CN1238801A - Detergent composition or component - Google Patents

Detergent composition or component Download PDF

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Publication number
CN1238801A
CN1238801A CN 97199997 CN97199997A CN1238801A CN 1238801 A CN1238801 A CN 1238801A CN 97199997 CN97199997 CN 97199997 CN 97199997 A CN97199997 A CN 97199997A CN 1238801 A CN1238801 A CN 1238801A
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Prior art keywords
component
alkyl
group
compound
segment
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Inventor
J·L·卡尔达雷利
S·C·阿斯库
G·A·索尔里
R·G·哈尔
T·A·亨斯曼
H·谭塔怀
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Procter and Gamble Co
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Procter and Gamble Co
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Priority claimed from GB9619928A external-priority patent/GB2317394A/en
Priority claimed from GBGB9713946.3A external-priority patent/GB9713946D0/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of CN1238801A publication Critical patent/CN1238801A/en
Pending legal-status Critical Current

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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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Abstract

The present invention relates to solid or ganular detergent composition or component or spray-dried particle containing one or more carboxylate-containing polyelectrolyte compounds, having builder or dispersant properties, and one or more cationic compounds, which are cationic, (partially) quaternized ethoxylated (poly)amine compounds with clay-soil removal/anti-redeposition properties, for use in laundry and dish washing processes.

Description

Detergent composition or component
Invention field
The present invention relates to be used for doing washing and the detergent composition or the component of wash up process, it contains and has the cation compound of removing great soil group dirt/particulate fouling/antiredeposition character and one or more have the polyelectrolyte compound that contains carboxylate radical of washing assistant or dispersion agent character.
Background of invention
The character of a particularly important of detergent composition is the ability of removing the granule type dirt in washing process from various fabrics.The important particulate fouling of one class is the great soil group dirt.The positively charged positively charged ion (for example calcium) that the soil dirt particles generally comprises electronegative silicoaluminate salt deposit and also keeps being attached thereto between the negative charge layer.
The various forms of compounds of removing great soil group dirt character that have can be proposed.A kind of pattern requires this compound to have two kinds of different propertiess.First kind of character is the ability that compound is adsorbed in the electronegative layer of soil particle; With in case be adsorbed, this compound repels (swelling) electronegative layer to make soil particle lose its sticking power and can be removed to ability in the washing water.
Except removing native dirt, in laundry (or wash up) working cycle, also need to make removed dirt to remain on suspended state.The dirt of removing and being suspended in the washing water from fabric can deposit on the fabric face again.This sedimentary again dirt can cause and tarnish or " become ash " effect that this is especially remarkable for white fabrics.In order to reduce this type of problem, in detergent composition, also usually comprise anti redeposition agent.
Other detergent compound that tradition is used in washing composition is dirt dispersant and anti-incrustation agent, for example contains the polyelectrolyte compound of carboxylate radical.
EP-B-111965 discloses and used cation compound in washing composition, and it has the great soil group dirt of removal and two kinds of character of antiredeposition.
US4659802 and US4664848 have described has the quaternary ammonium compound of removing great soil group dirt and antiredeposition character, and it can be used in combination with anion surfactant.
A kind of pattern that anti-redeposition proposed for these compounds is as follows.In washing water, positive charge molecules has given disperse properties for the soil particle molecule in the lip-deep absorption of soil particle.Along with increasing these compounds are adsorbed onto on the native dirt particles of suspension, native dirt particles just is enclosed in the hydrophilic layer.In laundry or wash up working cycle, this hydrophilic sealing dirt is suppressed and deposits to hydrophobic fabric more for example on the polyester.
Find that the cation compound of known removal great soil group dirt always can not be removed to soil particle the washing water fast and effectively from fabric face.This may be because soil and particulate fouling are connected together by the calcium bridging, and the calcium bridge can suppress to remove the native negative charge layer of cation compound repulsion of great soil group dirt, has suppressed soil particle thus and has lost its sticking power.
Find that also the antiredeposition character of the cation compound of these known removal great soil group dirts can slacken, promptly when having high-load free ca (and/or magnesium) in washing water in laundry or wash up process under the hard water condition.
The applicant finds that now these problems can pass through, containing the positively charged ion of removing great soil group dirt/antiredeposition character that has of specified quantitative, in the detergent component or detergent composition of (part) quaternised ethoxylation (gathering) amine, comprise that the polyelectrolyte compound that contains carboxylate radical of specified quantitative improves.An example of this component is spray-dired particle.Have now found that this detergent component or detergent composition than using one of the independent detergent composition of this two component that astonishing good removal soil/dirt and cleaning performance are provided.Ethoxylation (gathering) amine of also finding cationic quaternary ammoniumization is particularly preferred with the specified proportion that contains the polyelectrolyte compound of carboxylate radical, even when using every kind of component of very low amount, also can obtain good performance.
Discovery contains the polyelectrolyte compound and the positively charged ion of carboxylate radical, and the cleaning performance of the detergent composition of (part) quaternised ethoxylation (gathering) amine is to depend on the amount of the employed polyelectrolyte compound that contains carboxylate radical and its character (for example this polymkeric substance and the monomer segmental molecular weight that comprises in this polymkeric substance).For example, containing under the condition of washing assistant, the multi-carboxylic acid compounds of discovery copolymerization for example toxilic acid/acrylic copolymer has good (calcium) washing assistant/dispersing agent performance than the equal polymeric multi-carboxylic acid compounds with same molecular weight.Therefore, some preferred polymerizable compound of low amount is the same effective with other compound of higher amount.
An advantage more of the present invention is only after once washing circulation is finished, even just can be observed removal soil/dirt digestion.
All documents of quoting in this manual are cited for referencial use at relevant portion.
Summary of the invention
According to the present invention, a kind of solid is provided, preferably granulous detergent composition or its component, it comprises: the polyelectrolyte compound that (a) contains carboxylate radical; (b) have the water-soluble cationic compound of removing native dirt/antiredeposition performance, it is selected from:
1) have the ethoxylation positively charged ion monoamine of following formula:
Figure A9719999700101
2). have the ethoxylation cationic diamine of following formula: Or
Figure A9719999700103
Or
Figure A9719999700104
M wherein 1Be N+ or N group; Each M 2Be N+ or N group, at least one M 2It is the N+ group.
3) have the ethoxylation cationic polyamine of following formula:
Figure A9719999700105
4) their mixture; A wherein 1Be
Figure A9719999700106
Or R is H or C 1-C 4Alkyl or hydroxyalkyl, R 1Be C 2-C 12Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkyl arylene, or have the C of about 20 oxygen alkylidene units of 2- 2-C 3Oxyalkylene segment, condition are not form the O-N key; Each R 2Be C 1-C 4Alkyl or hydroxyalkyl, segment-L-X; Or two R 2In conjunction with formation-(CH 2) r-A 2-(CH 2) s-, A wherein 2Be-O-or-CH 2-, r is 1 or 2, and s is 1 or 2, and r+s is 3 or 4; Each R 3Be C 1-C 8Alkyl or hydroxyalkyl, benzyl, segment L-X, or two R 3Or R 2With a R 3In conjunction with forming segment-(CH 2) r-A 2-(CH 2) s-; R 4Be C with replacement of p the position of substitution 3-C 12Alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl; R 5Be C 1-C 12Alkenyl, hydroxy alkylidene, alkylene group, arylidene or alkyl arylene, or have the C of about 20 oxygen alkylidene units of 2- 2-C 3Oxyalkylene segment, condition are not form O-O or O-N key; X is selected from H, C 1-C 4The non-ionic group of alkyl or hydroxy alkyl ester or ether group and their mixture; L contains the polyoxy alkylidene segment :-[(R 6O) m(CH 2CH 2O) n]-hydrophilic chain; R wherein 6Be C 3-C 4Alkylidene group or hydroxy alkylidene, m and n are to make segment-(CH 2CH 2O) n-account for said polyoxy alkylidene segment at least about 50% numerical value; Work as M 2When being N+, d is 1, works as M 2When being N, d is 0; For said positively charged ion monoamine, n is at least about 16, and for said cationic diamine, n is that n is at least about 3 at least about 6 with for said cationic polyamine; P is 3-8; Q is 1 or 0; T is 1 or 0, and condition is when q is 1, and t is 1; Wherein (a) and ratio (b) are 1: 95 to 95: 1.(a) it is 1: 1 to 1: 6 with (b) preferred ratio.
In addition, found detergent composition, and particularly comprise with ethoxylation (gathering) amine of the cationic quaternary ammoniumization of certain content and ratio and contain the detergent component of polyelectrolyte compound of carboxylate radical and especially spray-dired particle is crisp with runny, with do not have agglutinating trend, and if they can adsorb other detergent compound when existing, for example negatively charged ion, positively charged ion and nonionogenic tenside.Therefore, this has reduced the cohesiveness of the composition that comprises this component or spray-dried granules.
Therefore, according to a preferred aspect of the present invention, its relate to comprise above-claimed cpd (a) and (b) and (a) and preferred proportion (b) be 1: 1-1: 10 spray-dired particle.
Preferred anionic counter ion for the cation water-soluble compound are halogen ion, for example Cl -Or Br -, most preferably be MeSO 4 -
Detailed Description Of The Invention
An essential feature of the present invention is the water-soluble cationic compound with removal particulate fouling/native dirt/antiredeposition character, and it is selected from positively charged ion monoamine, diamines and polyamine.
In the present composition or component, cation compound is 1 with the ratio that contains the polyelectrolyte compound of carboxylate radical: 95-95: 1, more preferably 1: 25-25: 1, most preferably 1: 5-5: 1.
When cation compound with contain under the low situation of the polyelectrolyte consumption of carboxylate radical, may be preferred the ratio preferably 1 of the polyelectrolyte compound that contains carboxylate radical in said component and water-soluble cationic compound: 1-1: 10, more preferably 1: 1-1: 4, most preferably 1: 1-1: 2.
If water-soluble cationic compound is present in according in the detergent composition of the present invention the time, by the weight of detergent composition, preferably its content is 0.01%-30%, more preferably 0.1%-15%, most preferably 0.2%-3.0%.
In spray-dired particle, be 1 particularly preferably in the ratio of polyelectrolyte compound that contains carboxylate radical in the said component and water-soluble cationic compound: 1-1: 10, more preferably 1: 1-1: 4, most preferably 1: 1-1: 2.
In spray-dried granules according to the present invention or detergent component; by the weight of spray-dried granules or detergent component, the preferred content of water-soluble cationic compound is 0.1%-30%, more preferably 0.5%-15%; even more preferably 0.5%-7%, most preferably 0.6%-2%.
This spray-dired particle or component preferably exist with granular detergent composition, and by the weight of said composition, it is 5%-90%, more preferably 20%-60%, most preferably 30%-50%.Cationic amine
Be applicable to that the water-soluble cationic compound of the present invention in detergent composition of the present invention or the component comprises ethoxylation positively charged ion monoamine, ethoxylation cationic diamine and ethoxylation cationic polyamine as defined above.
In the formula of above-mentioned cationic amine, R 1Can be side chain (for example:
Figure A9719999700121
Ring-type (for example
Figure A9719999700122
Or most preferably straight chain (for example-CH 2CH 2-,-CH 2CH 2CH 2-) alkylidene group, hydroxy alkylidene, alkylene group, alkyl arylene or oxyalkylene.For ethoxylation cationic diamine, R 1C preferably 2-C 6Alkylidene group.Each R 2Preferably methyl or segment-L-X; Each R 3C preferably 1-C 4Alkyl or hydroxyalkyl, most preferable.
The positive charge of N+ group is offset by the counter anion of proper number.The counter anion that is fit to comprises Cl-, Br-, SO 3 -2, PO 4 -2, MeSO 4 -Deng.Particularly preferred counter anion is Cl-and Br-, but MeSO most preferably 4 -
X can be a non-ionic group, and it is selected from hydrogen (H), C 1-C 4Alkyl or hydroxy alkyl ester or ether group, or their mixture.Preferred ester or ether are respectively acetic ester and methyl ether.Particularly preferred non-ionic group is H and methyl ether.
In following formula, hydrophilic chain L is usually fully by polyoxy alkylidene segment-[(R 6O) m(CH 2CH 2O) n-] form.This polyoxy alkylidene segmental-(R 6O) m-and-(CH 2CH 2O) n-segment may be mixed together or is preferably formed-(R 6O) m-and-(CH 2CH 2O) n-segmental block.R 6C preferably 3H 6(propylidene); M most preferably is 0 preferably 0 to about 5, and promptly this polyoxy alkylidene segment is fully by segment-(CH 2CH 2O) n-form.Segment-(CH 2CH 2O) n-preferably account for the polyoxy alkylidene segmental at least about 85% weight, 100% weight (m is 0) most preferably.
In following formula, for cationic diamine and polyamine, M 1With each M 2N+ group preferably.
Preferred ethoxylation positively charged ion monoamine and diamines have following formula:
Figure A9719999700131
Wherein X and n definition is the same, and a is 0-20, preferred 0-4 (for example ethylidene, propylidene, hexa-methylene), and b is 1 or 0.For preferred cation monoamine (b=0), n is preferably at least about 16, generally in about 20-35 scope.For preferred cation diamines (b=1), n is at least about 12, generally in about 12-42 scope.
In the ethoxylation cationic polyamine of following formula, R 4The C that (straight chain, side chain or ring-type) preferably replaces 3-C 6Alkyl, hydroxyalkyl or aryl; A 1Preferably: N is preferably at least about 12, generally in about 12-42 scope; P is 3-6 preferably.Work as R 4When being the aryl that replaces or alkaryl, q preferably 1, R 5C preferably 2-C 3Alkylidene group.Work as R 4Be the alkyl, hydroxyalkyl or the alkenyl that replace and when q is 0, R 5C preferably 2-C 3Oxyalkylene; When q is 1, R 5C preferably 2-C 3Alkylidene group.
These ethoxylation cationic polyamines can be derived from polyaminoamide, for example:
Figure A9719999700142
Figure A9719999700143
Or
Figure A9719999700144
These ethoxylation cationic polyamines amino propylene oxide derivative of autohemagglutination of also can deriving, for example:
-(OC 3H 6) c-NH 2
CH 3-(OC 3H 6) c-NH 2
-(OC 3H 6) c-NH 2Wherein the numerical value of each c is 2-about 20.The polyelectrolyte compound that contains carboxylate radical
A necessary component of the present invention is one or more polyelectrolyte compounds that contain carboxylate radical, and it has washing assistant or dispersing agent performance.
Preferred these compounds are all or the multi-carboxylic acid compounds of copolymerization, most preferably are the multi-carboxylic acid compounds of copolymerization, and wherein said multi-carboxylic acid compounds's acid mono comprises at least two carboxyls that separated by no more than 2 carbon atoms.These multi-carboxylic acid compounds' salt also is taken into account in the present invention.Aspect preferred, multi-carboxylic acid compounds of the present invention comprises at least 12 carboxylate group.
Contain the polyelectrolyte compound of carboxylate radical if be present in according in the detergent composition of the present invention, by the weight of this detergent composition, preferably its content is 0.01%-40%, more preferably 0.1%-10%, most preferably 0.2%-6%.
Contain the polyelectrolyte compound of carboxylate radical if be present in the detergent component of the present invention, by the weight of this detergent component, preferably its content is 0.05%-30%, more preferably 0.1%-15%, more preferably 0.15%-7%, most preferably 0.2%-2.0% or be more preferably to 1.2%.
In said component is under the situation of spray-dried granules, and by the weight of spray-dried granules, the content that contains the polyelectrolyte compound of carboxylate radical is preferably 0.2%-2.0%, or is more preferably to 1.2%.
This spray-dired particle or this component, by the weight of granular detergent composition, preferably with 5%-90%, more preferably 20%-60%, most preferably 30%-50% content is present in the granular detergent composition.
The polymer electrolyte metallic substance that contains carboxylate radical can be by polymerization or the suitable unsaturation monomer of copolymerization, and preferably the monomer of its sour form prepares.The unsaturation monomer acids that polymerizable forms suitable polymeric polycarboxylic acid is selected from vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.These this paper contain the monomer segment that does not contain carboxylate radical that exists in the polyelectrolyte compound of carboxylate radical for example vinyl methyl ether, vinylbenzene, ethene etc. also be fit to, condition is that this segment does not account for more than 40% weight.The material that contains carboxylate radical also can randomly comprise for example unit, nonionic interval of other monomeric unit.For example, the nonionic that is fit to can comprise vinyl alcohol or vinyl-acetic ester in the unit at interval.
The particularly preferred polyelectrolyte compound that contains carboxylate radical is based on the multipolymer of vinylformic acid/toxilic acid.This material comprises the water-soluble salt of the multipolymer of vinylformic acid and toxilic acid/maleic anhydride.The molecular-weight average of the multipolymer of this sour form preferably can be at 1000-100000, more preferably at 2000-75000, or even more preferably to 70000 scopes, but most preferably be that molecular-weight average is the multipolymer of 2500-20000, or in another embodiment preferred molecular-weight average 60000 to 75000 or even to 70000 scopes.In this multipolymer, the pulsating ratio of propylene acid group and maleate is generally 30: 1-1: 30, more preferably 10: 1-1: 1, and most preferably 4: 1-7: 3 scopes.The water-soluble salt of this vinylformic acid/maleic acid can comprise for example ammonium salt of basic metal, ammonium and replacement.Such vinylformic acid/the maleic acid that is fit to is known material, its be described in December 15 nineteen eighty-two disclosed European Patent Application No. 66915 and on September 3rd, 1986 disclosed EP193360 in.
Other polyelectrolyte compound that contains carboxylate radical that is fit to can be obtained by vinylformic acid.It is this that to be suitable for of the present invention be for example polyacrylic water-soluble salt based on the polymerizing acrylic acid thing.The molecular-weight average of the homopolymer of this sour form is preferably in the 1800-100000 scope, more preferably in the 2000-10000 scope, most preferably in the 3000-5000 scope.The water-soluble salt of this acrylate copolymer can comprise for example ammonium salt of basic metal, ammonium and replacement.The such polymkeric substance that is fit to is known material.The application of such polyacrylate in detergent composition has been disclosed in the United States Patent (USP) 3308067 that for example authorize the 7 days March in 1967 of Diehl.
Also be applicable to the present invention based on polyamino compound, comprise those that obtain by aspartic acid, for example be disclosed among EP-A-305282, EP-A-305283 and the EP-A-351629 those.
Be applicable to that the other example that the object of the invention contains the polyelectrolyte compound of carboxylate radical comprises toxilic acid/vinylformic acid/vinyl alcohol ter-polymers.This material also is disclosed among the EP193360, comprises for example ter-polymers of 45/45/10 vinylformic acid/toxilic acid/vinyl alcohol.
Contain the ter-polymers that is selected from toxilic acid, vinylformic acid and poly aspartic acid monomeric unit, those that particularly have a molecular-weight average 5000-20000 also are applicable to the present invention.
The polyelectrolyte compound that contains carboxylate radical of Shi Heing is the polyelectrolyte that contains ethylene glycol in addition, particularly molecular weight 1000-10000, more preferably 2000-8000, most preferably from about those of 4000.
Other polyelectrolyte compound that preferably contains carboxylate radical is those compounds that generally have hydrophilic skeleton and at least one hydrophobic side chain.
Preferred such polyelectrolyte compound that contains carboxylate radical has molecular weight between 500-100000, and more preferably at 1000-70000, particularly between the 1500-10000, or another embodiment preferred is from 2800-6000.Being used for the polyelectrolyte compound that contains carboxylate radical of the present invention can be for example by using conventional water based polymerization method to prepare, and the method that is fit to is described in for example GB8924477, among GB8924478 and the GB8924479.
The hydrophilic skeleton of general polymerization thing mainly is straight chain (main chain of this skeleton accounts at least 50% of this skeleton weight, preferably more than 75%, most preferably more than 90%), and the suitable monomer component of hydrophilic skeleton is for example unsaturated C 1-C 6Acid, ether, alcohol, aldehyde, ketone or ester, sugar unit, oxyalkyl units, maleic anhydride and saturated polyvalent alcohol be glycerine for example.Preferred hydrophobic side chain is made up of alkoxyl group, for example butylene oxide ring and/or propylene oxide and/or have the alkyl or the alkenyl chain of 5-24 carbon atom.Hydrophobic grouping can by hydrophilic relatively key for example the polyethoxye key link to each other with hydrophilic skeleton.
Preferred such polyelectrolyte compound that contains carboxylate radical is the polymkeric substance of describing in WO91/08281.
The preferred counter ion that contain the polyelectrolyte compound of carboxylate radical are for example sodium, magnesium or calcium ion.Spray-dried granules
Preferred ingredients comprises the spray-dried granules that can be used in the detergent composition according to the present invention.Detergent composition can be basically by this granulometric composition, but preferred detergent composition comprises this particle and has other component that different chemical is formed.
Spray-dried granules of the present invention is to make by the method that comprises the spraying drying step.This spraying drying step has produced spray-dried granules, and generally its free water content is lower than 10% weight, preferably is lower than 7%, or more preferably less than 6%.
Here said moisture content is by 2 gram detergent particles samples being placed on for example in the Petri dish, and this sample was placed 10 minutes in the heating chamber of height to 160 ℃, measured then because the weight loss that moisture evaporation causes.
Generally, particle of the present invention is to make by the following method, will comprise cation compound and contain carboxylate radical polyelectrolyte lotion or slip or mix thing and make particle and dry by spray-drying process well known in the art.
The method for preparing spray-dried granules comprises that preparation comprises the aqueous solution-dispersion of final grain fraction, is commonly referred to lotion or slip or mixes thing.
Other component (it will be included in the spray-dried granules) of mixing thing in adding before, cation compound and the polyelectrolyte that contains carboxylate radical can mix.In addition, other component (will be included in the final spray-dried granules) of mixing thing in adding before, cation compound and the polyelectrolyte that contains carboxylate radical can mix with other the organic compound in will being included in final spray-dried granules.In addition, cation compound can add crutcher simultaneously and mix in the thing with the polyelectrolyte that contains carboxylate radical with other component that will be included in the final spray-dried granules.
In order to save the energy and to increase the throughput of drying plant, mix thing have usually suitable highly filled, 40%-80% for example, the material of equal amount for example is a 10%-60% water.Can use more water, but can increase energy requirement, output of column reduces, and the product that obtains may be clamminess and have relatively poor flowability, and can not obtain required low density base-material and final detergent composition particle usually.This is mixed thing and preferably has 50 ℃ of-100 ℃ of temperature, generally has 80 ℃ before drying step.
Mix thing and spray in drying tower by one or more nozzles under high pressure (40-100 clings to usually, and preferred 70-90 crust is typically at about 80 crust) then, the dry air that passes through in drying tower is with the resulting droplet drying globulate particle of mixing thing.Also can use the atomizer that is equal to of other design to replace nozzle.The preferably spray drying tower is designed to adverse current, and the height of tower is 5-25 rice normally, and the hot gas flow that enters is the gaseous product of oil or gaseous combustion normally, and temperature is 150 ℃ of-400 ℃ of scopes, and the exit flow temperature is usually at 50 ℃-160 ℃.Also can use parallel tower, wherein obtain similar entrance and exit gas flow temperature.
Selectedly be used to produce the jet size of mixing the thing drop and should make and form particle, preferred 0.1mm to 3.0mm with preferred size.Preferably, when from the spray tower discharging, all particles but can be removed any out-of-size particle by screening in this size range basically, also size can be reduced to required size range and maybe can be circulated to identical or follow-up mixing in the thing.
Mixing the preferred component in addition of thing can be anion surfactant, cationic softener or cats product, nonionogenic tenside, vitriol and carbonate, and hydrotropic agent.
Randomly, after drying is finished, obtain particle at desired particle size range, other detergent compound or component can add in this particle, preferably (it can be a concentrated aqueous solution by this compound of fusion or component with this fused compound or component, but preferably not moisture) be ejected on the surface of the rolling basal granule in oblique-roller, by this cylinder, particle moves to discharge end by high feed end.
This particle can add in the detergent composition by any method well known in the art.Preferred this particle is to do to mix in other detergent component.Other detergent component
Also can contain other detergent component according to detergent composition of the present invention or component.The exact nature of these other components and its incorporation will depend on the physical form of component and the exact nature of its employed washing operation.
Preferably contain one or more according to component of the present invention or detergent composition and be selected from following other detergent component: tensio-active agent, other washing assistant, sequestrant, SYNTHETIC OPTICAL WHITNER, bleach precursor, bleach catalysts, other organic polyhydroxyl compound, enzyme, suds suppressor, other lime soap dispersing agent, other soil-suspending agent and anti redeposition agent, dirt release agent, spices and corrosion inhibitor.Cationic polymers
Preferred component in addition can be the other cationoid polymerisation ethoxylation amine compound with removal particulate fouling/native dirt/anti-redeposition, and it is selected from water-soluble cationic polymer.These polymkeric substance comprise polymer backbone, at least 2 M groups and at least one L-X group, and wherein M is connected with skeleton or becomes holistic cation group with skeleton; X is a non-ionic group, is selected from H, C 1-C 4Alkyl or hydroxy alkyl ester or ether group and their mixture; Be linking group M and X or X is connected to hydrophilic chain on the polymer backbone with L.
Here said term " polymer " skeleton " be meant that group M is connected with L-X or becomes holistic polymerized segment with it.In this term, comprise oligopolymer skeleton (2-4 unit) and real polymer backbone (5 or more a plurality of unit).
Here said term " connection " meaning is that this group hangs on the polymer backbone, and the example is represented by following general structural formula A and B:
Figure A9719999700191
Here it is the part that this group constitutes polymer backbone that said term " hangs over " meaning, and the example is represented by following general structural formula C and D:
Can use any polymer backbone, as long as the cationic polymers that forms is water miscible and has the great soil group of removal dirt/antiredeposition character.The polymer backbone that is fit to can get autohemagglutination urethane, polyester, polyethers, polymeric amide, pi etc., polyacrylate, polyacrylamide, polyvingl ether, polyethylene, polypropylene and similarly polyalkylene, polystyrene and similarly poly-alkyl arylene, polyalkylene amine, polyalkyleneimine, polyvinylamine, PAH, polydiene propyl group amine, polyvinylpyridine, polyaminotriazole, polyvinyl alcohol, amino gather 1, inferior urea of 3-and their mixture.
M can be any compatible cation group, and it comprises the positively charged center of N+ (quaternised).This quaternised positively charged center can be represented by following general structural formula E and F:
Particularly preferred M group is those groups that contain the quaternized center of being represented by general structural formula E.This cation group optimum position becomes an integral body near polymer backbone or with polymer backbone.
The positive charge at N+ center is offset by the counter anion of proper number.The counter anion that is fit to comprises Cl -, Br -, SO 3 2-, SO 4 2-, PO 4 2-, MeOSO 3 -Deng.Particularly preferred counter anion is Cl -And Br.
X can be a non-ionic group, is selected from hydrogen (H), C 1-C 4Alkyl or hydroxy alkyl ester or ether group and their mixture.Preferred ester or ether group are respectively acetic ester and methyl ether.Particularly preferred non-ionic group is H and methyl ether.
Be applicable to that the ratio that cationic polymers in the granular detergent component of the present invention generally has cation group M and a non-ionic group X is about 1: 1-1: 2.But for example (promptly contain group L-X) and blended cationic/nonionic monomer, the ratio of cation group M and non-ionic group X can change by suitable copolymerization positively charged ion, nonionic.The ratio of M and X group can be usually about 2: 1-1: 10 scopes.In the preferred cation polymkeric substance, this ratio is about 1: 1-1: 5.The polymkeric substance that is obtained by this copolymerization generally is random, and promptly positively charged ion, nonionic and blended cationic/nonionic monomer are with no tumor-necrosis factor glycoproteins copolymerization.
The unit that contains M and L-X group can account for 100% of cationic polymers of the present invention.But, also allow in polymkeric substance, to comprise other unit (preferred nonionic).Other unitary example comprises acrylamide, vinyl ether and contains non-season tertiary amine group (M 1) those unit of (it contains the N center).These other unit can account for polymkeric substance and (contain the unit of M and L-X group, comprise M 1-L-X group accounts for about 10%-100% of polymkeric substance) 0%-about 90%.Usually, these other unit accounts for the 0%-about 50% of polymkeric substance (unit that contains M and L-X group accounts for about 50%-100% of polymkeric substance).
The number of each M and L-X group is usually at about 2-200.Typically, the number of each M and L-X group is at about 3-100.The number of preferred each M and L-X group is at about 3-40.
Non-other segment that is used for linking group M and X or is connected polymer backbone, hydrophilic chain L is usually fully by polyoxy alkylidene segment-[(R ' O) m(CH 2CH 2O) n]-form.This polyoxy alkylidene segmental-(R ' O) m-and-(CH 2CH 2O) n-can mix, or preferably-(R ' O) m-and-(CH 2CH 2O) n-segment forms block.R ' is C preferably 3H 6(propylidene); M preferably 0-is about 5, most preferably is 0; Promptly this polyoxy alkylidene segment is fully by-(CH 2CH 2O) n-segment is formed.Segment-(CH 2CH 2O) n-preferably account for the polyoxy alkylidene segmental at least about 85%, 100% weight (m is 0) most preferably.For-(CH 2CH 2O) n-segment, n are usually at about 3-100.Preferred n is about 12-42.
(2 or more a plurality of) segment-L-X of plural number also can connect together and be connected on the group M or on the polymer backbone, the example is represented by following general structural formula G and H:
Figure A9719999700211
For example, by obtaining for example G and H structure with Racemic glycidol and group M or with the hydroxyl of polymer backbone reaction and the follow-up formation of ethoxylation.
The representational type of cationic polymers of the present invention is as follows: A. gathers urethane, polyester, polyethers, polymeric amide or similar polymkeric substance.
The cationic polymers that one class is fit to gets autohemagglutination urethane, polyester, polyethers, polymeric amide etc.These polymkeric substance comprise and are selected from the unit with formula I, II and III:
Figure A9719999700222
A wherein 1Be: Or
Figure A9719999700224
X is 0 or 1; R is H or C 1-C 4Alkyl or hydroxyalkyl; R 1Be C 2-C 12Alkylidene group, hydroxy alkylidene, alkylene group, cyclic alkylidene, arylidene or alkyl arylene or have the C of about 20 oxygen alkylidene units of 2- 2-C 3Oxyalkylene segment, condition be not with A 1Form O-O or O-N key; When x is 1, R 2Be-R 5-, unless work as A 1Be: Or-(OR 8) y-or-OR 5-time, condition be not with A 1Form O-O or O-N key, and R 3Be-R 5-, unless work as A 1Be:
Figure A9719999700231
Or-(R 8O) y-or-R 5During O-, condition be not with A 1Form O-O or O-N key; When x is 0, R 2Be:
Figure A9719999700232
Figure A9719999700233
Or
Figure A9719999700234
And R 3Be-R 5-; R 4Be C 1-C 4Alkyl or hydroxyalkyl, or segment-(R 5) k-[(C 3H 6O) m(CH 2CH 2O) n]-X; R 5Be C 1-C 12Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkyl arylene; Each R 6Be C 1-C 4Alkyl or hydroxyalkyl, or segment-(CH 2) r-A 2-(CH 2) s-, A wherein 2Be-O-or-CH 2-; R 7Be H or R 4R 8Be C 2-C 3Alkylidene group or hydroxy alkylidene; X is H,
Figure A9719999700235
-R 9Or its mixture, wherein R 9Be C 1-C 4Alkyl or hydroxyalkyl; K is 0 or 1; M and n are feasible-(CH 2CH 2O) n-segment accounts for-[(C 3H 6O) m(CH 2CH 2O) n]-segment is at least about 85% numerical value; M is 0-about 5; N is at least about 3; R is 1 or 2, s be 1 or 2 and r+s be 3 or 4; Y is 2-about 20; U, v and w numerical value are to make to have at least 2 N+ centers and at least 2 X groups.
In following formula, A 1Preferably:
Figure A9719999700241
Or
Figure A9719999700242
A 2Preferably-O-; X preferably 1; R is H preferably.R 1Can be straight chain (for example-CH 2-CH 2-CH 2-,
Figure A9719999700243
) or (for example prop up Alkylidene group, hydroxy alkylidene, alkylene group, cyclic alkylidene, alkyl arylene or oxyalkylene; Work as R 1Be C 2-C 3During the oxyalkylene segment, the preferably about 2-12 of the number of oxygen alkylidene unit; R 1C preferably 2-C 6Alkylidene group or phenylene most preferably are C 2-C 6Alkylidene group (for example ethylidene, propylidene, hexa-methylene).R 2Preferably-OR 5-or-(OR 8) y-; R 3Preferably-R 5O-or-(OR 8) y-; R 4And R 6Methyl preferably.Resemble R 1The same, R 5Can be straight or branched, preferably C 2-C 3Alkylidene group; R 7Preferably H or C 1-C 3Alkyl; R 8Ethylidene preferably; R 9Methyl preferably; X is H or methyl preferably; K preferably 0; M preferably 0, r and s each preferably 2; Y is 2-about 12 preferably.
In following formula, when the number of N+ center and X group was 2 or 3, n was preferably at least about 6; N most preferably is at least about 12, generally for u+v+w all in the 12-42 scope.For homopolymer (v and w are 0), the preferably about 3-20 of u.For random copolymers (u is at least 1 or is preferably 0), each preferably about 3-40 of v and w.
B. polyacrylate, polyacrylamide, polyvingl ether or similarly polymkeric substance.
Another kind of suitable cationic polymers derives from polyacrylate, polyacrylamide, polyvingl ether etc.These polymkeric substance comprise and are selected from the unit with formula IV, V and VI:
Figure A9719999700251
A wherein 1Be
Figure A9719999700252
Or
Figure A9719999700253
Figure A9719999700254
R is H or C 1-C 4Alkyl or hydroxyalkyl; R 1Be the C that replaces 2-C 12Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkyl arylene or C 2-C 3Oxyalkylene; Each R 2Be C 1-C 12Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkyl arylene; Each R 3Be C 1-C 4Alkyl or hydroxyalkyl, or segment-(R 2) k-[(C 3H 6O) m(CH 2CH 2O) n]-X, or in conjunction with formation-(CH 2) r-A 2-(CH 2) s-, A wherein 2Be-O-or-CH 2-; Each R 4Be C 1-C 4Alkyl or hydroxyalkyl, or two R 4In conjunction with formation-(CH 2) r-A 2-(CH 2) s-segment; X is H, -R 5Or its mixture, wherein R 5Be C 1-C 4Alkyl or hydroxyalkyl; J is 1 or 0; K is 1 or 0; M and n are feasible-(CH 2CH 2O) n-segment accounts for-[(C 3H 6O) m(CH 2CH 2O) n]-segment is at least about 85% numerical value; M is 0-about 5; N is at least about 3; R is 1 or 2, s be 1 or 2 and r+s be 3 or 4; U, v and w numerical value are to make to have at least 2 N+ centers and at least 2 X groups.
In following formula, A 1Preferably: Or
Figure A9719999700262
A 2Preferably-O-; R is H preferably.R 1Can be straight chain (for example-CH 2-CH-CH 2-,
Figure A9719999700263
) or side chain is (for example
Figure A9719999700264
The alkylidene group, hydroxy alkylidene, alkylene group, alkyl arylene or the oxyalkylene that replace; R 1The C of Qu Daiing preferably 2-C 6The C of alkylidene group or replacement 2-C 3Oxyalkylene, most preferably: Or
Figure A9719999700266
Each R 2C preferably 2-C 3Alkylidene group, each R 3And R 4Methyl preferably; R 5Methyl preferably; X is H or methyl preferably; J preferably 1; K preferably 0; M preferably 0; R and s each preferably 2.
In following formula, n, u, v and w can change according to n, u in poly-urethane and the similar polymkeric substance, v and w.C. polyalkylene amine, polyalkyleneimine or similarly polymkeric substance.
Another kind of suitable cationic polymers derives from polyalkylene amine, polyalkyleneimine etc.These polymkeric substance comprise and are selected from the unit with formula VII, VIII and IX:
Figure A9719999700271
R wherein 1Be C 2-C 12Alkylidene group, hydroxy alkylidene, alkylene group, cyclic alkylidene, arylidene or alkyl arylene or have the C of about 20 oxygen alkylidene units of 2- 2-C 3Oxyalkylene segment, condition are not form the O-N key; Each R 2Be C 1-C 4Alkyl or hydroxyalkyl, or segment-(R 3) k-[(C 3H 6O) m(CH 2CH 2O) n]-X; R 3Be C 1-C 12Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkyl arylene; M ' is N+ or N center; X be H, -R 4Or its mixture, wherein R 4Be C 1-C 4Alkyl or hydroxyalkyl; When M ' was N+, d was 1, and when M ' was N, d was 0; When M ' was N+, e was 2, and when M ' was N, e was 1; K is 1 or 0; M and n are feasible-(CH 2CH 2O) n-segment accounts for-[(C 3H 6O) m(CH 2CH 2O) n]-segment is at least about 85% numerical value; M is 0-about 5; N is at least about 3; X, y and z numerical value are to make to have at least 2 M ' groups, at least 2 N+ centers and at least 2 X groups.
In following formula, R 1Can be as the R in poly-urethane and the similar polymkeric substance 1Equally change; Each R 2Methyl or segment-(R preferably 3) k-[(C 3H 6O) m(CH 2CH 2O) n]-X; R 3C preferably 2-C 3Alkylidene group; R 4Methyl preferably; X is H preferably; K preferably 0; M preferably 0.
In following formula, when the number of M ' and X group was 2 or 3, n was preferably at least about 6; N most preferably is at least about 12, for x+y+z all in the typical range of about 12-42.Generally, x+y+z is that 2-is about 40, preferred 2-about 20.For the polymkeric substance of short chain, x+y+z can be in the 2-9 scope, and has 2-9 N+ center and 2-11 X group.For long chain polymer, x+y+z is at least 10, preferably in about 42 scopes of 10-.For the polymkeric substance of short chain and long-chain, M ' group generally is the mixture with about 50-100%N+ center and the about 50%N of 0-center.
The preferred cation polymkeric substance derives from C in this class 2-C 3Polyalkylene amine (x+y+z is 2-9) and polyalkyleneimine (x+y+z is at least 10, preferred 10-about 42).Particularly preferred positively charged ion polyalkylene amine and polyalkyleneimine are the poly-ethyleneamines (PEA) of positively charged ion and polyethylene imine based (PEI).These preferred cation polymkeric substance comprise the unit with following general formula:
Figure A9719999700282
R wherein 2(preferable methyl), M ', X, d, x, y, z and n definition are the same; A is 1 or 0.
Before ethoxylation, the PEA that uses in preparation cationic polymers of the present invention has following general formula:
Figure A9719999700292
Wherein x+y+z is 2-9, and a is 0 or 1 (the about 100-400 of molecular weight).Each hydrogen atom that is connected with each nitrogen-atoms is represented the activity site of follow-up ethoxylation.For preferred PEA, x+y+z is about 3-7 (the about 140-310 of molecular weight).These PEA can obtain through fractionation then by ammonia and ethylene dichloride reaction.Resulting general PEA is Triethylenetetramine (TETA) (TETA) and tetren (TEPA).More than five amine, i.e. hexamine, seven amine, eight amine and nine possible amine, they are the similar mixtures of deutero-, can not be by the distillation fractionation, and the material that may comprise other for example cyclammonium and particularly piperazine.Also may there be the cyclammonium of being with side chain, wherein has nitrogen-atoms.Referring to the United States Patent (USP) 2792372 of the Dickson that authorizes May 14 nineteen fifty-seven, it has described the preparation of PEA.
Minimum level for the native dirt of preferred removal/desired ethoxylation of antiredeposition performance can change according to the number of unit among the PEA.Be that n is preferably at least about 6 under 2 or 3 the situation at y+z.At y+z is under the situation of 4-9, when n is at least about 3 the time, can obtain desirable benefit.For preferred cation PEA, n is at least about 12, and the typical case is in about 12-42 scope.
Prepare the PEI that uses in the polymkeric substance of the present invention, had molecular weight at least about 440 before ethoxylation, its representative has at least about 10 unit.The preferred PEI that uses in these polymkeric substance of preparation has the about 600-1800 of molecular weight.The polymer backbone of these PEI can be represented by following general formula: Wherein the summation of x, y and z is represented enough big numerical value, to obtain having the polymkeric substance of afore mentioned rules molecular weight.Although the straight-chain polymer skeleton is possible, also may there be side chain.In this polymkeric substance, exist primary, the relative proportion of the second month in a season and tertiary amine can change, it depends on the preparation method.The distribution of amine groups is generally as follows:
-CH 2CH 2-NH 2????????????30％
-CH 2CH 2-NH-???????????40％
-CH 2CH 2Each hydrogen atom that-N-30% is connected with each nitrogen-atoms of PEI is represented the activity site of follow-up ethoxylation.These PEI can be by for example at catalyzer for example in the presence of carbonic acid gas, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, the acetate etc., and the polymerization ethylenimine prepares.The concrete grammar of preparation PEI is disclosed in the United States Patent (USP) 2182306 of the Ulrich that authorizes December 5 nineteen thirty-nine etc.; The United States Patent (USP) 3033746 of the Mayle that on May 8th, 1962 authorized etc.; The United States Patent (USP) 2208095 of the Esselmann that on July 16th, 1940 authorized; The United States Patent (USP) 2806839 of the Crowther that authorize September 17 nineteen fifty-seven; With in the United States Patent (USP) 2533696 of the Wilson that authorizes May 21 nineteen fifty-one (all quoting for referencial use) at this paper.
Define as following formula, for positively charged ion PEI, n is at least about 3.But it should be noted that the minimum level for the removal soil dirt/desired ethoxylation of antiredeposition performance that is fit to can increase with the increase of PEI molecular weight, particularly surpasses about 1800.In addition, the ethoxylation degree of preferred polymkeric substance is to increase along with the increase of PEI molecular weight.For having the PEI of molecular weight at least about 600, n is preferably at least about 12, generally in about 12-42 scope.For the PEI with molecular weight at least 1800, n is preferably at least about 24, generally in about 24-42 scope.
D. diallyl amine polymer
Another kind of suitable cationic polymers is derived from those of diallyl amine.These polymkeric substance comprise and are selected from the unit with formula X and XI:
Figure A9719999700311
R wherein 1Be C 1-C 4Alkyl or hydroxyalkyl, or segment-(R 2) k-[(C 3H 6O) m(CH 2CH 2O) n]-X; R 2Be C 1-C 12Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkyl arylene; Each R 3Be C 1-C 4Alkyl or hydroxyalkyl, or be combined together to form segment-(CH 2) r-A-(CH 2) s-, wherein A be-O-or-CH 2-; X is H,
Figure A9719999700313
-R 4Or its mixture, wherein R 4Be C 1-C 4Alkyl or hydroxyalkyl; K is 1 or 0; M and n are feasible-(CH 2CH 2O) n-segment accounts for-[(C 3H 6O) m(CH 2CH 2O) n]-segment is at least about 85% numerical value; M is 0-about 5; N is at least about 3; R is 1 or 2, s be 1 or 2 and r+s be 3 or 4; X is 1 or 0; When x was 0, y was 1, and when x was 1, y was 0; The numerical value of u and v is to make to have at least 2 N+ centers and at least 2 X groups.
In following formula, A preferably-O-; R 1Methyl preferably; Each R 2C preferably 2-C 3Alkylidene group; Each R 3Methyl preferably; R 4Methyl preferably; X is H preferably; K preferably 0; M preferably 0; R and s each preferably 2.
In following formula, when the number of N+ center and X group respectively was 2 or 3, n was preferably at least about 6, and n preferably at least 12, and general u+v is in about 12-42 scope.Generally, v is 0, and u is that 2-is about 40, preferred 2-about 20.Other tensio-active agent
Detergent composition of the present invention or component preferably contain other tensio-active agent, and it is selected from negatively charged ion, nonionic, positively charged ion, both sexes and zwitterionics and their mixture.
The type and the kind of typical negatively charged ion, nonionic, both sexes and zwitterionics in the US3929678 of the Laughlin of on December 30th, 1975 promulgation and Heuring, have been listed.Other example is listed in " tensio-active agent and washing composition " (volume I and II, Schwartz, Perry and Berch).Suitable cationic surfactants is listed in the US4259217 of the Murphy of promulgation on March 31st, 1981.
Both sexes and zwitterionics when existing, general and one or more negatively charged ion and/or nonionic surfactant combinations use.Anion surfactant
Detergent composition of the present invention or component preferably comprise other anion surfactant.Basically any anion surfactant that is used for washing purposes all can be included in detergent composition of the present invention.They can comprise anion sulfate, sulfonate, carboxylate salt and sarcosinate surfactant (comprise for example ammonium salt of sodium, potassium, ammonium and replacement, for example single, two and triethanolamine salt).The anion sulfate acid salt surfactant is preferred.
Other anion surfactant comprises isethionate, for example fatty acid amide, alkyl succinate and the sulfosuccinate of acyl isethinate, N-acyl taurine salt, N-methyltaurine, sulfosuccinic acid monoesters (especially saturated and undersaturated C 12-C 18Monoesters), sulfosuccinic acid diesters (especially saturated and unsaturated C 6-C 14Diester), N-acyl sarcosinate.Resinous acid and hydrogenated resin acid also are suitable, rosin, staybelite and the resinous acid and the hydrogenated resin acid that for example are present in or are obtained by tallow oil.The anion sulfate acid salt surfactant
Be suitable for anion sulfate tensio-active agent of the present invention and comprise straight chain and side chain primary and secondary alkyl-sulphate, alkyl ethoxy sulfate, fatty oil acylglycerol vitriol, alkyl phenol epoxy ethane ether salt, C 5-C 17Acyl group-N-(C 1-C 4Alkyl) and-N-(C 1-C 2Hydroxyalkyl) vitriol of glucosamine sulfate and alkyl poly glucoside, for example vitriol of alkyl polyglucoside (the not Sulfated compound of the nonionic of Miao Shuing herein).
Alkyl sulfate surfactant is preferably selected from straight chain and side chain uncle C 10-C 18Alkyl-sulphate, more preferably C 11-C 15Branched-chain alkyl vitriol and C 12-C 14Straight-chain alkyl sulfate.
Alkyl ethoxy sulfate surfactant is preferably selected from C 10-C 18Alkyl-sulphate, its per molecule by about 0.5 to about 20 moles of ethylene oxide ethoxylations.Alkyl ethoxy sulfate surfactant is more preferably C 11-C 18, C most preferably 11-C 15Alkyl-sulphate, its per molecule be by 0.5-7, preferred 1-5 moles of ethylene oxide ethoxylation.
Of the present invention especially preferred aspect, adopt the mixture of preferred alkyl-sulphate and alkyl ethoxy sulfate surfactant.This mixture is open in PCT patent application WO93/18124.The anion sulfoacid salt surfactant
Be applicable to that anionic sulphonate tensio-active agent of the present invention comprises C 5-C 20Linear alkylbenzene sulfonate, alkyl ester sulfonate, C 6-C 22Uncle or secondary paraffin sulfonate, C 6-C 24Alkene sulfonate, sulfonation poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil acylglycerol sulfonate and their any mixture.The anionic carboxylic acid salt surfactant
The anionic carboxylate tensio-active agent that is suitable for comprises alkyl ethoxy carboxylate, alkyl polyethoxye multi-carboxylate's tensio-active agent and soap (' alkyl carboxyl '), the secondary soap of some of Miao Shuing especially herein.
Suitable alkyl ethoxy carboxylate comprises formula RO (CH 2CH 2O) xCH 2COO -M +Compound, wherein R is C 6-C 18Alkyl, x are 0 to 10, and ethoxylate distribute to make by weight, and wherein to be that 0 amount of substance is less than about 20% for x, and M is a positively charged ion.Suitable alkyl polyethoxye multi-carboxylate tensio-active agent comprises formula RO-(CHR 1-CHR 2-O)-R 3Compound, wherein R is C 6-C 18Alkyl, x are 1 to 25, R 1And R 2Be selected from hydrogen, formyloxy, amber acidic group, hydroxy succinic acid base and their mixture, and R 3Be replacement or unsubstituted alkyl and their mixture that is selected from hydrogen, contains 1 to 8 carbon atom.
Suitable soap surfactant comprises secondary soap surfactant, and it contains the carboxyl unit that is connected in secondary carbon(atom).Being used for preferred secondary soap surfactant of the present invention is water miscible member, and it is selected from 2-methyl isophthalic acid-undecanoic acid, 2-ethyl-1-capric acid, 2-propyl group-1-n-nonanoic acid, 2-butyl-1-is sad and the water-soluble salt of 2-amyl group-1-enanthic acid.Can comprise that also some soap is as suds suppressor.The basic metal sarcosinate surfactant
Other suitable anion surfactant is formula R-CON (R 1) CH 2The basic metal sarcosinate of COOM, wherein R is C 5-C 17Straight or branched alkyl or alkenyl, R 1Be C 1-C 4Alkyl, M are alkalimetal ions.Preferred embodiment is the myristyl and the oleoyl methyl sarcosinate of sodium-salt form.Alkoxy-based non-ionic surface active agent
Basically any alkoxy-based non-ionic surface active agent all is applicable to the present invention, preferred ethoxylation and propoxylation nonionogenic tenside.
The preferred alkoxylated tensio-active agent can be selected from ethoxylate/propoxylated glycerine condenses and the ethoxylate of nonionic and the condensation product of propylene oxide/ethylenediamine adduct of propylene glycol of oxyethyl group/propoxylated fatty alcohol, the nonionic of ethoxylated alcohol, the nonionic of alkylphenol condensation, the nonionic of nonionic.Nonionic alcohol alcoxylates tensio-active agent
Fatty alcohol is applicable to the present invention with oxyalkylene, the especially oxyethane of about 1-25 mole and/or the condensation product of propylene oxide.The alkyl chain of fatty alcohol can be a straight or branched, and uncle or secondary is contained 6-22 carbon atom usually.Especially preferred be have 8-20 carbon atom alkyl alcohol with by every mol of alcohol, the condensation product of 2-10 moles of ethylene oxide.The nonionic polyhydroxy fatty acid amide surfactant
Be applicable to that polyhydroxy fatty acid amide of the present invention is a formula R 2CONR 1The compound of Z, wherein R 1Be hydrogen, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, oxyethyl group, propoxy-or their mixture, preferred C 1-C 4Alkyl, more preferably C 1Or C 2Alkyl, most preferably C 1Alkyl (being methyl); R 2Be C 5-C 31Alkyl, preferred straight chain C 5-C 19Alkyl or alkenyl, more preferably straight chain C 9-C 17Alkyl or alkenyl, most preferably straight chain C 11-C 17Alkyl or alkenyl or its mixture; Z has at least three hydroxyls directly to be connected polyhydroxy alkyl on the linear hydrocarbyl chain or its alkoxy derivative (preferred ethoxylation or propoxylation).Z is preferably obtained by reducing sugar in reductive amination process, and more preferably Z is a glycosyl.The nonionic fatty acid amide surfactant
The suitable fatty acids acidamide surfactant comprises having formula: R 6CON (R 7) 2Compound, R wherein 6Be to contain 7-21, the alkyl of preferred 9-17 carbon atom, each R 7Be selected from hydrogen, C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl and-(C 2H 4O) xH, wherein x is 1-3.Nonionic alkyl polysaccharide tensio-active agent
It is open at the US4565647 of the Llenado of on January 21st, 1986 promulgation to be used for suitable alkyl polysaccharide of the present invention, and it contains for example glycan glycosides hydrophilic radical of the hydrophobic grouping of 6-30 carbon atom and glycan, and it contains 1.3-10 sugar unit.
Preferred alkyl poly glucoside has following formula:
R 2O (C nH 2nO) t(glycosyl) xR wherein 2Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and their mixture, wherein alkyl contains 10-18 carbon atom; N is 2 or 3; T is 0-10, and x is 1.3-8.Glycosyl is preferably obtained by glucose.Amphoterics
Be applicable to that amphoterics of the present invention comprises amine oxide surfactant and alkyl both sexes carboxylic acid.
Suitable amine oxide comprises having formula R 3(OR 4) xN 0(R 5) 2Compound, R wherein 3Be selected from alkyl, hydroxyalkyl, amido propyl group and contain the alkyl phenyl of 8-26 carbon atom or their mixture; R 4Be alkylidene group or hydroxy alkylidene or their mixture that contains 2-3 carbon atom; X is 0-5, preferred 0-3; With each R 5Be alkyl or the hydroxyalkyl that contains 1-3 carbon atom, or contain the polyethylene oxide group of 1-3 ethylene oxide group.Preferred C 10-C 18Alkyl dimethyl amine oxide and C 10-C 18Amidoalkyl dimethyl oxidation amine.
The suitable example of alkyl both sexes carboxylic acid is by Miranol, Inc., Dayton, Miranol (TM) the C2M Conc. of NJ preparation.Zwitterionics
Zwitterionics also can add in detergent composition of the present invention or the component.These tensio-active agents broadly are described as the derivative of derivative, the heterocycle second month in a season and tertiary amine of secondary and tertiary amine or the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.Trimethyl-glycine and sultaine tensio-active agent are typically to be used for zwitterionics of the present invention.
Suitable trimethyl-glycine is to have formula R (R 1) 2N +R 2COO -Compound, wherein R is C 6-C 18Alkyl, each R 1C normally 1-C 3Alkyl and R 2Be C 1-C 5Alkyl.Preferred trimethyl-glycine is C 12-18Dimethyl Ammonium hexanoate and C 10-18Amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.The beet alkali surface activator title complex also is applicable to the present invention.Cats product
If cats product exists, the preferred cationic tensio-active agent is selected from cation mono alkoxylated amines tensio-active agent, positively charged ion dialkoxy amine tensio-active agent and their mixture.
The content of cats product, the weight by detergent composition is preferably 0.1%-20%, more preferably 0.4%-7%, most preferably 0.5%-3%.Cation mono alkoxylated amines tensio-active agent
Cats product can be a cation mono alkoxylated amines tensio-active agent, and it has formula I R wherein 1Be to contain 6-18 the carbon atom of having an appointment, preferred about 16 carbon atoms of 6-, the most preferably from about alkyl of 6-14 carbon atom or alkenyl; R 2And R 3Each contains the alkyl of about 3 carbon atoms of 1-, preferable methyl, most preferably R naturally 2And R 3It all is methyl; R 4Be selected from hydrogen (preferably), methyl and ethyl, X-provides electroneutral negatively charged ion, for example chlorine, bromine, methylsulfate, sulfate radical etc.A is an alkoxyl group, particularly oxyethyl group, propoxy-or butoxy; P is that 0-is about 30, and preferred 2-is about 15, and most preferably 2-is about 8, and preceding topic condition is if A is oxyethyl group, R 4Be that hydrogen and p are 1, R then 1Not C 12-C 14Alkyl.
In the formula I, preferred ApR 4Group has p=1 and is the hydroxyalkyl with no more than 6 carbon atoms, thus-and the OH group separated with quaternary nitrogen atoms by no more than 3 carbon atoms.Particularly preferred ApR 4Group is-CH 2CH 2OH ,-CH 2CH 2CH 2OH ,-CH 2CH (CH 3) OH and-CH (CH 3) CH 2OH ,-CH 2CH 2OH is particularly preferred.Preferred R 1Group has no more than 10 carbon atoms, or not even more than 8 or 9 carbon atoms.Preferred R 1Group is a straight chained alkyl.Have 8-11 carbon atom or have the straight chain R of 8-10 carbon atom 1Group is preferred.Highly preferred this cats product is R wherein 1Be C 8-C 10Alkyl, p are 1, and A is an oxyethyl group, R 2And R 3It is the formula I compound of methyl.
Be used for the highly preferred cation mono alkoxylated amines of another kind of the present invention tensio-active agent and have following formula:
Figure A9719999700362
R wherein 1Be C 10-C 18Alkyl and their mixture, particularly C 10-C 14Alkyl, preferred C 10And C 12Alkyl, X provide any negatively charged ion easily of charge balance, preferred chlorine or bromine.Positively charged ion dialkoxy amine tensio-active agent
Cats product can also be a positively charged ion dialkoxy amine tensio-active agent, and it has the general formula II:
Figure A9719999700371
R wherein 1Be to contain about 18 carbon atoms of the 8-that has an appointment, preferred about 16 carbon atoms of 10-, the most preferably from about alkyl of about 14 carbon atoms of 10-or alkenyl part; R 2Be the alkyl that contains 1-3 carbon atom, preferable methyl; R 3And R 4Can change independently, they are selected from hydrogen (preferably), methyl and ethyl; X -Be to be enough to provide electroneutral negatively charged ion, for example chlorine, bromine, methylsulfate, sulfate radical etc.A and A ' can change independently, respectively are selected from C 1-C 4Alkoxyl group, particularly oxyethyl group (promptly-CH 2CH 2O-), propoxy-, butoxy and their mixture; P is that 1-is about 30, and preferred 1-is about 4, and q is that 1-is about 30, and preferred 1-is about 4, and most preferably p and q are 1.
Be used for the highly preferred positively charged ion dialkoxy of the present invention amine tensio-active agent and have following formula: R wherein 1Be C 10-C 18Alkyl and its mixture, preferred C 10, C 12, C 14Alkyl and its mixture, X provides any suitable negatively charged ion of charge balance, preferred chlorine.About above-mentioned positively charged ion dialkoxy amine formula, in preferred compound, R 1Be by (coconut) C 12-C 14Moieties lipid acid obtains, R 2Be methyl, ApR 3And A ' pR 4All are monosubstituted ethoxies.
Be applicable to that other positively charged ion dialkoxy amine tensio-active agent of the present invention comprises the compound of following formula:
Figure A9719999700373
R wherein 1Be C 10-C 18Alkyl, preferred C 10-C 14Alkyl, p are that 1-is about 3 independently, and q is that 1-is about 3, R 2Be C 1-C 3Alkyl, preferable methyl, X is a negatively charged ion, particularly chlorine or bromine.
Other compound of the above-mentioned type comprises wherein oxyethyl group (CH 2CH 2O) unit (EO) is by butoxy (Bu), isopropoxy [CH (CH 3) CH 2O] and [CH 2CH (CH 3O] unit (i-Pr) or positive propoxy unit (Pr) or EO and/or Pr and/or i-Pr unit mixture displaced those.The water soluble detergency promoter compound
Detergent component or composition can contain other water soluble detergency promoter compound.
The water soluble detergency promoter compound that is fit to comprises carboxylate salt material, borate, phosphoric acid salt and any above-mentioned mixture.
The borate washing assistant and contain the washing assistant that forms borate substance (but its washing composition store or wash conditions under product borate) be the useful water soluble detergency promoter of the present invention.
The suitable example of water-soluble phosphate washing assistant is tripolyphosphate an alkali metal salt, trisodium phosphate, potassium and ammonium, sodium orthophosphate and potassium, partially poly-/sodium phosphate, and wherein extent of polymerization is the salt of about 6-21 and phytinic acid.
The carboxylate salt washing assistant that is applicable to detergent composition of the present invention or component can be monomer or oligomer types (containing 4 carboxylate group of as many as), but because cost and performance, the monomer multi-carboxylate is normally preferred.
The other carboxylate salt that is fit to that contains a carboxyl comprises the water-soluble salt of lactic acid, glycolic acid and their ether derivant.The carboxylate salt that contains two carboxyls comprises the water-soluble salt of succsinic acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid and ether carboxylic acid and sulfinyl carboxylic acid.The carboxylate salt that contains three carboxyls especially comprises water-soluble citrate, itaconate and citraconate and succinate derivative; for example the carboxymethyl oxygen base succinate of in English Patent 1379241, describing, the lactoyl oxygen base succinate of in English Patent 1389732, describing and the aminosuccinic acid salt of in Holland's application 7205873, describing and oxygen Quito carboxylate salt material of in English Patent 1387447, describing; 2-oxa--1 for example; 1,3-tricarballylic acid salt.
The carboxylate salt that contains four carboxyls is included in the oxygen di-succinate of describing in the English Patent 1261829,1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent carboxylate salt of sulfo group be included in English Patent 1398421 and 1398422 and US3936448 in the sulfo-succinic acid salt derivative described and the sulfonation pyrolysis Citrate trianion in English Patent 1439000, described.Preferred carboxylate salt in addition is that each molecule contains the nearly hydroxycarboxylate of three carboxyls, more preferably Citrate trianion.
The parent acid of monomer or two polymeric multi-carboxylate sequestrants or with their mixture of salt, for example citric acid or Citrate trianion/citric acid mixture also can be used as builder component.Be partly dissolved or undissolved washing-aid compound
Detergent component of the present invention or composition can contain and be partly dissolved or undissolved washing-aid compound, and its content in detergent composition is pressed composition weight meter, is generally 1%-80%, preferred 10%-70%, most preferably 20%-60%.
Basically the example that is not dissolved in the washing assistant of water comprises sodium silicoaluminate.
Suitable aluminosilicate zeolite has formula Na Z[(AlO 2) Z(SiO 2) Y] xH 2The unit structure cell of O, wherein z and y are at least 6; The mol ratio of z and y is 1.0-0.5, and x is at least 5, preferred 7.5-276, more preferably 10-264.Silico-aluminate is a hydrated form, preferably contains 10%-28%, more preferably the crystal of the bonding scheme water of 18%-22%.
Aluminosilicate zeolite can be naturally occurring material, but preferably synthetic obtaining.Synthetic crystal aluminosilicate ion exchange material is available with title zeolite A, zeolite B, zeolite P, X zeolite, zeolite HS and their mixture, and zeolite A has following formula:
Na 12[(AlO 2) 12(SiO 2) 12] xH 2O wherein x is 20-30, especially 27.X zeolite has following formula: Na 86[(AlO 2) 86(SiO 2) 106] 276H 2O.
Another kind of preferred aluminosilicate zeolite is a zeolite MAP builder.The content of zeolite MAP is pressed composition weight meter, is 1%-80%, more preferably 15%-40%.
Zeolite MAP is described among the EP384070A (Unilever).It is defined as is that the ratio with silicon and aluminium is not more than 1.33, preferably in the 0.9-1.33 scope, more preferably at the composite alkali aluminum-silicate of the zeolite P of 0.9-1.2 scope type.
Particularly advantageous is that the ratio of silicon and aluminium is not more than 1.15, the zeolite MAP more preferably no more than 1.07.
Aspect preferred, the zeolite MAP builder washing assistant has granularity, is expressed as d 50Value is 1.0-10.0 micron, more preferably 2.0-7.0 micron, most preferably 2.5-5.0 micron.
d 50The particulate diameter of value representation 50% weight is less than these data.Granular size can be passed through, and particularly for example uses the micro-determination techniques of scanning electronic microscope by the analytical technology of routine or measures by laser particle analyzer.Other determines d 50The method of value is disclosed among the EP384070A.Heavy metal ion chelating agent
Detergent component of the present invention or composition preferably contain the heavy metal ion chelating agent as optional ingredient.Heavy metal ion chelating agent has been meant the component of chelating heavy metal ion effect.These components can also have calcium and magnesium sequestering power, but preferred the demonstration in conjunction with heavy metal ion, for example selectivity of iron, manganese and copper.
Press composition weight meter, heavy metal ion chelating agent is usually with 0.005%-20%, preferred 0.1%-10%, and more preferably 0.25%-7.5%, most preferably the content of 0.5%-5% exists.
Be used for suitable heavy metal ion chelating agent of the present invention and include organic phosphonates, for example poly-(alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate and nitrilo trimethylene phosphonic salt of amino alkylidenyl.
Preferred above-mentioned substance is diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid salt), hexamethylene-diamine four (methylene phosphonic acid salt) and hydroxy ethylene 1,1 diphosphonate.
Be used for other suitable heavy metal ion chelating agent of the present invention and comprise nitrilotriacetic acid(NTA) and polyaminocarboxylic acid, for example ethylenediamine tetraacetic acid (EDTA), ethylidene pentaacetic acid, ethylenediamine disuccinic acid, quadrol two pentanedioic acids, 2-hydroxyl propylene diamine disuccinic acid or its any salt.Especially preferred quadrol-N, the ammonium salt of N '-disuccinic acid (EDDS) or its basic metal, alkaline-earth metal, ammonium or replacement or their mixture.
Being used for other suitable heavy metal ion chelating agent of the present invention is iminodiacetic acid derivatives, 2-hydroxyethyl oxalic acid of for example describing in EP-A-317542 and EP-A-399133 or glyceryl iminodiethanoic acid.Also can use iminodiethanoic acid-N-2-hydroxypropyl sulfonic acid and the aspartic acid N-carboxyl methyl N-2-hydroxypropyl-3-sulfonic acid sequestrant in EP-A-516102, described.Beta-alanine-the N that in EP-A-509382, describes, N '-oxalic acid, aspartic acid-N, single acetate of N '-oxalic acid, aspartic acid-N-and imino-diacetic succsinic acid sequestrant also are suitable for.
EP-A-476257 has described suitable amido functional group sequestrant.EP-A-510331 has described the suitable sequestrant that is obtained by collagen, Keratin sulfate or casein.EP-A-528859 has described suitable alkyl imino oxalic acid sequestrant.Lutidine acid and 2-phosphono-containing butane-1,2, the 4-tricarboxylic acid also is suitable.G-NH2-N, N '-disuccinic acid (GADS), quadrol-N-N '-two pentanedioic acid (EDDG) and 2-hydroxyl propylene diamine-N-N '-disuccinic acid (HPDDS) also is suitable.The organic peroxide acid bleach systems
The preferred feature of detergent composition of the present invention or component is the organic peroxide acid bleach systems.In a preferred embodiment, bleach systems contains hydrogen peroxide cource and organic peroxide acid bleach precursor compound.Situ reaction by precursor and hydrogen peroxide cource can produce organic peroxide acid.Preferred hydrogen peroxide cource comprises inorganic perhydrate SYNTHETIC OPTICAL WHITNER.In another preferred embodiment, the ready-formed organic peroxide acid directly adds in the composition.Also can imagine the composition that contains with the mixture of ready-formed organic peroxide acid blended hydrogen peroxide cource and organic peroxy acid precursor.Inorganic perhydrate SYNTHETIC OPTICAL WHITNER
Inorganic perhydrate salt is preferred hydrogen peroxide cource, and these salt are usually with basic metal, and the form of particular certain cancers adds, and is 1%-40% by its content of composition weight meter, more preferably 2%-30%, most preferably 5%-25%.
The example of inorganic perhydrate salt is perborate, percarbonate, superphosphate, persulphate and persilicate.Inorganic perhydrate salt is an alkali metal salt normally.The inorganic perhydrate salt that can comprise the crystalline solid forms of no supplementary protection; yet; for some perhydrate salt, in the preferred embodiment of this particulate composition, the perhydrate salt that uses coated form is to be provided at the preferable package stability of perhydrate salt in the granular product.Suitable coating compounds comprises inorganic salt, for example alkalimetal silicate, carbonate or borate or their mixture, or organic substance, for example paraffin, oil or fatty soap.
Sodium peroxoborate is preferred perhydrate salt, can be standard type NaBO 2H 2O 2Monohydrate form or formula NaBO 2H 2O 23H 2The tetrahydrate form of O.
Alkali metal percarbonate, especially SPC-D are preferred perhydrate of the present invention.SPC-D is to have corresponding to 2Na 2CO 33H 2O 2The addition compound of formula can have been bought with crystalline solid.
The peroxide Potassium peroxysulfate is another the inorganic perhydrate salt that is used for detergent composition of the present invention or its component.Peroxyacid bleach precursor
Peroxyacid bleach precursor is the compound that generates peroxy acid in crossing hydrolysis reaction with hydroperoxidation.Peroxyacid bleach precursor is expressed from the next usually: Wherein L is a leavings group, and X is any functional group basically, makes the structure of the peroxy acid that generated in crossing hydrolysis reaction be:
Figure A9719999700421
The peroxyacid bleach precursor compound preferably in by detergent composition weight with 0.5%-20%, more preferably 1%-15%, most preferably the content of 1.5%-10% adds.
Suitable peroxyacid bleach precursor compound contains one or more N-or O-carboxyl groups usually, the optional kind from wide region of this precursor.Suitable kind comprises the acyl derivative of acid anhydride, ester, inferior acid amides, lactan and imidazoles and oxime.The example of useful material is described in GB-A-1586789 in these kinds.Suitable ester GB-A-836988,864798,1147871,2143231 and EP-A-0170386 in open.Leavings group
Leavings group, L group hereinafter referred to as, it must have enough activity for crossing hydrolysis reaction, with in the time of the best (for example wash(ing)cycle) react.Yet if L is too active, this promoting agent is used for bleaching composition and will be difficult to stablize.
Preferred L group is selected from: With
Figure A9719999700423
Figure A9719999700424
With With their mixture, wherein R 1Be alkyl, aryl or the alkaryl that contains 1-14 carbon atom, R 3Be the alkyl chain that contains 1-8 carbon atom, R 4Be H or R 3, R 5Be that alkenyl chain and the Y that contains 1-8 carbon atom is H or solubilizing group.Any R 1, R 3And R 4Can comprise for example alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical, acid amides and ammonium or alkyl ammonium group replacement basically by any functional group.
Preferred solubilizing group is-SO 3 -M +,-CO 2 -M +,-SO 4 -M +,-N +(R 3) 4X -And O ← N (R 3) 3, most preferably-SO 3 -M +With-CO 2 -M +, R wherein 3Be the alkyl that contains 1-4 carbon atom, M provides deliquescent positively charged ion to bleach activator, and X provides deliquescent negatively charged ion to bleach activator.Preferred M is the ammonium cation of basic metal, ammonium or replacement, most preferably sodium and potassium, and X is halogenide, oxyhydroxide, methylsulfate or acetic acid anion.Alkyl percarboxylic acids bleach precursor
Alkyl percarboxylic acids bleach precursor forms percarboxylic acids in crossing hydrolysis reaction, the preferred precursor of this class provides peracetic acid through hydrolysis reaction.
The alkyl peroxycarboxylic acid precursors compound of preferred inferior acid amide type comprises N-, N, N 1N 1Tetra-acetylatedization Alkylenediamine, wherein alkylidene group contains 1-6 carbon atom, and especially wherein alkylidene group contains the compound of 1,2 and 6 carbon atom, and tetra acetyl ethylene diamine (TAED) is especially preferred.
Other preferred alkyl peroxycarboxylic acid precursors comprises 3,5,5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt (iso-NOBS), acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (NOBS), acetoxyl group benzene sulfonic acid sodium salt (ABS) and penta-acetyl glucose.The alkyl peroxy acids precursor that acid amides replaces
The alkyl peroxy acids precursor compound that amido replaces is applicable to the present invention, and it comprises the compound of following general formula:
Figure A9719999700441
Or
Figure A9719999700442
R wherein 1For comprising the alkyl of 1-14 carbon atom, R 2For comprising the alkylidene group of 1-14 carbon atom, R 5For H or contain the alkyl of 1-10 carbon atom, and L is essentially any leavings group.The bleaching activity immunomodulator compounds that this class acid amides replaces is described in EP-A-0170386.Peroxybenzoic acid precursors
The peroxybenzoic acid precursors compound provides peroxybenzoic acid in crossing hydrolysis reaction.Suitable O-acylations peroxybenzoic acid precursors compound comprises the benzoyl product of replacement and unsubstituted benzoyl oxygen base benzene sulfonate and Sorbitol Powder, glucose and all carbohydrates and benzoyl reagent, and the inferior amide compound of this class comprises the urea that N-benzoyl succinimide, four benzoyl quadrols and N-benzoyl replace.Suitable imidazole type peroxybenzoic acid precursors comprises N-benzoyl imidazoles and N-benzoyl benzo imidazoles.The peroxybenzoic acid precursors that contains the N-acyl group that other is useful comprises N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.The positively charged ion peroxyacid precursor
Positively charged ion peroxyacid precursor compound forms the positively charged ion peroxy acid through hydrolysis reaction.
The positively charged ion peroxyacid precursor is normally by replacing positively charged functional group, for example ammonium or alkyl ammonium group, and the peroxy acid of the suitable peroxyacid precursor compound of preferred ethyl or methyl ammonium partly forms.Usually as having suitable negatively charged ion, for example halogen ionic salt is present in the solid detergent composition positively charged ion peroxyacid precursor.
The peroxyacid precursor compound that is replaced by positively charged ion can be the precursor compound of the derivative of aforesaid peroxybenzoic acid or its replacement.In addition, the peroxyacid precursor compound can be the alkyl peroxy acids precursor that alkyl peroxycarboxylic acid precursors compound or acid amides hereinafter described replace.
The positively charged ion peroxyacid precursor US4904406,4751015,4988451,43977757,5269962,5127852,5093022,5106528, UK1382594, EP475512,458396 and 284292 and JP87-318332 in describe.
The example of preferred cation peroxyacid precursor is described in UK Patent Application 9407944.9 and US patent application 08/298903,08/298650,08/298904 and 08/298906.
Suitable positively charged ion peroxyacid precursor comprises alkyl or benzoyl oxygen base sulfonate, N-acylations hexanolactam and the tetra-acetylated glucose benzoyl peroxide of single benzoyl that any ammonium or alkylammonium replace.Preferred N-acylations hexanolactam cationoid peroxyacid precursor comprises trialkyl ammonium methylene radical benzoyl caprolactam and trialkyl ammonium methylene radical alkyl hexanolactam.Benzoxazine organic peroxy acid precursor
Also suitable is disclosed benzo oxazinyl precursor compound in for example EP-A-332294 and EP-A-482807, especially has formula:
Figure A9719999700451
R wherein 1Be H, alkyl, alkaryl, aryl or aralkyl.The ready-formed organic peroxide acid
Except or in addition the organic peroxide acid bleach precursor compound, the organic peroxide acid bleach systems can contain the ready-formed organic peroxide acid, presses composition weight meter, its content is 1%-15%, more preferably 1%-10% usually.
The compound that the acid amides that preferred organic peroxide acid type of compounds is following general formula replaces: R wherein 1Be alkyl, aryl or the alkaryl that contains 1-14 carbon atom, R 2Be alkylidene group, arylidene and the alkyl arylene that contains 1-14 carbon atom, R 5For H or contain alkyl, aryl or the alkaryl of 1-10 carbon atom.The organic peroxy carboxylic acid that this class acid amides replaces is described in EP-A-0170386.
Other organic peroxide acid comprises diacyl and four acyl peroxides, especially diperoxy dodecanedioic acid, diperoxy tetradecane diacid and diperoxy Thapsic acid.List and two is crossed nonane diacid, brassylic acid crossed by list and two and N-also is applicable to the present invention to benzoyl-amido peroxide hexanodioic acid.Enzyme
Another preferred ingredient that is used for detergent composition of the present invention or component is one or more additional enzymes.
Preferred additional enzymes material comprises industrial available cellulase, endolase, at, lipase, amylase, neutrality and Sumizyme MP, esterase, polygalacturonase, Sumylact L and the peroxidase that is routinely added in the detergent composition.Suitable enzyme is discussed in US3519570 and 3533139.
The proteolytic enzyme that preferred commercially available proteolytic enzyme comprises the proteolytic enzyme sold with trade(brand)name Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A/S (Denmark), sold with trade(brand)name Maxatase, Maxacal and Maxapem by Gist-Brocades, the proteolytic enzyme of selling by Genencor International and the proteolytic enzyme of selling with trade(brand)name Opticlean and Optimase by Solvay Enzymes.Proteolytic enzyme can add in the detergent composition of the present invention by the content of composition weight meter 0.0001%-4% organized enzyme.
Preferably amylase comprises, for example the α-Dian Fenmei that the special bacterial strain by bacillus licheniformis of detailed description obtains among the GB-1269839 (Novo).Preferred industrial available amylase comprises the amylase of for example being sold with trade(brand)name Termamyl and BAN with trade(brand)name Rapidase sale and Novo IndustriesA/S by Gist-Brocades.Amylase can add in the detergent composition of the present invention by the content of composition weight meter 0.0001%-2% organized enzyme.
Lipolytic enzyme can be by composition weight meter with 0.0001%-2%, preferred 0.001%-1%, and most preferably the active lipolytic enzyme content of 0.001%-0.5% exists.
Lipase can be fungi or bacterial origin, for example by the detritus enzyme belong to, the bacterial strain of the generation lipase of Thermomicrobium (Thermomyces) or Rhodopseudomonas, comprise that pseudomonas pseudoalcaligenes or Pseudomonas fluorescens obtain.The lipase that is obtained by the chemistry or the gene modification mutation of these bacterial strains also can be used among the present invention.Preferred lipase is obtained by pseudomonas pseudoalcaligenes, and it is described in the EP-B-0218272 that authorizes.
The gene that obtains by Humicola fetal hair bacterium by the clone described in another preferred lipase of the present invention such as the EP-A-0258068 and aspergillus oryzae as the host in the lipase that obtains of expressing gene, by Novo Industri A/S Bagsvaerd, Denmark obtains with trade(brand)name Lipolase industrial for it.Describe among the US4810414 of the Huge-Jinsen that this lipase is also issued on March 7th, 1989 etc.The suds suppressor system
When detergent composition of the present invention or component are used for the use in washing machine composition when preparation, preferably contain preferred 0.05%-10%, most preferably the suds suppressor system of 0.1%-5% content existence by composition weight meter 0.01%-15%.
Be used for suitable suds suppressor system of the present invention and can mainly contain any known defoaming compounds, comprise for example polysiloxane defoaming compounds and 2-alkyl chain triacontanol defoaming compounds.
Defoaming compounds is meant to play and for example suppresses detergent composition solution herein, especially the mixture of foaming or generation any compound of foamy or compound under the situation of stirred solution.
Be used for especially preferred defoaming compounds of the present invention and be the polysiloxane defoaming compounds of any defoaming compounds that comprises silicone components that defines herein.This polysiloxane defoamers also contains silica component usually.Reach herein at industrial normally used term " polysiloxane " and comprise the various relative high molecular weight polymers that contains siloxane unit and all kinds alkyl.Preferred polysiloxane defoamers compound is a siloxanes, especially contains the unitary polydimethylsiloxane of trimethyl silyl end-blocking.
Other suitable defoaming compounds comprises mono carboxylic lipid acid and its water-soluble salt.These materials are described in the US2954347 of the Wayne St.John of promulgation on September 27 nineteen sixty.Mono carboxylic lipid acid and its salt as suds suppressor contain 10-24 carbon atom usually, the hydrocarbyl chain of preferred 12-18 carbon atom.Suitable salt comprises an alkali metal salt, for example sodium, potassium and lithium salts and ammonium and alkanol ammonium salts.
Other suitable defoaming compounds comprises, for example high molecular weight fatty acid ester (for example triglyceride), the fatty acid ester of monovalent alcohol, aliphatic C 18-C 40Ketone (for example stearone) N-alkylation aminotriazine, for example as cyanuric chloride and two or three moles contain that the product of the uncle of 1-24 carbon atom or secondary amine forms three-to six-alkyl melamine or two-to the tetraalkyl diammonium chloride for triazine, propylene oxide, distearyl acid acid amides and single stearyl two basic metal (for example sodium, potassium, lithium) phosphoric acid salt and phosphate ester.
Preferred suds suppressor system contains: (a) defoaming compounds, preferred polysiloxane defoaming compounds, the polysiloxane defoaming compounds that most preferably contains following combined composition: (ⅰ) by polysiloxane defoaming compounds weight with 50%-99%, the polydimethylsiloxane that preferred 75%-95% content exists; (ⅱ) by polysiloxane/silicon-dioxide defoaming compounds weight, content is 1%-50%, the silicon-dioxide of preferred 5%-25%; Wherein said silicon-dioxide/polysiloxane defoaming compounds is with 5%-50% by weight, and the content of preferred 10%-40% adds; (b) compound dispersing agent, the thick multipolymer that most preferably comprises silicone glycol and polyoxyalkylene, wherein the content of polyoxyalkylene is 72-78%, the ratio of oxyethane and propylene oxide is 1: 0.9-1: 1.1, its content is 0.5%-10% by weight, preferred 1%-10%; The thick multipolymer of especially preferred this class silicone glycol is the industrial DOC544 that can be obtained with trade(brand)name DC0544 by DOW Coming; (c) inert support fluid cpds, most preferably containing degree of ethoxylation is 5-50, the C of preferred 8-15 16-C 18Ethoxylated alcohol; Its content is 5%-80% by weight, preferred 10%-70%.
Preferred granular suds suppressing agent system is described in EP-A-0210731, and it comprises polysiloxane Xiao, and to steep compound and fusing point be 50 ℃-85 ℃ organic carrier, and wherein the organic carrier material comprises monoglyceride and contains the lipid acid of the carbochain of 12-20 carbon atom.EP-A-0210721 discloses other preferred granular suds suppressing agent system, and wherein organic carrier is that fusing point is 45 ℃-80 ℃ the lipid acid with the carbochain that contains 12-20 carbon atom or alcohol or their mixture.The polymeric dye transfer inhibitor
Detergent component of the present invention or composition also contain 0.01%-10% by weight, preferred 0.05%-0.5% polymeric dye transfer inhibitor.
The polymeric dye transfer inhibitor is preferably selected from multipolymer, polyvinylpyrrolidonepolymers polymers or their mixture of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole, and wherein these polymkeric substance can be crosslinked polymkeric substance.A) polyamine N-oxide pllymers is applicable to that polyamine N-oxide pllymers of the present invention contains the unit with following structural formula:
Figure A9719999700481
Wherein P is that polymerisable unit and A are X is 0 or 1; R is aliphatic series, aliphatic, the aromatic series of ethoxylation, heterocycle or carbon ring group or its any combination, the part that the nitrogen of N-O group can nitrogen coupled or wherein N-O group is these groups.
The N-O group can be represented by following general structural formula: Or Wherein R1, R2 and R3 are aliphatic group, aromatic series, heterocycle or carbon ring group or their combination, and x and/or y and/or z are 0 or 1, wherein the part that the nitrogen of N-O group can be connected with it or wherein the nitrogen of N-O group constitutes these groups.The N-O group can be the part of polymerizable unit (P) or can link to each other with polymer main chain or both combination.
Wherein the suitable polyamine N-oxide of the part of N-O group formation polymerizable unit comprises polyamine N-oxide, and wherein R is selected from aliphatic series, aromatic series, carbocyclic ring or heterocyclic group.The above-mentioned polyamine N-oxide of one class comprises one group of polyamine N-oxide, and wherein the nitrogen of N-O group constitutes the part of R-group.Preferred polyamine N-oxide compound is that wherein R is a heterocyclic group, for example the polyamine N-oxide of pyridine, pyrroles, imidazoles, pyrroline, piperidines, quinoline, acridine and their derivative.
Other suitable polyamine N-oxide is the polyamine oxide compound that is connected with polymerizable unit of N-O group wherein.These polyamine N-oxide of preferred type are the polyamine N-oxide with logical formula I, and wherein R is aromatic series, heterocycle or carbon ring group, and wherein the nitrogen of N-O functional group is the part of described R group.The example of this compounds is the polyamine oxide compound, and wherein R is a heterogeneous ring compound, for example pyridine, pyrroles, imidazoles and their derivative.
Polyamine N-oxide of the present invention can almost obtain with any extent of polymerization.Extent of polymerization is not crucial, as long as material has required water-soluble and dye suspension ability.Molecular-weight average is generally 500-1000000.B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole
Be suitable for the molecular-weight average that N-vinyl imidazole of the present invention and N-vinylpyrrolidone copolymer have 5000-50000.The N-vinyl imidazole of preferred multipolymer and the mol ratio of N-vinyl pyrrolidone are 1-0.2.C) Polyvinylpyrolidone (PVP)
Detergent component of the present invention or composition can also use the Polyvinylpyrolidone (PVP) (" PVP ") of molecular-weight average as 2500-400000.Suitable Polyvinylpyrolidone (PVP) commercial by ISP Corporation, New York, NY and Montreal obtain, by Canadian ProductName PVPK-15 (viscosity-average molecular weight is 10000), PVPK-30 (molecular-weight average 40000), PVPK-60 (molecular-weight average 160000) and PVPK-90 (molecular-weight average 360000) obtain.PVPK-15 also can be obtained by ISP Corporation.What other was suitable comprises Sokalan HP165 and Sokalan HP12 at the commercial Polyvinylpyrolidone (PVP) that is obtained by BASFCooperation.D) Ju Yi Xi oxazolidinone
Detergent component of the present invention or composition also can use Ju Yi Xi oxazolidinone as the polymeric dye transfer inhibitor, and said Ju Yi Xi oxazolidinone has the molecular-weight average of 2500-400000.E) polyvinyl imidazol
Detergent component of the present invention or composition also can use polyvinyl imidazol as the polymeric dye transfer inhibitor, and described polyvinyl imidazol has the molecular-weight average of 2500-400000.White dyes
Detergent component of the present invention or composition also optionally contain the hydrophilic white dyes of about by weight some type of 0.005% to 5%.
The hydrophilic white dyes of Shi Yonging comprises those with following structural formula in the present invention: R wherein 1Be selected from anilino, the two hydroxyethyls of N-2-and NH-2-hydroxyethyl; R 2Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chlorine and amino; M is a salt-forming cation, for example sodium or potassium.
When in above-mentioned formula, R 1Be anilino, R 2Be N-2-two-hydroxyethyl and M are positively charged ions, for example during sodium, this whitening agent is 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid and its disodium salt.This concrete whitening agent material is sold with trade(brand)name Tinopal-UNPA-GX by Ciba-Geigy company commercial.Tinopal-UNPA-GX is the preferred hydrophilic white dyes that is used for detergent composition of the present invention.
When in above-mentioned formula, R 1Be anilino, R 2Be that N-2-hydroxyethyl-N-2-methylamino and M are positively charged ions, for example during sodium, this whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid disodium salt.This concrete whitening agent material is sold with trade(brand)name Tinopal 5BM-GX by Ciba-Geigy company commercial.
When in above-mentioned formula, R 1Be anilino, R 2Be that morpholino and M are positively charged ions, for example during sodium, this whitening agent is 4,4 '-two [(4-anilino-6-morpholino-s-triazine-2-yl) amino] 2,2 '-stilbene disulfonic acid, its sodium salt.This concrete whitening agent is sold with trade(brand)name Tinopal AMS-GX by Ciba-Geigy commercial.The polymerization dirt release agent
Can randomly use known polymerization dirt release agent in detergent component of the present invention or the composition, hereinafter referred is " SRA ".If you are using, SRA ' s generally accounts for 0.01% to 10.0% of composition weight, is typically 0.1% to 5%, and preferred 0.2% to 3.0%.
Preferred SRA ' s typically has the hydrophilic segment that makes hydrophobic fiber such as polyester and nylon surface hydrophilic, with be deposited on the hydrophobic fiber and in whole washing and rinse cycle, keep the hydrophobic part of adhesion with it, so it is as the fixture of hydrophilic segment.This can be so that spot easier being cleaned in washing process afterwards that produces subsequently of handling with SRA.
Preferred SRA ' s comprises the terephthalate of oligomerisation, and it generally by comprising the method preparation of at least a transesterification/oligomerisation reaction, carries out under metal catalyst such as titanium alkoxide (IV) usually.This ester can use can by one, two, three, four or more position add other monomers preparations of ester structure, certainly, do not form fine and close full crosslinking structure.
SRA ' the s that is fit to comprises the sulfonated products of the ester oligomer that is straight chain basically; it contains oligomer ester skeleton and the oxyalkylene oxygen repeating unit and the allyl group deutero-sulfonation terminal portions covalently bound with skeleton of terephthaloyl, for example described in the U.S. Pat 4968451 of J.J.Scheibel that authorizes in November 6 nineteen ninety and E.P.Gosselink like that.This ester oligomer can prepare through the following steps: (a) ethoxylation allyl alcohol; (b) product and terephthalic acid dimethyl ester (" DMT ") and 1 that will (a) in two step transesterification/oligomerizations, 2-propylene glycol (" PG ") reacts; (C) in water with the product of (b) and sodium metabisulfite reaction; Other SRA ' s comprises the nonionic end capped 1 in the people's such as Gosselink that authorized on December 8th, 1987 the U.S. Pat 4711730,2-propylidene/polyoxyethylene terephthalic acid polyester, for example by poly-(ethylene glycol) methyl ether, DMT, the product of transesterification/oligomerisation preparation of PG and poly-(ethylene glycol) (" PEG "); Other SRA ' s example comprises part and the whole end capped oligomer esters of negatively charged ion in the United States Patent (USP) 4721580 of the Gosselink that authorized on January 26th, 1988, as derive from ethylene glycol (" EG "), PG, DMT and 3, the oligopolymer of 6-two oxa-s-8-hydroxyl perfluorooctane sulfonate; Nonionic end-blocking block polyester oligomerisation compound in the United States Patent (USP) 4702857 of the Gosselink that on October 27th, 1987 authorized, for example by DMT, methyl (Me)-end capped PEG and EG and/or PG preparation, perhaps by DMT, EG and/or PG, the product of the mixture preparation of end capped PEG of Me-and dimethyl-5-sulfoisophthalic acid sodium; With the Maldonado that authorized on October 31st, 1989; negatively charged ion in people's such as Gosselink the U.S. Pat 4877896; especially the end capped terephthalate of sulfo group aroyl; the latter is typical useful SRA ' s in laundry and fabric-conditioning product; one example be by-sulfosalicylic acid list sodium salt, the ester composition of PG and DMT preparation, but randomly preferably also contain the PEG of adding; for example, PEG3400.
SRA ' s also comprises: the simple segmented copolymer of ethylene terephthalate or terephthalic acid propylene glycol ester and polyethylene oxide or poly(propylene oxide) terephthalate, referring to the U.S. Pat 3959230 of the Hay on May 25th, 1976 and the U.S. Pat 3893929 of the Basadur on July 8th, 1975; Derivatived cellulose such as the hydroxy ethers cellulose polymer compound bought from Dow with METHOCEL; C 1-C 4Alkylcellulose and C 4Hydroxy alkyl cellulose is referring to the people's such as Nicol on December 28th, 1976 U.S. Pat 4000093.And methyl cellulose ether, its each anhydroglucose unit has average replacement (methyl) degree and is about 1.6-2.3, and the aqueous solution by 2% is about 80-120 centipoise at 20 ℃ of soltion viscosities of measuring down.This material can METOLOSE SM100 and METOLOSE SM200 buy, they are trade(brand)names of the methyl cellulose ether produced by Shin-etsu Kagaku Kogyo KK.
Another kind of SRA ' s comprises: (I) uses vulcabond coupler and polyester construction banded nonionic terephthalate, referring to people's such as people's such as Violland U.S. Pat 4201824 and Lagasse U.S. Pat 4240918; (II) has the SRA ' s of carboxylate radical end group, and the conversion terminal hydroxy group becomes the trimellitate preparation among known SRA ' s by trimellitic acid 1,2-anhydride is added for it.By suitable selecting catalyst, trimellitic acid 1,2-anhydride forms the end group banded key with polymkeric substance, and this is to carry out by the isolated carboxylicesters of trimellitic acid 1,2-anhydride rather than by opening the acid anhydride key.Nonionic or negatively charged ion SRA ' s can be used as starting raw material, as long as have can esterified hydroxyl end groups for they, referring to people's such as Tung U.S. Pat 4525524; Other type comprises: (III) links the SRA ' s based on the negatively charged ion terephthalate of urethanes, referring to people's such as Violland U.S. Pat 4201824; Other optional ingredient
Other optional ingredient that can be included in component of the present invention or the composition comprises spices, pigment and filling salt, and sodium sulfate is preferred filling salt.Detergent formulations near neutral washing pH
Though detergent component of the present invention, particularly detergent composition comprises and can wash pH (for example about 5-12) component of operation down at wide region, but when they are formulated into when having near neutral washing pH (when concentration is for about 0.1%-2% weight in water under 20 ℃, initial pH is about 7.0-10.5), be particularly suitable.Preparation near neutral washing pH all is preferably for the stability of enzyme with for the set that suppresses dirt.In this preparation, the preferably about 7.0-10.5 of washing pH, more preferably from about 8.0-10.5, most preferably 8.0-9.0.
In the european patent application 83200688.6 that apply for the May 16 nineteen eighty-three that preferred detergent formulations near neutral washing pH is disclosed in J.H.M.Wertz and P.C.E.Goffinet.
The neutralizing agent, buffer reagent, phase modifier, hydrotropic agent that highly preferred component of this type or composition also preferably contain have an appointment 2%-10% weight citric acid and a small amount of (for example being lower than about 20% weight) be tosylate, xylenesulfonate or cumene sulfonate, enzyme stabilizers, foaming regulator, opalizer, antioxidant, sterilant, dyestuff, spices and whitening agent for example, for example those (they quote for referencial use at this paper) of describing in the United States Patent (USP) 4285841 of the Barrat that authorizes on August 25th, 1981 etc.The form of component and composition
Detergent component of the present invention can pass through prepared in various methods, comprise the mixture of all cpds that agglomeration or extruding comprise or be included in the mixture of all cpds in the detergent component, but preferably comprise water-soluble cationic compound and contain the mixture or the slip of the polyelectrolyte compound of carboxylate radical by spraying drying.This can be undertaken by any spray drying process well known in the art.Therefore, the preferably spray-dired particle of detergent component of the present invention or particle or powder.
When component of the present invention was agglomerant particle form, the cation water-soluble compound preferably combined with carrier substance.
Detergent component of the present invention preferably constitutes the part of detergent composition.Various physical form be can adopt according to composition of the present invention, particle, tablet, cake, lozenge and strips comprised.The especially so-called concentrated granular detergent composition of the present composition, it is adapted to pass through the diverting device that is placed in the machine roll of adorning dirty fabric and adds in the washing machine.
Component of the present invention or composition also can be used for or for example comprise the combination of compositions of chlorine bleach with the bleaching compositions of additives.
The water-soluble cationic that comprises in the particulate composition of the present invention is removed the mean particle size of the component of native dirt/antiredeposition compound and should be made preferably that diameter is no more than 40% greater than the particle of 1.8mm, more preferably no more than 15%; Diameter is no more than 40% or preferably be no more than 15% less than the particle of 0.25mm.Preferred average particle size makes the 10%-50% particle have diameter 0.2mm-0.7mm.
Herein Ding Yi term average particle size particle size be by with composition sample on one group of sieve, preferred Tyler sieve sieves into that mass part (common 5 parts) calculates.The weight fraction that obtains is with respect to the aperture curve that draws of sieve, and average particle size particle size is by weight the pore size that 50% sample passes through.
The bulk density of granular detergent composition of the present invention is 500g/l, more preferably 600g/l-1200g/l at least usually.When detergent component was spray-dired particle, particle or powder, the low bulk density composition that contains this component was preferred.Bulk density is measured by simple funnel and cup device, and described device is made up of the conical funnel of installing perpendicular to the bottom, and funnel bottom is equipped with vacuum breaker makes the material in the funnel enter in the cylinder cup of coaxial placement under funnel.Funnel is 130 millimeters high, and the interior diameter at two ends is respectively 130 millimeters and 40 millimeters up and down.Funnel is installed in its lower end and is higher than 140 millimeters places of upper base surface, and the height overall of cup is 90 millimeters, and internal height is 87 millimeters, and internal diameter is 84 millimeters, and normal volume is 500 milliliters.
For measuring, in funnel,, open vacuum breaker with the hand powder of packing into, make powder from the top is packed cup into.The cup of filling is taken out from framework, and by the instrument with straight flange, for example pocket knife was scraped the cup upper edge and was removed excessive powder.The cup of weighing then and filling obtains bulk density value g/l with 2 with the powder weight that obtains is on duty.Need carry out repeated experiments.
Can use for example film-making of any suitable densification process, briquetting or extruding, preferred flaking method is produced closely knit solid.The tablet that is used for the wash up method preferably uses the Rotarytabletpress of standard to produce, applying pressure 5-13KN/cm 2, more preferably 5-11KN/cm 2, make this closely knit solid measure by the C100 experiment of hardness that the I.Holland instrument provides, have minimum hardness 176N-275N, preferred 195N-245N.This method can be used for preparing the homogeneous or the stratiform tablet of virtually any size or shape.Preferred tablet is symmetric, to guarantee this tablet uniform dissolution in washing soln.Clothes washing method
Machine clothes washing method of the present invention generally includes and is used in containing dissolving or disperseing the machine washing detergent component of the present invention of significant quantity in the washing machine, but preferably contains the dirty fabric of aqueous cleaning solution-treated of the composition of this component.The detergent composition of significant quantity is meant, as is generally used for the typical products consumption and washing soln volume in the conventional machine washing method, dissolves or is dispersed in the product that 5-65 rises the 10g-300g in the volume washing soln.
Aspect preferred use, in washing methods, use diverting device.Diverting device is equipped with Betengent product, is used for directly adding product at the washing machine rotating cylinder before beginning wash(ing)cycle.Its volume capacity should be able to make it contain the enough Betengent products that are generally used in the washing methods.
Before washing beginning or before washing machine is packed clothes into or simultaneously or afterwards, the diverting device that Betengent product is housed is placed in the cylinder.After beginning the wash(ing)cycle of washing machine, in rotating cylinder, add entry, the rotation of rotating cylinder synchronism ground.The design diverting device makes it that dry detergent product is housed, but then in wash(ing)cycle in response to the stirring action of rotating cylinder rotation with owing to discharge these products with contacting of washing water.
Can discharge Betengent product for making in washing process, device should have the opening that many products can pass through.In addition, device should be by liquid permeable but the material manufacturing of impermeable solid phase prod, thereby allows to discharge the dissolved product.Betengent product preferably discharges rapidly when begin wash(ing)cycle, thereby in this stage wash(ing)cycle, provides temporary transient partial product high density in the washing machine rotating cylinder.
Preferred diverting device is reusable, and design makes container at dried state with keep globality in wash(ing)cycle.The especially preferred diverting device that is used for composition of the present invention is described in following patent: GB-B-2157717, GB-B-2157718, EP-A-0201376, EP-A-0288345 and EP-A-0288346.In Manufacturing Chemist in November, 1989, the especially preferred diverting device that is used for the granular laundry product also described in the article that the 41-46 page or leaf is delivered by J.Bland, and it is to be commonly referred to " granulette " type.The diverting device of another detergent composition preferred for the present invention is open in PCT patent application WO94/11562.
Especially preferred diverting device is open in EP0343069 and 0343070.Back one application discloses a kind of device, and it comprises the curved envelope of the bag shape form of being extended by sustained ring, and described ring defines a hole, the adequate prod of a wash(ing)cycle that is used for washing methods to be suitable for packing in bag.Part washing medium is gone in the bag by orifice flow, dissolved product, and solution outwards flows in the washing medium by the hole subsequently.Sustained ring is equipped with shield cap and runs off to avoid product that wet, undissolved, and this device generally includes the similar structures that has spiral form by radially wall extension or its mesospore of centre strut expansion with spoke wheel structure formation.
In addition, diverting device can be flexible container, for example bag or box.Bag can be to apply the fibrous texture of protecting materials of impermeable water to keep content, for example in EP0018678 disclosed like that.In addition, as disclosed among the EP0011500,0011501,0011502 and 0011968, it can be made by the synthetic polymeric material that is not dissolved in water, has edge sealing or closure designs with isolated water-bearing media.Meet closing form easily that yew looses comprise be used for handling and sealing by the impervious polymeric film of water, the water-soluble binder at an edge of the box made of polyethylene or polypropylene for example.Machine wash up method
It is contemplated that the machine wash up or clean any appropriate methodology of contaminated tableware, particularly contaminated silverware.
Preferred machine wash up method comprises with the aqueous solution that contains dissolving or disperseed the machine wash up component of significant quantity of the present invention or preferably contained the composition of this component handles contaminated article, is selected from pottery, glassware, holloware, silverware and cutter and its mixture.The machine dishwashing compositions of the significant quantity meaning is to rise dissolving or dispersion 8g-60g product in the washing soln of volume at 3-10, and it is typical products consumption and the washing soln volume that is generally used in the conventional machine wash up method.
That uses among the embodiment writes a Chinese character in simplified form
In detergent composition, the component of writing a Chinese character in simplified form has following implication: LAS: straight chain C 11-13Sodium alkyl benzene sulfonate TAS: tallow alkyl sodium sulfate C XyAS: C 1X-C 1YSodium alkyl sulfate C46SAS:C 14-C 16Secondary (2,3) sodium alkyl sulfate C XyE zS: with the C of Z moles of ethylene oxide condensation 1X-C 1YSodium alkyl sulfate C XYE Z: with the condensation of Z moles of ethylene oxide mainly be the C of straight chain 1X-C 1Y
Primary alconol QAS: R 2N +(CH 3) 2(C 2H 4OH), R 2=C 12-C 14QAS1: R 2N +(CH 3) 2(C 2H 4OH), R 2=C 8-C 11QAS2: R 2N +(CH 3) 2(C 2H 4OH), R 2=C 8APA: C 8-C 10Amido propyl-dimethyl amine soap: straight-chain alkyl carboxylic acid's sodium, by 80/20 of butter and coconut fatty acid
Mixture obtains STS: the stupid sodium sulfonate CFAA of first: C 12-C 14(coconut) alkyl N-methyl glucose amide TFAA: C 16-C 18Alkyl N-methyl glucose amide TPKFA: C 12-C 14Top full cut lipid acid STPP: anhydrous sodium tripolyphosphate TSPP: tetrasodium pyrophosphate zeolite A: formula Na 12(AlO 2SiO 2) 1227H 2The hydrated sodium aluminosilicate of O, main
Particle size is 0.1-10 micron (weight of representing by moisture-free basis) NaSKS-6: formula δ-Na 2Si 2O 5The crystalline layered silicate citric acid: Citric Acid, usp, Anhydrous Powder borate: Sodium Tetraborate carbonate: particle size is the anhydrous sodium carbonate supercarbonate of 200-900 micron: size distribution is the anhydrous sodium bicarbonate silicate of 400-1200 micron: amorphous sodium silicate (SiO 2: Na 2O ratio=2.0: 1) vitriol: anhydrous sodium sulphate sal epsom: anhydrous magnesium sulfate Citrate trianion: citrate trisodium dihydrate, activity 86.4%, particle size branch
Cloth is 425-850 micron MA/AA1: 3: 7 toxilic acid/acrylic copolymer, the about 70000MA/AA2 of molecular-weight average: 4: 6 toxilic acid/acrylic copolymer, the about 3000MA/AA3 of molecular-weight average: 4: 6 toxilic acid/acrylic copolymer, the about 12000AA of molecular-weight average: the polyacrylic acid sodium polymer CM of molecular-weight average 4500: the plain ether of sodium carboxyme-thylcellulose fibre: the polymerization degree is 650 methyl cellulose ether, by Shin Etsu
Chemicals buys proteolytic enzyme: sold with trade(brand)name Savinase by Novo Industries A/S
Proteolytic ferment, have 3.3% weight organized enzyme proteolytic enzyme I: the proteolytic ferment of describing in WO95/10591 has 4%
The weight organized enzyme, sell Alcalase by Genencor Int.Inc.: the proteolytic ferment by Novo Industries A/S sells has
5.3% weight organized enzyme cellulase: sell with trade(brand)name Carezyme by Novo Industries A/S
Cellulase has 0.23% weight organized enzyme amylase: by Novo Industries A/S trade(brand)name Termamyl 120T
The amylase of selling has 1.6% weight organized enzyme lipase: sold by Novo Industries A/S trade(brand)name Lipolase
Lipolytic enzyme has 2.0% weight organized enzyme lipase (1): gone out with trade(brand)name Lipolase Ultra by Novo Industries A/S
The lipolytic enzyme of selling has 2.0% weight organized enzyme Endolase: the Endoglucanase enzyme, sell by Novo Industries A/S,
Has 1.5% weight organized enzyme PB4: formula NaBO 23H 2OH 2O 2Sodium perborate tetrahydrate PB1: formula NaBO 2H 2O 2Anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER SPC-D: formula 2Na 2CO 33H 2O 2SPC-D NOBS: nonanoly acyloxy benzene sulfonate; sodium-salt form NAC-OBS: (6-nonanoyl caproyl) oxygen benzene sulfonate TAED: tetraacetyl ethylene diamine DTPA: diethylene triaminepentaacetic acid(DTPA) DTPMP: diethylenetriamine five (methylene phosphonic acid), by Meng Shan all with commodity
Name Dequest 2060 sells EDDS: quadrol-N, N '-disuccinic acid, (S, S) isomer, sodium
The bleaching of salt form photoactivation: the bleaching of sulfonation phthalocyanine phthalocyanine zinc agent (1) photoactivation of sealing with the cyclodextrin soluble polymer: aluminum phthalocyanine agent (2) whitening agent of sealing with the cyclodextrin soluble polymer 1: 4,4 '-two (2-sulfo group styryl) biphenyl disodium whitening agent 2: 4,4 '-two (4-phenylaminos-6-morpholino-1,3,5-triazine-2-yl) amino)
Stilbene-2:2 '-disulfonic acid disodium HEDP: hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid PEG x: polyoxyethylene glycol, molecular weight is x (general 4000) PEO: polyoxyethylene, molecular-weight average 50000TEPAE: ethoxylation tetren PVI: polyvinyl imidazol, molecular-weight average 20000PVP: polyvinylpyrrolidonepolymers polymers, molecular-weight average 60000PVNO: polyvinylpyridine N-oxide polymer, molecular-weight average 50000PVPVI: the multipolymer of Polyvinylpyrolidone (PVP) and vinyl imidazole, average
Molecular weight 20000QEA1: MeSO 4 -Two ((C 2H 5O) (C 2H 4O) n(CH 3)-N +-C 6H 12-N +-
(CH 3) two ((C 2H 5O)-(C 2H 4O) n), n=20-30QEA2 wherein: two ((C 2H 5O)-(C 2H 4O) n) (CH 3) N +R 1Salt, R wherein 1
Be C 4-C 12Alkyl and n=20-30QEA3: three { (two ((C 2H 5O)-(C 2H 4O) n) (CH 3) N +)-(CONC 3H 6)-
C 3H 6The salt of O, wherein n=20-26SRP1: the end capped polyester SRP2 of negatively charged ion: the short block of diethoxyization poly-(1,2 propylidene phthalic ester) altogether
Polymers PEI: polyethylene imine based, molecular-weight average 1800, each nitrogen-atoms is flat
All ethoxylation degree is 7 ethylidene oxygen residue polysiloxane froth breakings: polydimethylsiloxane foam control agent and polysiloxane-agent oxyalkylene copolymers as dispersion agent, the weight of described foam control agent and described dispersion agent
Than being 10: 1-100: 1 opalizer: water base single styrene latex mixture, by BASF
Aktiengesellschaft sells wax with trade(brand)name Lytron621: paraffin
In following embodiment, all content are that the % with composition weight meter represents: embodiment 1
The following high density granular laundry detergent composition A-F that is applied to especially under the European washing machine condition is according to embodiments of the invention:
????A ?????B ????C ????D ????E ?????F
?LAS ???8.0 ????8.0 ????8.0 ????8.0 ????8.0 ????8.0
?C25E3 ???3.4 ????3.4 ????3.4 ????3.4 ????3.4 ????3.4
?C46AS ???1.0 ????2.0 ????2.5 ????- ????3.0 ????4.0
?C68AS ???3.0 ????2.0 ????5.0 ????7.0 ????1.0 ????0.5
?QAS ???- ????- ????0.8 ????- ????- ????0.8
Zeolite A ???18.1 ????18.1 ????16.1 ????18.1 ????18.1 ????18.1
Zeolite MAP ???- ????4.0 ????3.5 ????- ????- ????-
Carbonate ???13.0 ????13.0 ????13.0 ????27.0 ????27.0 ????27.0
Silicate ???1.4 ????1.4 ????1.4 ????3.0 ????3.0 ????3.0
Vitriol ???26.1 ????26.1 ????26.1 ????26.1 ????26.1 ????26.1
?MA/AA1 ???0.6 ????0.8 ????0.3 ????1.0 ????0.5 ????0.3
?CMC ???0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2
?PB4 ???9.0 ????9.0 ????9.0 ????9.0 ????9.0 ????9.0
?TAED ???1.5 ????1.5 ????1.0 ????1.5 ????- ????1.5
The Mn catalyzer ???- ????0.03 ????0.07 ????- ????- ????-
?DTPMP ???0.25 ????0.25 ????0.25 ????0.25 ????0.25 ????0.25
HEDP ????0.3 ????0.3 ????0.2 ????0.2 ????0.3 ????0.3
EDDS ????- ????- ????0.4 ????0?2 ????- ????-
QEA1 ????1.O ????0.8 ????0.7 ????1.2 ????- ????0.5
QEA2 ????- ????- ????- ????- ????1.O ????0.5
Proteolytic enzyme ????0.26 ????0.26 ????0.26 ????0.26 ????0.26 ????0.26
Amylase ????0.1 ????0.1 ????0.4 ????0.3 ????0.1 ????0.1
The SYNTHETIC OPTICAL WHITNER of photoactivation (ppm) ????15ppm ????15 ????ppm ????15ppm ????15ppm ????15ppm ????15 ????ppm
Whitening agent 1 ????0.09 ????0.09 ????0.09 ????0.09 ????0.09 ????0.09
Spices ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3
The polysiloxane kilfoam ????0.5 ????0.5 ????0.5 ????0.5 ????0.5 ????0.5
Other/accessory constituent to 100%
Density g/ liter ?????850 ????850 ????850 ????850 ????850 ????850
Embodiment 2
The following high density granular laundry detergent composition G-L that is applied to especially under the European washing machine condition is according to embodiments of the invention:
????G ?????H ?????I ????J ????K ?????L
?LAS ???8.0 ?????8.0 ????8.0 ????8.0 ????8.0 ????8.0
?C25E3 ???3.4 ?????3.4 ????3.4 ????3.4 ????3.4 ????3.4
?C46AS ???1.0 ?????2.0 ????2.5 ?????- ????3.0 ????4.0
?C68AS ???3.0 ?????2.0 ????5.0 ????7.0 ????1.0 ????0.5
?QAS ????- ??????- ????0.8 ?????- ?????- ????0.8
Zeolite A ??18.1 ????18.1 ???16.1 ???18.1 ???18.1 ???18.1
Zeolite MAP ????- ?????4.0 ????3.5 ?????- ?????- ?????-
Carbonate ??13.0 ????13.0 ???13.0 ???27.0 ???27.0 ???27.0
Silicate ???1.4 ?????1.4 ????1.4 ????3.0 ????3.0 ????3.0
Vitriol ??26.1 ????26.1 ???26.1 ???26.1 ???26.1 ???26.1
?MA/AA1 ???0.5 ?????0.8 ????0.3 ????1.0 ????0.5 ????0.3
?CMC ???0.2 ?????0.2 ????0.2 ????0.2 ????0.2 ????0.2
?PB4 ???9.0 ?????9.0 ????9.0 ????9.0 ????9.0 ????9.0
?TAED ???1.5 ?????1.5 ????1.0 ????1.5 ?????- ????1.5
The Mn catalyzer ????- ????0.03 ???0.07 ?????- ?????- ?????-
?DTPMP ??0.25 ????0.25 ???0.25 ???0.25 ????0.25 ???0.25
?HEDP ????0.3 ????0.3 ????0.2 ????0.2 ????0.3 ????0.3
?EDDS ?????- ?????- ????0.4 ????0.2 ?????- ?????-
?QEA1 ????1.0 ????0.8 ????0.7 ????1.2 ?????- ????0.5
?QEA2 ?????- ?????- ?????- ?????- ????1.0 ????0.5
Proteolytic enzyme ????0.26 ????0.26 ????0.26 ????0.26 ????0.26 ????0.26
Amylase ????0.1 ????0.1 ????0.4 ????0.3 ????0.1 ????0.1
The SYNTHETIC OPTICAL WHITNER of photoactivation (ppm) ????15 ????ppm ????15 ????ppm ????15 ????ppm ????15 ????ppm ????15 ????ppm ????15 ????ppm
Whitening agent 1 ????0.09 ????0.09 ????0.09 ????0.09 ????0.09 ????0.09
Spices ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3
The polysiloxane kilfoam ????0.5 ????0.5 ????0.5 ????0.5 ????0.5 ????0.5
Other/accessory constituent to 100%
Density g/ liter ????850 ????850 ????850 ????850 ????850 ????850
Embodiment 3
Bulk density is that the following granular laundry detergent compositions M-O of 750g/l is according to composition of the present invention:
????M ????N ????O
?LAS ????5.25 ????5.61 ????4.76
?TAS ????1.25 ????1.86 ????1.57
?C45AS ????- ????2.24 ????3.89
?C25AE3S ????- ????0.76 ????1.18
?C45E7 ????3.25 ????- ????5.0
?C25E3 ????- ????5.5 ????-
?QAS ????0.8 ????2.0 ????-
?QAS1 ????0.4 ????1.0 ????2.5
?STPP ????19.7 ????- ????-
Zeolite A ????19.5 ????19.5
NaSKS-6/ citric acid (79: 21) ????10.6 ????10.6
Carbonate ????6.1 ????21.4 ????21.4
Supercarbonate ????- ????2.0 ????2.0
Citric acid ????0.3 ????0.2 ????-
Silicate ????6.8 ?????- ????-
Sodium sulfate ????39.8 ?????- ???7.0
?PB4 ????5.0 ????12.7 ????-
?TAED ????0.5 ????0.2 ????-
?DPDA ?????- ????- ???0.3
?NACOBS ????1.0 ????2.2 ????-
?DTPMP ????0.25 ????0.2 ???0.2
?HEDP ?????- ????0.3 ???0.3
Proteolytic enzyme ????0.26 ?????- ????0.85 ???0.85
Lipase ????0.15 ?????- ????0.15 ???0.15
Cellulase ????0.28 ????0.28 ???0.28
Amylase ????0.1 ?????- ????0.1 ???0.1
?MA/AA ????0.5 ????0.8 ???0.4
?QEA1 ????1.0 ????1.5 ????-
?QEA2 ?????- ????- ???0.8
?CMC ????0.2 ????0.4 ???0.4
?PVP ?????- ????- ???0.8
The SYNTHETIC OPTICAL WHITNER of photoactivation (ppm) ??15ppm ??27ppm ?27ppm
Whitening agent 1 ??0.08 ??0.19 ??0.19
Whitening agent 2 ???- ??0.04 ??0.04
Spices ??0.3 ??0.3 ??0.3
Polysiloxane kilfoam 1 ??0.5 ??2.4 ??2.4
Other/accessory constituent to 100% ??n.a. ??n.a.
Embodiment 4
The following detergent formulations that is applied to especially under the European washing machine condition is according to embodiments of the invention:
????P ????Q ????R ????S
The powder of blowing
??????????????LAS ????6.0 ????5.0 ???11.0 ????6.0
??????????????TAS ????2.0 ?????- ?????- ????2.0
Zeolite A ?????- ???27.0 ?????- ???20.0
??????????????STPP ???24.0 ?????- ???24.0 ?????-
Vitriol ????9.0 ????6.0 ???13.0 ?????-
????????????MA/AA2 ????2.0 ?????- ?????- ????4.0
????????????MA/AA1 ?????- ????1.0 ????0.5 ?????-
Silicate ????7.0 ????3.0 ????3.0 ????3.0
???????????????CMC ????1.0 ????1.0 ????0.5 ????0.6
??????????????QEA1 ????0.8 ????1.0 ????3.0 ????0.5
??????????????QEA2 ?????- ?????- ?????- ????0.5
Whitening agent ????0.2 ????0.2 ????0.2 ????0.2
The polysiloxane kilfoam ????1.0 ????1.0 ????1.0 ????0.3
?????????????DTPMP ????0.4 ????0.4 ????0.2 ????0.4
Spraying
?????????????C45E7 ?????- ?????- ?????- ????5.0
?????????????C45E2 ????2.5 ????2.5 ????2.0 ?????-
?????????????C45E3 ????2.6 ????2.5 ????2.0 ?????-
Spices ????0.3 ????0.3 ????0.3 ????0.2
The polysiloxane kilfoam ????0.3 ????0.3 ????0.3 ?????-
Dried additive
Vitriol ????3.0 ????3.0 ????5.0 ???10.0
Carbonate ????6.0 ???13.0 ???15.0 ???14.0
???????????????PB1 ?????- ?????- ?????- ????1.5
???????????????PB4 ???18.0 ???18.0 ???10.0 ???18.5
??????????????TAED ????3.0 ????2.0 ?????- ????2.0
??????????????EDDS ?????- ????2.0 ????2.4 ?????-
Proteolytic enzyme ????1.0 ????1.0 ????1.0 ????1.0
Lipase ????0.4 ????0.4 ????0.4 ????0.2
Amylase ????0.2 ????0.2 ????0.2 ????0.4
The SYNTHETIC OPTICAL WHITNER of photoactivation ?????- ?????- ?????- ????0.15
Amount to ??100.0 ??100.0 ??100.0 ???100.0
Embodiment 5
The following detergent formulations that is applied to especially under the European washing machine condition is according to embodiments of the invention:
????T ????U ????V ?????W
The powder of blowing
?????????????LAS ????6.0 ????5.0 ????1.0 ????6.0
?????????????TAS ????2.0 ?????- ?????- ????2.0
Zeolite A ???24.0 ?????- ?????- ???20.0
????????????STPP ?????- ???27.0 ???24.0 ?????-
Vitriol ????9.0 ????6.0 ???13.0 ????5.0
????????????QAS1 ????0.5 ????0.8 ?????- ????1.0
??????????MA/AA1 ????0.4 ????0.9 ?????- ?????-
??????????MA/AA2 ?????- ?????- ????0.4 ????0.5
????????????QEA1 ????1.0 ????1.2 ????0.7 ?????-
????????????QEA3 ?????- ?????- ?????- ????0.5
Silicate ????1.0 ????7.0 ????3.0 ????3.0
?????????????CMC ????1.0 ????1.0 ????0.5 ????0.6
Whitening agent 1 ????0.2 ????0.2 ????0.2 ????0.2
The polysiloxane kilfoam ????1.0 ????1.0 ????1.0 ????0.3
Carbonate ????5.0 ????3.0 ?????- ????4.0
?????????????STS ????0.3 ????0.5 ?????- ????0.2
???????????DTPMP ????0.4 ????0.4 ????0.2 ????0.4
Spraying
Whitening agent ???0.02 ?????- ?????- ????0.02
???????????C45E7 ?????- ?????- ?????- ????5.0
???????????C45E2 ????2.5 ????2.5 ????2.0 ?????-
???????????C45E3 ????2.6 ????2.5 ????2.0 ?????-
Spices ????0.5 ????0.3 ????0.5 ????0.2
The polysiloxane kilfoam ????0.3 ????0.3 ????0.3 ?????-
Dried additive
?????????????QEA ?????- ?????- ?????- ????0.5
????????????EDDS ????0.3 ?????- ?????- ?????-
Vitriol ????2.0 ????3.0 ????5.0 ???10.0
Carbonate ????6.0 ???10.0 ???12.0 ????9.0
Citric acid ????2.5 ?????- ?????- ????2.0
?????????????QASⅡ ????0.5 ?????- ?????- ????0.5
?????????????SKS-6 ???10.0 ?????- ?????- ?????-
Percarbonate ???18.5 ?????- ?????- ?????-
???????????????PB4 ?????- ???18.0 ???10.0 ???21.5
??????????????TAED ????2.0 ????2.0 ?????- ????2.0
???????????NAC-OBS ????3.0 ????2.0 ????4.0 ?????-
Proteolytic enzyme ????1.0 ????1.0 ????1.0 ????1.0
Lipase ?????- ????0.4 ?????- ????0.2
Lipase (1) ????0.4 ?????- ????0.4 ?????-
Amylase ????0.2 ????0.2 ????0.2 ????0.4
Whitening agent ????0.05 ?????- ?????- ????0.05
Other/accessory constituent to 100%
Embodiment 6
Following granulated detergent preparation is an embodiment according to the present invention:
?????X ?????Y ?????Z ????AA ????BB ????CC
The powder of blowing
?????????????LAS ???23.0 ????8.0 ????7.0 ????9.0 ????7.0 ????7.0
?????????????TAS ?????- ?????- ?????- ?????- ????1.0 ?????-
???????????C45AS ????6.0 ????6.0 ????5.0 ????8.0 ?????- ?????-
??????????C45AES ?????- ????1.0 ????1.0 ????1.0 ?????- ?????-
??????????C45E35 ?????- ?????- ?????- ?????- ????2.0 ????4.0
Zeolite A ???10.0 ???18.0 ???14.0 ???12.0 ???10.0 ???10.0
???????????MA/AA ?????- ????0.5 ????0.4 ?????- ?????- ????0.3
????????MA/AA(1) ????0.9 ?????- ?????- ?????- ?????- ?????-
??????????????AA ?????- ?????- ????0.1 ????1.0 ?????- ????0.2
????????????QAS1 ????0.5 ????0.6 ?????- ?????- ????1.0 ????1.0
Vitriol ????5.0 ????6.3 ???14.3 ???11.0 ???15.0 ???15.3
Silicate ???10.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0
????????????QEA1 ????0.9 ????1.1 ?????- ?????- ?????- ????0.5
????????????QEA2 ?????- ?????- ????1.0 ????1.5 ?????- ?????-
????????????QEA3 ?????- ?????- ?????- ?????- ?????- ????0.5
Carbonate ???15.0 ???20.0 ???10.0 ???20.7 ????8.0 ????6.0
?????????PEG4000 ????0.4 ????1.5 ????1.5 ????1.0 ????1.0 ????1.0
?????????????STS ????0.2 ?????- ?????- ????0.5 ????0.3 ????0.2
????????????DTPA ?????- ????0.3 ????0.3 ?????- ?????- ????0.4
Whitening agent 2 ????0.3 ????0.2 ????0.3 ?????- ????0.1 ????0.3
Spraying ?????- ?????- ?????- ?????- ?????- ?????-
???????????C45E7 ?????- ????2.0 ?????- ?????- ????2.0 ????2.0
???????????C25E9 ????3.0 ?????- ?????- ?????- ?????- ?????-
???????????C23E9 ?????- ?????- ????1.5 ????2.0 ?????- ????2.0
Spices ????0.3 ????0.3 ????0.3 ????2.0 ????0.3 ????0.3
Agglomerate
???????????C45AS ?????- ????5.0 ????5.0 ????2.0 ?????- ????5.0
?????????????LAS ?????- ????2.0 ????2.0 ?????- ?????- ????2.0
????????????????QEA1 ?????- ?????- ?????- ?????- ????0.8 ?????-
??????????????MA/AA1 ?????- ?????- ?????- ?????- ????0.8 ?????-
Zeolite ?????- ????7.5 ????7.5 ????8.0 ?????- ????7.5
Carbonate ?????- ????4.0 ????4.0 ????5.0 ?????- ????4.0
?????????????PEG4000 ?????- ????0.5 ????0.5 ?????- ?????- ????0.5
Other (water etc.) ?????- ????2.0 ????2.0 ????2.0 ?????- ????2.0
Dried additive
?????????????QAS(Ⅰ) ?????- ?????- ?????- ?????- ????1.0 ?????-
Citrate trianion ?????- ????0.4 ?????- ?????- ????2.0 ????0.5
?????????????????PB4 ?????- ?????- ?????- ?????- ???12.0 ????1.0
?????????????????PB1 ????4.0 ????1.0 ????3.0 ????2.0 ?????- ?????-
Percarbonate ?????- ?????- ?????- ?????- ????2.0 ???10.0
Carbonate ?????- ????5.3 ????1.8 ?????- ????4.0 ????4.0
????????????????NOBS ????4.0 ?????- ????6.0 ?????- ?????- ????0.6
Methylcellulose gum ????0.2 ?????- ?????- ?????- ?????- ?????-
???????????????SKS-6 ????8.0 ?????- ?????- ?????- ?????- ?????-
?????????????????STS ?????- ?????- ????2.0 ?????- ????1.0 ?????-
Cumene sulfonic acid ?????- ????1.0 ?????- ?????- ?????- ????2.0
Lipase ????0.2 ?????- ????0.2 ?????- ????0.2 ????0.4
Cellulase ????0.2 ????0.2 ????0.2 ????0.3 ????0.2 ????0.2
Amylase ????0.2 ?????- ????0.1 ?????- ????0.2 ?????-
Proteolytic enzyme ????0.5 ????0.5 ????0.5 ????0.3 ????0.5 ????0.5
???????????????PVPⅥ ?????- ?????- ?????- ?????- ????0.5 ????0.1
?????????????????PVP ?????- ?????- ?????- ?????- ????0.5 ?????-
????????????????PVNO ?????- ?????- ????0.5 ????0.3 ?????- ?????-
?????????????????QEA ?????- ?????- ?????- ?????- ????1.0 ?????-
????????????????SRP1 ????0.2 ????0.5 ????0.3 ?????- ????0.2 ?????-
The polysiloxane kilfoam ????0.2 ????0.4 ????0.2 ????0.4 ????0.1 ?????-
Sal epsom ?????- ?????- ????0.2 ?????- ????0.2 ?????-
Other/accessory constituent to 100%
Embodiment 7
Be used in particular for washing the detergent formulations that does not contain SYNTHETIC OPTICAL WHITNER of band look clothes below the preparation, it is an embodiment according to the present invention:
????DD ????EE ???FF
The powder of blowing
Zeolite A ???15.0 ???15.0 ?????-
Vitriol ????0.0 ???10.0 ?????-
?????????????LAS ????3.0 ????3.0 ?????-
???????????DTPMP ????0.4 ????0.5 ?????-
?????????????CMC ????0.4 ????0.4 ?????-
????????????QEA1 ????1.0 ????0.2 ?????-
????????????QEA2 ?????- ????1.0 ?????-
??????????MA/AA1 ????0.5 ?????- ?????-
??????????????AA ?????- ????0.6 ?????-
Carbonate ?????- ????5.0 ?????-
?????????????STS ?????- ????0.2 ?????-
????????????QAS1 ?????- ????1.0 ?????-
Agglomerate ?????-
???????????C45AS ?????- ?????- ???11.0
?????????????LAS ????6.0 ????5.0 ?????-
?????????????TAS ????3.0 ????2.0 ?????-
Silicate ????4.0 ????4.0 ?????-
Zeolite A ???10.0 ???15.0 ???13.0
????????????QEA1 ?????- ?????- ????1.0
?????????????CMC ?????- ?????- ????0.5
???????????MA/AA ?????- ?????- ????0.8
Carbonate ????9.0 ????7.0 ????7.0
Spraying
Spices ????0.3 ????0.3 ????0.5
???????????C45E7 ????4.0 ????4.0 ????4.0
???????????C25E3 ????2.0 ????2.0 ????2.0
Dried additive
?????????????????MA/AA ?????- ?????- ????3.0
???????????????NaSKS-6 ?????- ?????- ???12.0
Citric acid ???10.0 ?????- ????8.0
Supercarbonate ????7.0 ????3.0 ????5.0
Carbonate ????8.0 ????5.0 ????7.0
????????????PVPVI/PVNO ????0.5 ????0.5 ????0.5
??????????????Alcalase ????0.5 ????0.3 ????0.9
Lipase ????0.4 ????0.4 ????0.4
Amylase ????0.6 ????0.6 ????0.6
Cellulase ????0.6 ????0.6 ????0.6
The polysiloxane kilfoam ????5.0 ????5.0 ????5.0
Citrate trianion ?????- ????1.0 ?????-
Vitriol ????0.0 ????9.0 ????0.0
Other/accessory constituent to 100% ??100.0 ??100.0 ??100.0
Density (g/ liter) ????700 ????700 ????700
Embodiment 8
The following granular detergent composition that is applied to especially under the European wash conditions is according to embodiments of the invention:
????EE ????FF
The powder of blowing
Zeolite A ???20.0 ?????-
????????????????STPP ?????- ???20.0
?????????????????LAS ????6.0 ????6.0
???????????????C68AS ????2.0 ????2.0
Silicate ????3.0 ????8.0
??????????????MA/AA1 ????4.0 ????2.0
??????????????MA/AA2 ?????- ????2.0
?????????????????CMC ????0.6 ????0.6
????????????????QEA1 ????0.9 ????0.6
????????????????QEA3 ????0.1 ?????-
Whitening agent 1 ????0.2 ????0.2
???????????????DTPMP ????0.4 ????0.4
Spraying
???????????????C45E7 ????5.0 ????5.0
The polysiloxane kilfoam ????0.3 ????0.3
Spices ????0.2 ????0.2
Dried additive
Carbonate ???14.0 ????9.0
?????????????????PB1 ????1.5 ????2.0
?????????????????PB4 ???18.5 ???13.0
????????????????TAED ????2.0 ????2.0
The SYNTHETIC OPTICAL WHITNER of photoactivation ??15ppm ??15ppm
Proteolytic enzyme ????1.0 ????1.0
Lipase ????0.2 ????0.2
Amylase ????0.4 ????0.4
Cellulase ????0.1 ????0.1
Vitriol ???10.0 ???20.0
Equipoise (water and other)
Density (g/ liter) ???700 ???700
Embodiment 9
Following detergent composition is an embodiment according to the present invention:
????GG ????HH ????II
The powder of blowing
Zeolite A ???15.0 ???15.0 ???15.0
Sodium sulfate ????0.0 ????5.0 ????0.0
?????????????LAS ????3.0 ????3.0 ????3.0
?????????????QAS ?????- ????1.5 ????1.5
???????????DTPMP ????0.4 ????0.2 ????0.4
?????????????CMC ????0.4 ????0.4 ????0.4
??????????MA/AA1 ?????- ?????- ????2.0
??????????MA/AA2 ????2.0 ?????- ?????-
??????????????AA ?????- ????4.0 ?????-
Agglomerate
?????????????LAS ????5.0 ????5.0 ????5.0
?????????????TAS ????2.0 ????2.0 ????1.0
Silicate ????3.0 ????3.0 ????4.0
????????????QEA1 ????1.0 ????2.5 ????0.6
The Mn catalyzer ???0.03 ?????- ?????-
Zeolite A ????8.0 ????8.0 ????8.0
Carbonate ????8.0 ????8.0 ????4.0
Spraying
Spices ????0.3 ????0.3 ????0.3
???????????C45E7 ????2.0 ????2.0 ????2.0
???????????C25E3 ????2.0 ?????- ?????-
Dried additive ?????- ?????- ?????-
Citrate trianion ????5.0 ?????- ????2.0
Supercarbonate ?????- ????3.0 ?????-
Carbonate ????8.0 ???15.0 ???10.0
Percarbonate ?????- ????7.0 ???10.0
????????????TAED ????6.0 ????2.0 ????5.0
???????????????PB1 ????14.0 ????7.0 ???10.0
??????????????EDDS ?????- ????2.0 ?????-
Polyoxyethylene MW 5,000,000 ?????- ?????- ????0.2
Wilkinite ?????- ?????- ???10.0
Proteolytic enzyme ????1.0 ????1.0 ????1.0
Lipase ????0.4 ????0.4 ????0.4
Amylase ????0.6 ????0.6 ????0.6
Cellulase ????0.6 ????0.6 ????0.6
The polysiloxane kilfoam ????5.0 ????5.0 ????5.0
Dried additive
Sodium sulfate ????0.0 ????3.0 ????0.0
Equipoise (water and other) ??100.0 ??100.0 ??100.0
Density (g/ liter) ????850 ????850 ????850
Embodiment 10
Following granulated detergent preparation is an embodiment according to the present invention:
????JJ ????KK ????LL ????MM
Basic granules
Zeolite A ???30.0 ???22.0 ???24.0 ???10.0
Vitriol ???10.0 ????5.0 ???10.0 ????7.0
??????????MA/AA1 ?????- ????0.5 ?????- ?????-
??????????????AA ????0.9 ?????- ????1.0 ?????-
??????????MA/AA2 ?????- ?????- ?????- ????1.0
????????????QEA1 ?????- ????1.2 ????1.2 ?????-
????????????QEA3 ????1.5 ?????- ?????- ????3.0
????????????QAS2 ?????- ????1.0 ????0.5 ?????-
?????????????LAS ???14.0 ???10.0 ????9.0 ???20.0
???????????C45AS ????8.0 ????7.0 ????9.0 ????7.0
??????????C45AES ?????- ????1.0 ????1.0 ?????-
Silicate ?????- ????1.0 ????0.5 ???10.0
Soap ?????- ????2.0 ?????- ?????-
Whitening agent 1 ????0.2 ????0.2 ????0.2 ????0.2
Carbonate ????6.0 ????9.0 ???10.0 ???10.0
?????????PEG4000 ?????- ????1.0 ????1.5 ?????-
????????????DTPA ?????- ????0.4 ?????- ?????-
Spraying
???????????C25E9 ?????- ?????- ?????- ????5.0
???????????C45E7 ????1.0 ????1.0 ?????- ?????-
???????????C23E9 ?????- ????1.0 ????2.5 ?????-
Spices ????0.2 ????0.3 ????0.3 ?????-
Dried additive
Carbonate ????5.0 ???10.0 ???18.0 ????8.0
??????PVPVI/PVNO ????0.5 ?????- ????0.3 ?????-
Proteolytic enzyme ????1.0 ????1.0 ????1.0 ????0.5
Lipase ????0.4 ?????- ?????- ????0.4
Amylase ????0.1 ?????- ?????- ????0.1
Cellulase ????0.1 ????0.2 ????0.2 ????0.1
??????????????????NOBS ?????- ????4.0 ?????- ????4.5
???????????????????PB1 ????1.0 ????5.0 ????1.5 ????6.0
Vitriol ????4.0 ????5.0 ?????- ????5.0
??????????????????SRPI ?????- ????0.4 ?????- ?????-
Suds suppressor ?????- ????0.5 ????0.5 ?????-
Other/accessory constituent to 100%
Embodiment 11
Following granular detergent composition is an embodiment according to the present invention:
????NN ????OO ?????PP ????QQ ????RR ????SS ????TT ????UU
The powder of blowing
Zeolite A ???20.0 ?????- ???15.0 ???15.0 ???15.0 ???15.0 ???15.0 ???15.0
????????????????STPP ?????- ???20.0 ?????- ?????- ?????- ?????- ?????- ?????-
Vitriol ?????- ?????- ???15.0 ???15.0 ???15.0 ???15.0 ???15.0 ???15.0
Carbonate ?????- ?????- ????5.0 ????5.0 ????5.0 ????5.0 ????5.0 ????5.0
?????????????????TAS ?????- ?????- ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0
?????????????????LAS ????6.0 ????6.0 ????6.0 ????6.0 ????6.0 ????6.0 ????6.0 ????6.0
Silicate ????3.0 ????8.0 ?????- ?????- ?????- ?????- ?????- ?????-
????????????????QEA1 ????1.2 ????1.5 ????0.9 ????0.9 ????0.9 ????0.9 ????0.9 ????0.9
????????????????QAS1 ????1.2 ?????- ????0.9 ?????- ????0.9 ?????- ?????- ?????-
?????????????????QAS ?????- ????1.5 ?????- ????0.9 ?????- ????0.9 ?????- ?????-
??????????????MA/AA1 ????1.7 ????1.7 ????0.5 ????0.5 ????0.5 ????0.5 ????0.5 ????0.5
?????????????????CMC ????0.4 ????0.4 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2
Whitening agent 1 ????0.2 ????0.2 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1
???????????????DTPMP ????0.2 ????0.2 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1
?????????????????STS ?????- ????1.0 ????1.0 ????1.0 ?????- ?????- ????1.0 ?????-
Spraying
???????????????C45E7 ????5.0 ????5.0 ????4.0 ????4.0 ????4.0 ????4.0 ????4.0 ????4.0
The polysiloxane kilfoam ????0.3 ????0.3 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1 ????0.1
Spices ????0.2 ????0.2 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3
Dried additive
?????????????????QEA ????1.0 ????1.0 ?????- ?????- ?????- ?????- ?????- ?????-
Carbonate ???14.0 ????9.0 ???10.0 ???10.0 ???10.0 ???10.0 ???10.0 ???10.0
?????????????????PB1 ????1.5 ????2.0 ?????- ?????- ?????- ?????- ?????- ?????-
?????????????????PB4 ???18.5 ???13.0 ???13.0 ???13.0 ???13.0 ???13.0 ???13.0 ???13.0
????????????????TAED ????2.0 ????2.0 ????2.0 ????2.0 ????2.0 ????2.0 ????2.0 ????2.0
????????????????QAS1 ????1.0 ????1.0 ?????- ?????- ?????- ?????- ????1.0 ????1.0
The SYNTHETIC OPTICAL WHITNER of photoactivation ?????15 ????ppm ?????15 ????ppm ?????15 ????ppm ?????15 ????ppm ?????15 ????ppm ?????15 ????ppm ?????15 ????ppm ?????15 ????ppm
?????????????SKS-6 ?????- ?????- ????3.0 ????3.0 ????3.0 ????3.0 ????3.0 ????3.0
Proteolytic enzyme ????1.0 ????1.0 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2
Lipase ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2
Amylase ????0.4 ????0.4 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2
Cellulase ????0.1 ????0.1 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2 ????0.2
Vitriol ???10.0 ???20.0 ????5.0 ????5.0 ????5.0 ????5.0 ????5.0 ????5.0
Other/accessory constituent to 100%
Density (g/ liter) ????690 ????690 ????690 ????690 ????690 ????690 ????690 ????690
Embodiment 12
Following laundry bars detergent composition is an embodiment according to the present invention:
???VV ???WW ???XX ???YY ???ZZ ????AB ????AC ????AD
?LAS ???- ???- ?19.0 ?15.0 ??21.0 ???6.75 ????8.8 ?????-
?C28AS ?30.0 ?13.5 ???- ???- ????- ??15.75 ???11.2 ???22.5
Sodium laurate ??2.5 ??9.0 ???- ???- ????- ?????- ?????- ?????-
Zeolite A ??2.0 ?1.25 ???- ???- ????- ???1.25 ???1.25 ???1.25
Carbonate ?20.0 ??3.0 ?13.0 ??8.0 ??10.0 ???15.0 ???15.0 ???10.0
Lime carbonate ?21.5 ???- ???- ???- ????- ?????- ?????- ?????-
Vitriol ??5.0 ???- ???- ???- ????- ?????- ?????- ?????-
?TSPP ??5.0 ???- ??5.0 ???- ???5.0 ????5.0 ????2.5 ????5.0
?STPP ??5.0 ?15.0 ???- ???- ????- ????5.0 ????8.0 ???10.0
Wilkinite ???- ?10.0 ???- ???- ???5.0 ?????- ?????- ?????-
?DTPMP ???- ??0.7 ??0.6 ???- ???0.6 ????0.7 ????0.7 ????0.7
?MA/AA1 ??0.4 ??1.0 ???- ???- ???0.2 ????0.4 ????0.5 ????0.4
?MA/AA2 ???- ???- ??0.9 ??1.2 ???0.8 ????0.8 ?????- ?????-
?SRP1 ??0.3 ??0.3 ??0.3 ??0.3 ???0.3 ????0.3 ????0.3 ????0.3
Proteolytic enzyme ???- ?0.12 ???- ?0.08 ??0.08 ?????- ?????- ????0.1
Lipase ???- ??0.1 ???- ??0.1 ????- ?????- ?????- ?????-
Amylase ???- ???- ??0.8 ???- ????- ?????- ????0.1 ?????-
Cellulase ???- ?0.15 ???- ???- ??0.15 ?????- ?????- ?????-
?PEO ???- ??0.2 ???- ??0.2 ???0.3 ?????- ?????- ????0.3
Spices ??1.6 ???- ???- ???- ????- ?????- ?????- ?????-
Embodiment 13
Following compact-type high-density (0.96Kg/l) dishwashing detergent composition NN-SS is according to embodiments of the invention, and the component symbol of writing a Chinese character in simplified form that uses in this dishwashing detergent composition has to give a definition: metasilicate: Starso (SiO 2: Na 2O=1.0) nonionic: have average degree of ethoxylation 3.8 and average propoxylation degree
4.5 C 13-C 15Mixed ethoxylated/propoxylation fat
Alcohol, by BASF GmbH with trade(brand)name PlurafacLF404
Sell (low bubble) PAAC: five amine cobaltous acetate (III) salt BzP: benzoyl peroxide paraffin: by the paraffin of Wintershall with trade(brand)name Winog70 sale
Oil BTA: benzotriazole Bismuth trinitrate: Bismuth trinitrate salt ter-polymers: the ter-polymers of molecular-weight average about 7000, it comprises
Weight ratio is 60: 20: 20 a vinylformic acid: toxilic acid: ethyl
Acrylic Acid Monomer 480N: the random copolymers of 3: 7 vinylformic acid/methylacrylic acids, average mark
Son amount about 3500
????AE ????AF ????AG ????AH ????AI ????AJ
???STPP ???24.80 ???24.80 ???25.00 ???28.39 ???28.50 ???20.00
Citrate trianion ????- ????- ????- ????- ???10.00 ???10.00
Carbonate ????- ????- ???17.50 ???17.50 ????- ????-
???QEA1 ???0.5 ???1.5 ???2.0 ???1.0 ???1.3 ???0.8
Silicate ???20.36 ???20.36 ???14.81 ???14.81 ???14.81 ????-
Metasilicate ???2.50 ???2.50 ???2.50 ????- ????- ????-
???PB1 ???7.79 ???7.79 ???9.74 ???14.28 ???9.74 ????-
???PB4 ????- ????- ????- ????- ????- ???10.4
Percarbonate ????- ????- ????- ????- ????- ???6.70
Nonionic ???1.50 ???1.50 ???2.00 ???1.50 ???2.00 ???2.60
???TAED ???2.39 ???2.00 ???2.70 ???2.00 ???3.60 ???4.00
???HEDP ???0.46 ???0.46 ???1.00 ????- ???0.83 ????-
???DETPMP ????- ????- ???0.65 ????- ????- ????-
???PAAC ????- ????- ????- ???0.20 ????- ????-
???BzP ????- ????- ????- ???4.44 ????- ????-
Paraffin ???0.50 ???0.50 ???0.50 ???0.50 ????- ???0.20
Proteolytic enzyme ???2.20 ???2.20 ???2.20 ???2.20 ???2.00 ???0.50
Amylase ???1.50 ???1.50 ???1.20 ???1.50 ???1.00 ???1.10
???BTA ???0.30 ???0.30 ???0.30 ???0.30 ????- ????-
Bismuth trinitrate ????- ????- ???0.30 ????- ????- ????-
Ter-polymers ????- ????- ????- ???4.00 ????- ????-
???MA/AA2 ???0.5 ???1.0 ???1.00 ???0.50 ???0.7 ???0.8
Vitriol ???8.44 ???8.44 ???20.77 ????- ???23.24 ???1.00
Other and moisture are to balance
PH (1% solution) ???10.90 ???10.90 ???11.00 ???10.80 ???10.90 ???9.60

Claims (27)

1. solid, preferred granular detergent composition or its component, it comprises: the polyelectrolyte compound that (a) contains carboxylate radical; (b) have the water-soluble cationic compound of removing native dirt/antiredeposition performance, it is selected from:
1) have the ethoxylation positively charged ion monoamine of following formula:
Figure A9719999700021
2). have the ethoxylation cationic diamine of following formula:
Figure A9719999700022
Or M wherein 1Be N+ or N group; Each M 2Be N+ or N group, at least one M 2It is the N+ group.
3) have the ethoxylation cationic polyamine of following formula:
Figure A9719999700025
4) their mixture; A wherein 1Be
Figure A9719999700026
Figure A9719999700031
Or
Figure A9719999700032
R is H or C 1-C 4Alkyl or hydroxyalkyl, R 1Be C 2-C 12Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkyl arylene, or have the C of about 20 oxygen alkylidene units of 2- 2-C 3Oxyalkylene segment, condition are not form the O-N key; Each R 2Be C 1-C 4Alkyl or hydroxyalkyl, segment-L-X; Or two R 2In conjunction with formation-(CH 2) r-A 2-(CH 2) s-, A wherein 2Be-O-or-CH 2-, r is 1 or 2, and s is 1 or 2, and r+s is 3 or 4; Each R 3Be C 1-C 8Alkyl or hydroxyalkyl, benzyl, segment L-X, or two R 3Or R 2With a R 3In conjunction with forming segment-(CH 2) r-A 2-(CH 2) s-; R 4Be C with replacement of p the position of substitution 3-C 12Alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl; R 5Be C 1-C 12Alkenyl, hydroxy alkylidene, alkylene group, arylidene or alkyl arylene, or have the C of about 20 oxygen alkylidene units of 2- 2-C 3Oxyalkylene segment, condition are not form O-O or O-N key; X is selected from H, C 1-C 4The non-ionic group of alkyl or hydroxy alkyl ester or ether group and their mixture; L contains the polyoxy alkylidene segment :-[(R 6O) m(CH 2CH 2O) n]-hydrophilic chain; R wherein 6Be C 3-C 4Alkylidene group or hydroxy alkylidene, m and n are to make segment-(CH 2CH 2O) n-account for said polyoxy alkylidene segment at least about 50% numerical value; Work as M 2When being N+, d is 1, works as M 2When being N, d is 0; For said positively charged ion monoamine, n is at least about 16, and for said cationic diamine, n is that n is at least about 3 at least about 6 with for said cationic polyamine; P is 3-8; Q is 1 or 0; T is 1 or 0, and condition is when q is 1, and t is 1; Wherein (a) and ratio (b) are 1: 95 to 95: 1.
2. according to the detergent composition or the component of claim 1, wherein said ratio is 1: 25-25: 1.
3. according to the detergent component of claim 1, wherein said ratio is 1: 1-1: 10.
4. according to the detergent component of claim 1 or 3, wherein said ratio is 1: 1-1: 2.
5. the detergent component of a spray-dried granules, it comprises: the polyelectrolyte compound that (a) contains carboxylate radical; (b) have the water-soluble cationic compound of removing native dirt/antiredeposition performance, it is selected from:
1) have the ethoxylation positively charged ion monoamine of following formula:
2). have the ethoxylation cationic diamine of following formula:
Figure A9719999700042
Or
Figure A9719999700043
Figure A9719999700044
M wherein 1Be N+ or N group; Each M 2Be N+ or N group, at least one M 2It is the N+ group.
3) have the ethoxylation cationic polyamine of following formula:
Figure A9719999700045
4) their mixture; A wherein 1Be
Figure A9719999700046
Figure A9719999700051
R is H or C 1-C 4Alkyl or hydroxyalkyl, R 1Be C 2-C 12Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkyl arylene, or have the C of about 20 oxygen alkylidene units of 2- 2-C 3Oxyalkylene segment, condition are not form the O-N key; Each R 2Be C 1-C 4Alkyl or hydroxyalkyl, segment-L-X; Or two R 2In conjunction with formation-(CH 2) r-A 2-(CH 2) s-, A wherein 2Be-O-or-CH 2-, r is 1 or 2, and s is 1 or 2, and r+s is 3 or 4; Each R 3Be C 1-C 8Alkyl or hydroxyalkyl, benzyl, segment L-X, or two R 3Or R 2With a R 3In conjunction with forming segment-(CH 2) r-A 2-(CH 2) s-; R 4Be C with replacement of p the position of substitution 3-C 12Alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl; R 5Be C 1-C 12Alkenyl, hydroxy alkylidene, alkylene group, arylidene or alkyl arylene, or have the C of about 20 oxygen alkylidene units of 2- 2-C 3Oxyalkylene segment, condition are not form O-O or O-N key; X is selected from H, C 1-C 4The non-ionic group of alkyl or hydroxy alkyl ester or ether group and their mixture; L contains the polyoxy alkylidene segment :-[(R 6O) m(CH 2CH 2O) n]-hydrophilic chain; R wherein 6Be C 3-C 4Alkylidene group or hydroxy alkylidene, m and n are to make segment-(CH 2CH 2O) n-account for said polyoxy alkylidene segment at least about 50% numerical value; Work as M 2When being N+, d is 1, works as M 2When being N, d is 0; For said positively charged ion monoamine, n is at least about 16, and for said cationic diamine, n is that n is at least about 3 at least about 6 with for said cationic polyamine; P is 3-8; Q is 1 or 0; T is 1 or 0, and condition is when q is 1, and t is 1; Wherein (a) is 1 with (b) ratio of compound: 1-1: 10.
6. according to the detergent composition or the component of any aforementioned claim, wherein the content of cation compound by detergent component or particulate weight, is 0.5%-15%.
7. according to the detergent composition or the component of any aforementioned claim, wherein the content of cation compound by the weight of said composition, is 0.01%-30%.
8. according to the detergent composition or the component of any aforementioned claim, wherein the content of cation compound by the weight of said composition, is 0.2%-3%.
9. according to the detergent composition or the component of any aforementioned claim, wherein said cation compound is an ethoxylation positively charged ion monoamine, is characterised in that a R 2Be methyl, two R 2Be segment L-X, m is 0, and n is at least about 20.
10. according to any detergent composition or the component of claim 1-8, wherein said cation compound is the ethoxylation cationic diamine, is characterised in that R 1Be C 2-C 6Alkylidene group.
11. according to any detergent composition or the component of claim 1-8 or 10, wherein said ethoxylation cationic diamine is characterised in that R 1It is hexa-methylene.
12. according to any detergent composition or the component of claim 1-8, wherein said cation compound is the ethoxylation cationic polyamine, is characterised in that R 4Be the C that replaces 3-C 6Alkyl, hydroxyalkyl or aryl; A1 is: With p be 3-6.
13. according to any detergent composition or the component of claim 10-12, wherein said cation compound is characterised in that each R 2Be methyl or segment-L-X, each R 3Be methyl, M 1With each M 2Be N +Group.
14. according to any detergent composition or the component of claim 10-13, wherein m is 0, n is at least 12.
15. according to the detergent composition or the component of claim 10 or 11, wherein m is 0, n is at least 20.
16. according to the detergent composition or the component of any aforementioned claim, wherein the cation water-soluble compound has one or more MeSO 4 -The anionic counter-ion of form.
17. according to the detergent composition or the component of any aforementioned claim, wherein contain the content of the polyelectrolyte compound of carboxylate radical,, be 0.01%-40% by the weight of said composition.
18. according to the detergent component of claim 17, wherein contain the content of the polyelectrolyte compound of carboxylate radical,, be 0.1%-15% by the weight of this component.
19. according to the detergent component of claim 18, wherein contain the content of the polyelectrolyte compound of carboxylate radical, by this component or particulate weight, be 0.2%-2.0%, preferred 1.2%.
20. according to any detergent composition or the component of claim 1-19, the polyelectrolyte compound that wherein contains carboxylate radical is toxilic acid/acrylic copolymer or acrylate homopolymer.
21. according to the detergent composition or the component of claim 20, wherein the molecular-weight average of toxilic acid/acrylic copolymer is 2500-20000, or 60000-70000.
22., wherein have cation mono-or dialkoxy amine tensio-active agent according to the detergent composition or the component of any aforementioned claim.
23. detergent composition or component according to any aforementioned claim wherein exist carbonate and vitriol.
24. preparation is according to the method for the detergent component of the spray-dried granules of any aforementioned claim, this method may further comprise the steps: a) preparation cation compound and contain the polyelectrolyte of carboxylate radical and the mixture of additional detergent components randomly, wherein cation compound is 1 with the ratio that contains the polyelectrolyte of carboxylate radical: 95-95: 1, preferred 10: 1-1: 1; B) spraying drying mixture a).
25. preparation is according to the method for the detergent component of the spray-dried granules of any aforementioned claim, this method may further comprise the steps: a) preparation 1: 95-95: 1, preferred 10: 1-1: the cation compound of 1 ratio and the mixture that contains the polyelectrolyte of carboxylate radical; B) in the mixture of step a), add additional detergent component and form second kind of mixture; C) second kind of mixture b of spraying drying).
26. according to the method for claim 25, wherein additional detergent component is an organic constituent.
27. according to the method for claim 26, wherein second kind of mixture added in the other additional detergent components before the spraying drying step.
CN 97199997 1996-09-24 1997-09-22 Detergent composition or component Pending CN1238801A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9619928.6 1996-09-24
GB9619928A GB2317394A (en) 1996-09-24 1996-09-24 Detergent compositions
GB9713946.3 1997-07-02
GBGB9713946.3A GB9713946D0 (en) 1997-07-02 1997-07-02 Detergent composition or component

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BR (1) BR9712839A (en)
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JP5013758B2 (en) * 2005-06-14 2012-08-29 ライオン株式会社 Cleaning composition for automatic dishwasher
JP5225543B2 (en) * 2005-06-29 2013-07-03 株式会社Ａｄｅｋａ Detergent composition for automatic dishwasher
SG173230A1 (en) * 2010-01-25 2011-08-29 Rohm & Haas Laundry detergent bar composition
JP5723655B2 (en) * 2011-04-01 2015-05-27 ライオン株式会社 Detergent for dishwasher
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