from C 1-C 4Alkyl and C 4The Mierocrystalline cellulose of hydroxyalkyl; See the United States Patent (USP) 4,000,093 that was presented to people such as Niccol on December 28th, 1976.
With poly-(vinyl ester) hydrophobic segment is that the soil releasing agent of feature comprises the graft copolymer of poly-(vinyl ester), for example C 1-C 6Vinyl ester preferably will gather (vinyl-acetic ester) and be grafted on the polyoxygenated alkene skeleton, for example on the polyoxyethylene skeleton.See the people's such as storehouse moral that on April 22nd, 1987 announced european patent application 0219048.This class stain remover that can buy on market comprises the preparation of SOKALAN type, for example the SOKALAN that can buy from BASF (West Germany).
The preferred soil releasing agent of one class is the multipolymer that contains the random block of ethylene terephthalate and polyoxyethylene (PEO) terephthalate.The molecular weight of this polymeric soil releasing agent is 25,000-55,000.See that the United States Patent (USP) that was presented to Hai Si on May 25th, 1976 was presented to the United States Patent (USP) 3,893,929 of Barcelona moral on July 8th, 3,959,230 and 1975.
Another kind of preferred polymerization soil releasing agent is the polyester that contains the ethylene terephthalate repeating unit, it contains the ethylene terephthalate unit of 10-15% (weight) and the polyoxyethylene terephthalate unit of 90-80% (weight), be to be 300-5 by molecular-weight average, 000 polyoxyethylene glycol deutero-.The example of this polymkeric substance is included in the preparation ZELCON 5126 (from Dupont) and the MILEASE T (from ICI) that can buy on the market.Be distributed to the United States Patent (USP) 4,702,857 of Ge Silinke on October 27th, also visible.
Another kind of preferred polymerization soil releasing agent is the sulfonated products of linear ester oligopolymer basically, and this oligopolymer comprises the oligomer ester skeleton that is made of terephthaloyl and alkane dioxy support repeating unit and is connected to terminal side chain on the skeleton with covalent linkage.Be presented in November 6 nineteen ninety in the United States Patent (USP) 4,968,451 of J.J. Scheibel and E.P. Ge Silinke and narrated these soil releasing agents fully.Other suitable polymerization soil releasing agent is included in the United States Patent (USP) 4 that was presented to people such as Ge Silinke on December 8th, 1987,711, terephthalate polyester in 730, the United States Patent (USP) 4 that was presented to Ge Silinke on January 26th, 1988,721, the United States Patent (USP) 4 that the end capped oligomer ester of negatively charged ion in 580 and on October 27th, 1987 are presented to Ge Silinke, block polyester oligomerisation compound in 702,857.
Preferred polymerization soil releasing agent also is included in the soil releasing agent in the United States Patent (USP) 4,877,896 that was presented to people such as Maldonado on October 31st, 1989, this patent disclosure negatively charged ion, particularly sulfo group aroyl, end capped terephthalate polyester.
If employing soil releasing agent, its content are generally the 0.01%-10.0% (weight) of this paper detergent composition, be generally 0.1%-5%, be preferably 0.2%-3.0%.
Also having another kind of preferred soil releasing agent, is to contain terephthaloyl unit between multiple terephthaloyl unit, sulfo group, the support of second dioxy and oxidation-1, the oligopolymer of 2-propylene units.These repeating units constitute the skeleton of oligopolymer, and preferably use the isethionate end cap end-blocking of modification.The particularly preferred soil releasing agent of this class comprises 1 sulfo group isophthaloyl unit, 5 second dioxy supports and 1 that terephthaloyl unit, ratio are 1.7-1.8,2-third dioxy support unit and two 2-(2-hydroxyl-oxethyl)-ethane sulfonic acid sodium end cap unit.Described soil releasing agent also contains the stablizer that crystal is reduced, and its content is the 0.5%-20% (weight) of oligopolymer, and preferably from xylenesulfonate, cumene sulfonate, tosylate and composition thereof. The dye transfer inhibitor-composition of the present invention can comprise that also one or more can suppress the preparation of dyestuff on from a kind of fabric dye transfer to another kind of fabric effectively in washing process.This class dye transfer inhibitor generally comprises multipolymer, manganese phthalocyanine, peroxidase of polyvinylpyrrolidonepolymers polymers, polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole and composition thereof.If adopt these reagent, its content is generally the 0.01%-10% (weight) of composition, is preferably 0.01%-5%, and 0.05%-2% more preferably.
Especially specifically, to contain general structure be R-A in order to be used for this paper preferred polyamine N-oxide polymer xThe unit of-P, P is a polymerizable unit in the formula, and the N-O group is connected on this unit, or the N-O group can constitute this unitary part the N-O group is connected on two unit; A kind of in the following array structure of A :-NC (O)-,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; With R be aliphatics, aromatic series, heterocycle or the alicyclic group of aliphatics, ethoxylation or their arbitrary combination, can make nitrogen in the N-O group be connected on these groups or the N-O group is the part in these groups.Preferred polyamine N-oxide compound is that wherein R is for example compound of pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines and derivative thereof of heterocyclic group.
The N-O group can be represented by following general structure: R in the formula 1, R 2, R 3Be aliphatics, aromatic series, heterocycle or alicyclic group or its combination; X, y and z are 0 or 1, and the nitrogen in the N-O group can be connected or constitute the part of arbitrary aforementioned group.The unitary pKa of the amine oxide of polyamine N-oxide＜10, preferred pKa＜7, more preferably pKa＜6.
As long as the amine oxide polymers that generates is water miscible and has the performance that suppresses dye transfer, just can adopt any polymer backbone.The example of suitable polymer blend skeleton is polyethylene kind, polyalkenes class, polyester, polyethers, polyamide-based, poly-imines class, polyacrylate(s) and composition thereof.These polymkeric substance comprise random or segmented copolymer, and wherein a kind of monomer is that amine n-oxide and another kind of monomer are the N-oxide compounds.Amine is generally 10 with the ratio of amine n-oxide in the amine n-oxide polymkeric substance: 1-1: 1,000,000.But can change the quantity of amine oxide group in the polyamine oxide polymer by suitable interpolymerization or suitable N-degree of oxidation.Almost can prepare the polyamine oxide compound with arbitrary polymerization degree.Its molecular-weight average is generally 500-1, and 000,000; More preferably 1,000-500,000, most preferably be 5,000-100,000.The preparation of this priority can be described as " PVNO ".
The most preferred polyamine N-oxide that is suitable for this paper detergent composition is poly-(4-vinylpridine-N-oxide compound), and its molecular-weight average is 50,000, and the ratio of amine and amine n-oxide is 1: 4.
The multipolymer of also preferred N-vinyl pyrrolidone and N-vinyl imidazole polymkeric substance (being referred to as " PVPVI " level) is used for this paper.The molecular-weight average of PVPVI is preferably 5,000-1,000,000, more preferably 5,000-200,000 and most preferably be 10,000-20,000.(average molecular weight range is by the people showed at Bath etc. Chemical analysisLight scattering method described in 113 volumes " modernism of polymer characterization " determines that its disclosure is hereby incorporated by.) mol ratio of N-vinyl imidazole and N-vinyl pyrrolidone is generally 1 in the PVPVI multipolymer: 1-0.2: 1, more preferably 0.8: 1-0.3: 1, most preferably be 0.6: 1-0.4: 1.These multipolymers both can be straight chain also can be side chain.
It is 5 that composition of the present invention also can adopt molecular-weight average, 000-400, and 000 Polyvinylpyrolidone (PVP) (" PVP ") is preferably 5,000-200,000, and more preferably 5,000-50,000.PVP ' s has been known to the technician of detergent applications; Referring to for example EP-A-262,897 and EP-A-256,696, be hereby incorporated by.It is 500-100 that the composition that contains PVP also can contain molecular-weight average, and 000 polyoxyethylene glycol (" PEG ") is preferably 1,000-10,000.By the ppm that is reached in washing soln, PEG is preferably 2 with the ratio of PVP: 1-50: 1, and more preferably 3: 1-10: 1.
The detergent composition of this paper also can be chosen the wetting ability white dyes that also works some type that suppresses the dye transfer effect that contains 0.005%-5% (weight) wantonly.If adopt this fluorescent bleaches, its content is preferably the 0.01-1% (weight) of this paper composition.
Be applicable to that wetting ability white dyes of the present invention is to have structural formula to be Compound, R wherein 1Be selected from anilino, N-2-two-hydroxyethyl and NH-2-hydroxyethyl; R 2Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chloro and amino; With M be salifiable positively charged ion, for example sodium or potassium.
R in following formula 1Be anilino, R 2Be N-2-two-hydroxyethyl and M are positively charged ions for example during sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-guanamine-yl) amino]-2,2 '-Stilbene disulfonic acid and disodium salt.Ciba-Geigycorporation sells the special whitening agent of this class on market, product are called Tinopal-UNPA-GX.Tinopal-UNPA-GX is the wetting ability white dyes that preferably is applicable to this paper detergent composition.
R in following formula 1Be anilino, R 2For N-2-hydroxyethyl-N-2-methylamino-and M are positively charged ion for example during sodium, whitening agent is 4,4 '-two [(4-anilino-6-) N-2-hydroxyethyl-N-methylamino-)-guanamine-yl) amino] 2,2 '-Stilbene disulfonic acid disodium salt.Giba-Geigy Corporation sells this special whitening agent with the Tinopal 5BM-GX name of an article on market.
As R in following formula 1Be anilino, R 2For morpholino and M are positively charged ions for example during sodium, whitening agent is 4,4 '-two [(4-anilino-6-morpholino-guanamine-yl) amino] 2,2 '-Stilbene disulfonic acid, sodium salt.Ciba Geigy Corporation sells this special whitening agent with the Tinopal AMS-GX name of an article on market.
When being selected to extraordinary white dyes of the present invention and selected above-mentioned polymerization dye transfer inhibitor and being used, can produce especially effectively dye transfer rejection.This selected class polymeric material (for example PVNO and/or PVPVI) cooperates with selected this fluorescent bleaches (for example Tinopal UNPA-GX, Tinopa 5BM-GX and/or Tinopal AMS-GX), the dye transfer restraining effect that is produced in wash water solution, any during than these two kinds of detergent composition compositions of independent use is all much better than.Under the situation of bound by theory not, it is such to think why this class whitening agent plays a part, and is because they have very big avidity to fabric in washing soln, and therefore they can be quite promptly attached on these fabrics.The degree that various whitening agent adhere on fabric in washing soln can be defined by the parameter that is called " consumption coefficient "." consumption coefficient " generally with a) and b) recently the expression, be a) attached to the whitening agent material on the fabric, b) be the starting point concentration of whitening agent in wash water solution.Under situation of the present invention, the higher whitening agent of consumption coefficient is suitable for suppressing dye transfer most.
Nature should be appreciated that the optical brightener compounds that can randomly use other general type in this composition, so that common fabric has " brightness " (brightness) effect, rather than real dye transfer restraining effect.For detergent formulation, this usage is usual in well-known. Whitening agent-any white dyes known in the art or other whitening agent or whitening agent can be joined in the detergent composition of this paper, its content is generally the 0.05%-1.2% (weight) of detergent composition.Can will be applicable to that commodity white dyes of the present invention is divided into some subclasses, comprising, but be not necessarily limited to Stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methine cyanine, dibenzothiophene-5, the heterocyclic derivative of 5-dioxide, azoles, 5-and 6-joint-ring and other all ingredients.At John Wiley ﹠amp; The M. that Sons publishes in New York praises the rad Buddhist nun and restrains some examples that disclose this class whitening agent in " production of white dyes and application " (1982) of showing.
The specific examples that is applicable to the white dyes of this composition is to be presented to determined those compounds in the United States Patent (USP) 4,790,856 of Wilson on December 13rd, 1988.These whitening agent comprise the PHORWHITE whitening agent of being sold by Verona.Disclosed other whitening agent comprises in this reference: Tinopal UNPA, TinopalCBS and the Tinapal 5BM that can buy from Giba-Geigy; Can be from being positioned at ArticWhite CC and the Artic White CWD that gondola Hilton-Davis has bought; 2-(4-styryl-phenyl)-2H-naphtho-[1,2-d] triazole; 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-aminocoumarin; 1, the two (ethene of benzimidazolyl-2 radicals-yl) of 2-; 1,3-phenylbenzene-pyrazoline; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-styryl-naphtho-[1,2-d] oxazole; And 2-(Stilbene base-4)-2H-naphtho-[1,2-d] triazole.Be also shown in the United States Patent (USP) 3,646,015 that was presented to Hamilton on February 29th, 1972.This paper is the negatively charged ion whitening agent preferably. Fabric softener-in this composition, can choose wantonly and use various fabric washing softening agents.The particularly Si Tuomu of on December 13rd, 1977 issue and the United States Patent (USP) 4 of Na Sikeer, 062, fine terre verte in 647 and other softening agent clay known in the art, its content is generally 0.5%-10% (weight), so that increase the soft degree of fabric in laundering of textile fabrics.Can with the clay softening agent with for example March nineteen eighty-three people such as Coco Crisp on the 1st United States Patent (USP) 4,375,416 and the people's such as Harris of on September 22nd, 1981 issue United States Patent (USP) 4,291,071 in disclosed amine and cationic softener be used. Other compositionThe composition of-this paper can comprise all other compositions that are applicable to detergent composition, comprising the solvent of other activeconstituents, carrier, solubility promoter, processing auxiliary agent, dyestuff or pigment, liquid formulations, the solid weighting agent of bar compositions etc.
Can be covered with hydrophobic layer then on described matrix randomly by described composition is absorbed on the porous hydrophobic base, the various decontamination compositions that make in this composition to be adopted are further stablized.Preferably before the decontamination composition is absorbed by porous matrix, it is mixed with tensio-active agent.In use, the decontamination composition is discharged in the wash water solution from matrix, thereby plays the soil-removing action of its expection.
In order to illustrate in greater detail this technology, with porous hydrophobic silicon-dioxide (trade mark is SIPERNAT D10, is sold by DeGussa) with contain 3%-5%C 13-15The proteolytic enzyme solution of the alcohol of ethoxylation (EO7) nonionogenic tenside mixes.Enzyme/surfactant soln is 2.5 times of silica weight normally.Utilizing to stir is dispersed in the silicone oil (can use viscosity to be 500-12,500 various silicone oils) powder that makes.Directly be added in the final washing composition matrix with the silicone oil dispersion system emulsification of making or with it.By this method; can washing composition will be used for; comprising being used for the various compositions of liquid laundry with detergent composition, enzyme for example mentioned above, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, photocatalyst, dyestuff, fluorescent agent, fabric finishing agent and hydrolyzable tensio-active agent " protection " get up.
Liquid detergent compositions can comprise water and as other solvent of carrier.Low-molecular-weight primary alconol and secondary alcohol for example methyl alcohol, ethanol, propyl alcohol and Virahol all suit.With regard to the solubleness that increases tensio-active agent, preferred unary alcohol, but also can adopt polyvalent alcohol for example contains the polyvalent alcohol (for example 1, ammediol, ethylene glycol, glycerol and 1,2-propylene glycol) of 2-6 carbon atom and 2-6 hydroxyl.Some composition can contain this class carrier of 5%-90%, generally contains 10%-50%.
When the detergent composition that this paper preferably prepares was used for the washing operation, the pH of washing water was 6.5-11, is preferably 7.5-10.5.
The pH that is preferred for washing the liquid product prescription of dish is 6.8-9.0.The pH of the product that is used to do washing is generally 9-11.The method of control pH comprises use buffer reagent, bases and acids etc. under the consumption of recommending, and those skilled in the art is very familiar to these methods.
Detergent composition of the present invention all is effective in soft water and hard water, and can be used in the Gao Zhuxi prescription, wherein the content of washing assistant is at least 125% (weight) of preparation, also can be used on low helping and washes in the prescription, and wherein the content of washing assistant is lower than 15% (weight) of preparation.
Illustrate the present invention with following non-limiting examples, in these embodiments, except as otherwise noted, all percentage ratio all is by weight.
In detergent composition, the composition symbol connotation of condensing is as follows: LAS: C 12Linear alkylbenzene sulphonic acid XYAS: C 1x-C 1ySodium alkyl sulfate APG: general formula is C 12-(glucosyl group) xThe alkyl poly glucoside tensio-active agent, in the formula
X is 1.524EY: mainly be C 12-C 14Straight chain primary alcohol, be with average Y mole ethylene oxide
The 45EY of condensation: mainly be C 12-C 15Straight chain primary alcohol, be Zhou Pingjun Y mole ethylene oxide
The XYEZS of condensation: C 1x-C 1yAlkyl sodium sulfonate, every mole is with the condensation of Z mole ethylene oxide
NaSKS-6: general formula is δ-Na 2Si 2O 5Crystalline layered silicate carbonate: anhydrous sodium carbonate (Carbonate) MA/AA: toxilic acid/vinylformic acid is 1: 4 multipolymer, and about 80, the 000 zeolite A of molecular-weight average: general formula is Na 12(AlO 2SiO 2) 1227H 2The hydrated aluminum silicate of O, this granularity of its base (Zeolite A) is a 1-10 μ Citrate trianion: two hydration trisodium citrate (Citrate) lemons: citric acid (Citric) percarbonate: empirical formula is 2Na 2CO 33H 2O 2Anhydrous SPC-D SYNTHETIC OPTICAL WHITNER, be Na with (Percarbonate) general formula 2SO 4.n.Na 2CO 3Mixing salt coat, n is 0.29 in the formula,
Wherein percarbonate and mixing salt weight ratio be 39: 1TAED: tetra acetyl ethylene diamine proteinase: the proteolytic enzyme (enzymic activity about 2%) that Novo Industries A/S sells is product Savinase lipase by name (Protease): the lipolytic enzyme (enzymic activity about 2%) that Novo Industries A/S sells (Lipase) product is called the Lipo1ase cellulase: the cellulase of Novo Industries A/S sale; product are called Carezyme (Cellulase) Endo A: the name of an article PVNO of the cellulase that Novo Industries A/S sells: polyvinylpyridine N-oxide polymer; molecular weight is 10,000MgSO 4: anhydrous magnesium sulfate SRP: the negatively charged ion polyester soil release polymers CMC of modification: Xylo-Mucine EDDS: quadrol-N, N '-two Succinic Acid, [S, S] isomer silicone of sodium-salt form: 25% paraffin (50 ℃ of melting temperatures), 17% hydrophobicity titanium dioxide (Silicone) silicon, 58% paraffin oil The foam test method
Take by weighing 110g detergent formulations as herein described, then it is added in Miele 698 washing machines, 1.5kg cleaning, new thick towel are housed in the washing machine as ballast.90 ℃, main wash the cycle, use under the condition of soft water (3 ° of Clark) product is tested.
Measure foam %, and utilize following formula to calculate: Every kind of product is repeated 4 times. Embodiment 1I) detergent composition
Prepare following composition and it is carried out frothing test.What the embodiment of preparing the composition 1 of washing composition and composition of the present invention 2 according to the composition A of prior art preparation washings, according to the present invention illustrated dissimilar amido acids and acid amides peracid presses down the bubble effect.
All the other are water and other component i i for A 1 2TAED 5--6-caprylamide/6 decyl amide amyl phenyl ketone-5-sulfocarbolate (50: 50 admixtures) 6-caprylamide/6 decyl amide caproic acids--5 (50: 50 admixtures) C45AS 10 10 10C25AE3S 22 2C2,4E5 33 3N-methyl glucoside acid amides 333 Wessalith CSs 17 17 17SKS-6 12 12 12 citric acids 33 3MA/AA 55 5CMC 0.4 0.4 0.4PEG 0.5 0.5 0.5Savinase 2.4 2.4 2.4Lipolase 0.2 0.2 0.2 cellulases 0.2 0.2 0.2Endo A 0.2 0.2 0.2SRP 0.4 0.4 0.4PVNO 0.02 0.02 0.02 carbonate 666 zinc phthalocyanine sulfonate 20ppm 20ppm 20ppm silicone 0.4 0.4 0.4 percarbonate 20 20 20) the foam test result
Estimate the foaming effect of above-mentioned composition in hard water medium (12 ° of Clark) with described foaming process above.
A 12 foams, % (30 minutes) 85 28 6
The amido acid that uses has the very effective bubble effect that presses down to the foam of surfactant system generation separately. Embodiment 2I) detergent composition
Prepare following composition and it is carried out frothing test.The bubble effect that presses down of the amido acid and the acid amides peracid of different content is shown according to composition A, B, the C of prior art preparation washings and the composition 1,2,3,4 of preparing washings according to the present invention.
A B C 123 4LAS 10--10---C45AS-10 10-10 10 10 silicone 0.3 0.3 0.3 0.3-0.3 0.3TAED 5 5----36-caprylamides/6 decyl amide---5553 amyl phenyl ketone sulfocarbolates (50: 50 admixtures) C45E7,4444444 Wessalith CSs, 18 18 18 18 18 18 18SKS-6,8888888 citric acids, 444444 4MA/AA, 444444 4SRP, 0.3 0.3 0.3 0.3 0.3 0.3 0.3CMC, 0.3 0.3 0.3 0.3 0.3 0.3 0.3EDDS, 0.4 0.4 0.4 0.4 0.4 0.4 0.4MgSO40.4 all the other are water and other component i i for 0.4 0.4 0.4 0.4 0.4 0.4 percarbonate, 18 18 18 18 18 18 18 carbonate, 4.5 4.5 4.5 4.5 4.5 4.5 4.5Savinase, 1.2 1.2 1.2 1.2 1.2 1.2 1.2Lipo1ase, 0.4 0.4 0.4 0.4 0.4 0.4 0.4 cellulases 0.1 0.1 0.1 0.1 0.1 0.1 0.1) the foam test result
A B C 1234 foams, % (30 minutes) 70 100 100 65 60 12 25
According to above-mentioned foam test, LAS is than the low tensio-active agent of coconut AS foaming power as can be seen.
After the foam test of being emphasized is carried out 30 minutes, adulterant is crossed be hydrolyzed into the form of its peracid, described peracid discharges acid.The mixture of prepared amido acid and acid amides peracid froth suppressor has reduced the foaming effect of LAS and AS.The foaming effect that can see the AS tensio-active agent reduces manyly. Embodiment 3I) detergent composition
Prepare following composition and it is foamed and detergency test.The composition 1,2,3 of preparing washings according to the composition A of prior art preparation washings and B, according to the present invention illustrates the bubble effect that presses down of the amido acid and the acid amides peracid of different content.
A B 1 2 3TAED-6-4-6-／6--5 3 3 （ 50∶50 ） ----4C45AS 10 10 10 10 10C25AE3 S 2 2 2 2 2C24E5 3 3 3 3 3N- 3 3 3 3 3A 17 17 17 17 17SKS-6 12 12 12 12 12 3 3 3 3 3MA／AA 5 5 5 5 5CMC 0.4 0.4 0.4 0.4 0.4PEG 0.5 0.5 0.5 0.5 0.5Savinase 2.4 2.4 2.4 2.4 2.4Lipo1ase 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2Endo A 0.2 0.2 0.2 0.2 0.2SRP 0.4 0.4 0.4 0.4 0.4PVNO 0.02 0.02 0.02 0.02 0.02 6 6 6 6 6 20ppm 20ppm 20ppm 20ppm 20ppm 0.4 0.4 0.4 0.4 0.4 20 20 20 20 20ii ） 。
Estimate the foaming effect of above-mentioned composition and adopt laundrometer to estimate above-mentioned composition in 40 ℃, hard water (12 ° of Clark), with described foaming process above the usefulness of the dense dirt of hydrophobicity.
A B 123 foams, % (30 minutes) 100 100 15 30 22 performance A B 123 (psu vs A) lipstick 0+0.5+4.0s+3.0s+3.5s shoe polish 0+0.6+4.0s+3.0s+3.6s tea 0+3.0+1.5+2.8+3.3 coffees 0+2.8+1.3+2.5+3.1
Can play very effective but the bubble effect by the mixture of amido acid and acid amides peracid preparation to the foaming of surfactant system, and the hydrophobicity dirt of object lipstick shoe polish and so on also have effective detergency ability.
In addition, when preparing detergent composition of the present invention, still kept suds suppressing properties and to the decontamination usefulness of the wetting ability spot of hydrophobicity spot and object tea and coffee and so on the precursor that adds such as TAED or benzoyl hexanolactam. Embodiment 4I) detergent composition
Prepare following composition and it is carried out frothing test.What the composition 1,2,3 of preparing washings according to the composition A of prior art preparation washings and B, according to the present invention illustrated the amido acid of different content and acid amides peracid presses down the bubble effect.
A B 1 2 3TAED-6-4-6-/6--5 3 3 ( 50∶50 ) ----4C45AS 5 5 5 5 5C12-C14 ( N-5 5 5 5 5-N,N- ) C25AE3S 2 2 2 2 2C24E7 3 3 3 3 3N- 3 3 3 3 3A 17 17 17 17 17SKS-6 12 12 12 12 12 3 3 3 3 3MA/AA 5 5 5 5 5CMC 0.4 0.4 0.4 0.4 0.4PEG 0.5 0.5 0.5 0.5 0.5Savinase 2.4 2.4 2.4 2.4 2.4Lipolase 0.2 0.2 0.2 0.2 0.2Carezyme 0.2 0.2 0.2 0.2 0.2Endo A 0.2 0.2 0.2 0.2 0.2SRP 0.4 0.4 0.4 0.4 0.4PVNO 0.02 0.02 0.02 0.02 0.02 6 6 6 6 6 20ppm 20ppm 20ppm 20ppm 20ppm 0.4 0.4 0.4 0.4 0.4 20 20 20 20 20ii )
Estimate above-mentioned composition foaming effect of (12 ° of Clark) in the hard water medium with described foaming process above.
A B 123 foams, % (30 minutes) 100 95 35 45 41
It is very effective to the foam that suppresses AS/ cats product mixed system to cross the acid mixture suds suppressor by the amido acid of amido acid precursor preparation and acid amides. Embodiment 5I) detergent composition
Prepare following composition and it is carried out frothing test.What the composition 1 and 2 of preparing washings according to the composition A of prior art preparation washings, according to the present invention illustrated the amido acid of different content/type and acid amides peracid presses down the bubble effect.
All the other are water and other component i i for A 1 2TAED 4.5--6-nonanoyl amyl phenyl ketone sulfocarbolate-3-(molecular weight 287) pelargonamide peroxide adipic acid--1.9 (molecular weight 287) C45AS 10 10 10C25AE3S 22 2C2,4E5 33 3N-methyl glucoside acid amides 333 Wessalith CSs 17 17 17SKS-6 12 12 12 citric acids 33 3MA/AA 55 5CMC 0.4 0.4 0.4PEG 0.5 0.5 0.5Savinase 2.4 2.4 2.4Lipolase 0.2 0.2 0.2Carezyme 0.2 0.2 0.2Endo A 0.2 0.2 0.2SRP 0.4 0.4 0.4PVNO 0.02 0.02 0.02 carbonate 666 zinc phthalocyanine sulfonate 20ppm 20ppm 20ppm silicone 0.4 0.4 0.4 percarbonate 20 20 20) the foam test result
Estimate the foaming effect of above-mentioned composition in soft water (3 ° of Clark) and hard water (18 ° of Clark) with described foaming process above.Foam, % (20 minutes) A 12 soft water 80 35 49 hard water 81 31 43
By the amido acid of amido acid precursor preparation and the mixture of amido acid suds suppressor is the effective suds suppressor of high foaming surfactant in hard water and soft water.Described suds suppressor mixture also has than pelargonamide peroxide hexanodioic acid and better presses down the bubble effect. Embodiment 6I) detergent composition
Prepare following composition and it is foamed and detergency test.According to the composition A of prior art preparation washings, what the composition 1,2,3,4,5 of preparing washings simultaneously according to the present invention illustrated the amido acid of different content and type and acid amides peracid presses down the bubble effect.
A 1 2 3 4 5 17-17 8 25 17-12-6--6-/6-3 3 3 3- ( 50∶50 ) 6-----3 C45AS 10 10 10 10 10 10C25AE3S 2 2 2 2 2 2C24E5 3 3 3 3 3 3N- 3 3 3 3 3 3A 17 17 17 17 17 17SKS-6 12 12 12 12 12 12 3 3 3 3 3 3MA/AA 5 5 5 5 5 5CMC 0.4 0.4 0.4 0.4 0.4 0.4PEG 0.5 0.5 0.5 0.5 0.5 0.5Savinase 2.4 2.4 2.4 2.4 2.4 2.4Lipolase 0.2 0.2 0.2 0.2 0.2 0.2Carezyme 0.2 0.2 0.2 0.2 0.2 0.2Endo A 0.2 0.2 0.2 0.2 0.2 0.2SRP 0.4 0.4 0.4 0.4 0.4 0.4PVNO 0.02 0.02 0.02 0.02 0.02 0.02 6 6 6 6 6 6 20 20 20 20 20 20
All the other are water and other component i i for ppm ppm ppm ppm ppm ppm silicone 0.4 0.4 0.4 0.4 0.4 0.4) foam and performance test result
Estimate the foaming effect of above-mentioned composition in hard water medium (12 ° of Clark) with described foaming process above.
A 12345 foams, % (25 minutes) 100 30 44 60 65 35 performances (40 ℃) A 12 34 5 lipsticks 0+1.6+3.8+3.5+3.6+4.0 shoe polish 0+1.4+3.6+3.2+3.6+4.0
All play suds suppressor by the amido acid of amido acid precursor preparation or the mixture of amido acid and acid amides peracid, and the hydrophobicity dirt of lipstick and shoe polish and so on is had effective detergency ability.
By The above results as seen, the ratio of percarbonate and amido acid precursor can change and be unlikely and reduces its usefulness or suds suppressing properties significantly. Embodiment 7I) detergent composition
Prepare following composition and it is carried out frothing test.What the composition 1,2,3,4,5,6,7 of preparing washings according to the present invention illustrated amido acid and acid amides peracid presses down the bubble effect.
All the other are water, enzyme and other composition for 123456 76-caprylamides/6 decyl amide, 3333333 amyl phenyl ketone sulfocarbolates (50: 50 admixtures) benzoyl caprolactam, 4444444 percarbonate, 17 17 17 17 17 17 17C45 AS, 12 6-9,12 14.3 10C38 AS, 3 3-2,3 3.7 3.7C25 AES, 3 1.5 32 3--C24 E3 5----5,5 palm N-methyl, 4 9-4,944 glucose amide APG--9 5---oil base sarcosinate-7.5 15 5---amine oxides------, 4 Wessalith CSs, 555555 5SKS-6,7777777 citric acid/citrate, 3333333 carbonate, 999999 9MA/AA, 555555 5EDDS, 0.25 0.25 0.25 0.25 0.25 0.25 0.25 silicone 0.6 0.6 0.6 0.6 0.6 0.6 0.6
Use with various mixed surfactant systems by the amido acid of amido acid precursor preparation and the mixture of acid amides peracid, be equivalent to very effective suds suppressor and the hydrophobicity dirt is had good bleaching action.

Claims (7)

1. a water-washing liquid contains
(a) detersive surfactant of 1%-80% weight, wherein detersive surfactant contains C 10-C 20Alkyl-sulphate;
(b) be selected from the composition of sulfonated zinc phthalocyanine class, sulfonation aluminium phthalocyanine class and composition thereof, its content is 0.025%-1.25%; With
(c) the suds suppressor compound of 0.025%-20% weight, its general formula is
Figure C9519469500021
Or
Figure C9519469500022
Wherein said suds suppressor is formed by the suds suppressor precursor of following formula:
Figure C9519469500023
Or Wherein, R 1Be alkyl, aryl or the alkaryl that contains 1-14 carbon atom, R 2Be alkylidene group, arylidene or the alkyl arylene that contains 1-14 carbon atom, R 5Be that H or alkyl, aryl or the alkaryl that contains 1-10 carbon atom and L are leavings groups.
2. according to the water-washing liquid of claim 1, wherein also include the additional suds suppressor that is selected from silicone, Yelkin TTS and contain paraffin and the froth breaking mixture of bisamide.
3. according to the water-washing liquid of claim 1, wherein L is selected from following group and composition thereof, With
Figure C9519469500032
R wherein 1Defined identical with claim 1, R 3Be the alkyl chain that contains 1 to 8 carbon atom, R 4Be H or R 3And Y is H or solubilizing group.
4. according to the water-washing liquid of claim 3, wherein the general formula of L is:
Figure C9519469500033
5. according to the water-washing liquid of claim 1, the content of wherein said suds suppressor precursor is at least 0.1%.
6. the method for control foaming foam comprises adding the step that is selected from following compound or their mixture in detergent composition: R in the formula 1Be alkyl, aryl or the alkaryl that contains 1 to 14 carbon atom, R 2Be alkylidene group, arylidene or the alkyl arylene that contains 1 to 14 carbon atom, R 5Be that H or alkyl, aryl or alkaryl and the L that contains 1 to 10 carbon atom are leavings groups;
Wherein detergent composition contains C 10-C 20Alkyl-sulphate and the composition that is selected from sulfonated zinc phthalocyanine class, sulfonation aluminium phthalocyanine class and composition thereof.
7. according to the method for claim 6, wherein L is selected from following groups: With R wherein 1Be alkyl, aryl or the alkaryl that contains 1-14 carbon atom, R 3Be the alkyl chain that contains 1 to 8 carbon atom, R 4Be H or R 3And Y is H or solubilizing group.
CN95194695A 1994-05-21 1995-04-18 Detergent compositions having suds suppressing properties Expired - Fee Related CN1104488C (en)

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CN107308883B (en) * 2017-06-26 2019-03-01 江南大学 A kind of stable foam formed by abietyl amino acid surfactant
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JPS50150701A (en) * 1974-05-24 1975-12-03
US4852989A (en) * 1987-05-08 1989-08-01 The Procter & Gamble Company Bleaching compounds and compositions comprising fatty peroxyacids salts thereof and precursors therefor having amide moieties in the fatty chain

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Publication number Priority date Publication date Assignee Title
JPS50150701A (en) * 1974-05-24 1975-12-03
US4852989A (en) * 1987-05-08 1989-08-01 The Procter & Gamble Company Bleaching compounds and compositions comprising fatty peroxyacids salts thereof and precursors therefor having amide moieties in the fatty chain

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