CN1113953C - Detergent particle - Google Patents
Detergent particle Download PDFInfo
- Publication number
- CN1113953C CN1113953C CN97199894A CN97199894A CN1113953C CN 1113953 C CN1113953 C CN 1113953C CN 97199894 A CN97199894 A CN 97199894A CN 97199894 A CN97199894 A CN 97199894A CN 1113953 C CN1113953 C CN 1113953C
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- Prior art keywords
- group
- alkyl
- particle
- acid
- compound
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Classifications
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0034—Fixed on a solid conventional detergent ingredient
-
- 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
Abstract
The present invention relates to a particle containing cationic compounds with particulate/clay-soil removal/anti-redeposition properties and a carrier material, for use in detergent compositions or components thereof and a process for making the particle.
Description
Technical field
The present invention relates to be used for containing of detergent composition or their component has particle/clay soil removal/anti cation compound of deposit properties and particle and this particulate method of preparation of carrier substance again.
Background of invention
A character that is even more important of detergent composition is its ability of removing the grain type dirt in laundry processes from various fabrics.Most important particulate fouling may be the loam mould dirt.The clay soil particle contains the negative charge layer and the positive charge positively charged ion (for example calcium) of silico-aluminate usually, and they combine the negative charge layer between the negative charge layer.
Except removing clay soil, also the dirt that need keep removing in laundry (or dishwashing detergent) periodic process suspends.Dirt that remove from fabric and that be suspended in the washing water can be deposited on the surface of fabric again.These sedimentary again dirts cause darkness or " becoming ash " effect, are especially tangible to white fabrics.For reducing this problem, can in detergent composition, comprise anti redeposition agent.
For example EP-B-111965 discloses and used cation compound in washing composition, and it has clay soil simultaneously and removes and antiredeposition character.
US4659802 and US4664848 have described quaternary ammonium, and it has clay soil removes and antiredeposition character, and it can be used in combination with anion surfactant.
Prior art discloses these cation compounds and can add in the detergent composition through aqueous slurry, subsequently aerosol and spraying drying.
Yet people have found described in this area, add above-mentioned cation compound and can cause such as the stink of final washing composition and the problem of the decolouring of (white) final washing composition in granular detergent composition or its component.
The applicant has now found that ratio that these problems can be by using the careful cation compound of selecting and carrier substance or improves when special carrier substance absorption or the quaternized ethoxylation of encapsulate capsule positively charged ion (part) (gathering) amine (they have clay soil removal/anti deposit properties again) time.Therefore, the invention provides a kind of particle, wherein cation compound absorb by this way in conjunction with or the encapsulate capsule, the particle that make to form be water miscible, flowable and (temperature) stable, thereby in final washing composition, have acceptable smell and color.
Another advantage that is used for carrier substance of the present invention is that they also have detergent property, for example the washing assistant ability.
Be found to be very effectively according to the particle of preparation particulate preferred method of the present invention production, have especially good flowability, stability and solvability, overcome stink and decolouring problem simultaneously.
The invention still further relates to and contained this particulate detergent composition or its component.
The relevant portion of all documents of quoting is in this manual introduced the present invention as civilian reference.
Summary of the invention
The present invention relates to contain one or more cation compounds and carrier substance and the particle of other material optionally, described cation compound is to have the particle/clay soil removal/anti quaternized ethoxylation of the positively charged ion of deposit properties (part) (gathering) amine compound again.In addition, the invention still further relates to this particulate method of preparation and their purposes in detergent composition or its component.
More particularly, the present invention relates to a kind of particle, it contains:
(a) have the clay soil removal/anti water-soluble cationic compound of deposit properties again, it is selected from:
1) have the ethoxylation positively charged ion monoamine of following formula:
2) have the ethoxylation cationic diamine of following formula:
Or
Or
M wherein
1Be N+ or N group; Each M
2Be N+ or N group and at least one M
2It is the N+ group;
3) have the ethoxylation cationic polyamine of following formula:
4) their mixture;
A wherein
1Be
Or-O-,
R is H or C
1-C
4Alkyl or hydroxyalkyl, R
1Be C
2-C
12Alkylidene group, hydroxy alkylidene, alkenylene, arylidene or alkarylene, or C with about 20 oxyalkylene units of 2-
2-C
3Oxyalkylene part, its prerequisite are not form the O-N key; Each R
2Be C
1-C
4Alkyl or hydroxyalkyl, group-L-X, or two R
2Form group-(CH together
2)
r-A
2-(CH
2)
s-, A wherein
2Be-O-or-CH
2-, r is 1 or 2, s be 1 or 2 and r+s be 3 or 4; Each R
3Be C
1-C
8Alkyl or hydroxyalkyl, benzyl, group-L-X, or two R
3Or R
2With a R
3Form group-(CH together
2)
r-A
2-(CH
2)
s-; R
4Be the C that replaces
3-C
12Alkyl, hydroxyalkyl, thiazolinyl, aryl or have the alkaryl of p the position of substitution; R
5Be C
1-C
12Thiazolinyl, hydroxy alkylidene, alkenylene, arylidene or alkarylene or C with about 20 oxyalkylene units of 2-
2-C
3Oxyalkylene part, its prerequisite are not form O-O or O-N key; X is selected from H, C
1-C
4The non-ionic group of alkyl or hydroxyalkyl acrylate or ether group and their mixture; L contains polyalkylene oxide groups-[(R
6O)
m(CH
2CH
2O)
n]-; R wherein
6Be C
3-C
4The numerical value of alkylidene group or hydroxy alkylidene and m and n makes group-(CH
2CH
2O)
n-account for by weight described polyalkylene oxide groups at least about 50%; Work as M
2D is 1 and works as M when being N+
2D is 0 when being N; For described positively charged ion monoamine n is at least about 16, is at least about 6 and be at least about 3 for described cationic polyamine n for described cationic diamine n; P is 3-8; Q is 1 or 0; T is 1 or 0, and its prerequisite is that q is that 1 o'clock t is 1; With
(b) powder carrier material, wherein (a) and ratio (b) are by weight 1: 15-4: 1.
The invention still further relates to a kind of particle, it contains:
(a) have clay soil to remove/water-soluble cationic compound of antiredeposition character, it is selected from the compound of mentioning in above-mentioned (a); With
(b) aluminosilicate carrier material.
Detailed Description Of The Invention
Particle
In a first aspect of the present invention, particle of the present invention contains with by weight 1: 15-4: 1, more preferably 1: 7-1: 1, most preferably by weight 1: 4-1: the water-soluble cationic compound that 1.5 ratio exists and one or more powder carrier materials.In second aspect, the invention provides the particle that contains water-soluble cationic compound and one or more aluminosilicate carrier materials.
Optionally, other detergent component can exist by particle, preferably anion surfactant and/or polyoxyethylene glycol (as described herein).
Particulate particle size of the present invention should preferably make and be no more than 15% particulate diameter greater than 1.8mm, is no more than 15% particulate diameter less than 0.25mm.The particle that preferred average particle size particle size is 10%-50% has the particle size of diameter 0.2mm-0.7mm.
The term average particle size particle size of this paper definition by with composition sample at a series of sieves, preferred Tyler sieve top sieve is divided into mass part (common 5 parts) and calculates.The wt part that obtains thus is with respect to the aperture size of the sieve curve that draws.Average particle size particle size is by the aperture size of 50% sample by weight.
Cation compound
Principal character of the present invention is a water-soluble cationic compound, and it has particle/clay soil removal/anti deposit properties again, and be selected from cation mono-, two-and polyamine.
In particle of the present invention, cation compound and powder carrier material preferably are by weight 1 with the ratio of aluminosilicate carrier material: 15-4: 1, more preferably 1: 7-1: 1, most preferably by weight 1: 4-1: 1.5.
If particle of the present invention is present in the detergent composition, then water-soluble cationic compound is preferably in by detergent composition weight 0.01%-30%, more preferably 0.1%-15%, and most preferably the content of 0.2%-3.0% is present in the detergent composition.
When if cation compound does not have required color, especially when compound was not white, then cation compound can be with any standard method decolouring before adding particle of the present invention.
Cationic amine
The water-soluble cationic compound of the present invention that is used for granular detergent composition or its component comprises ethoxylation positively charged ion monoamine, ethoxylation cationic diamine and ethoxylation cationic polyamine as defined above.
In the chemical formula of above-mentioned cationic amine, R
1Can be side chain (for example
Ring-type (for example,
),
Or most preferably straight chain (for example-CH
2CH
2-,-CH
2CH
2CH
2-) alkylidene group, hydroxy alkylidene, alkenylene, alkarylene or oxyalkylene group.For ethoxylation cationic diamine R
1C preferably
2-C
6Alkylidene group.Each R
2Preferably methyl or group-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 suitable number, and suitable counter anion comprises Cl-, Br-, SO
3 2-, PO
4 2-, MeOSO
3 -Deng, especially preferred counter anion is Cl-and Br-.
X is selected from H, C
1-C
4The non-ionic group of alkyl or hydroxyalkyl acrylate or ether group or their mixture.Preferred ester or ether are respectively acetic ester and methyl ether.Especially preferred non-ionic group is H and methyl ether.
In above-mentioned chemical formula, hydrophilic chain L is usually all by polyalkylene oxide groups-[(R
6O)
m(CH
2CH
2O)
n]-form.Polyalkylene oxide groups-(R
6O)
m-and-(CH
2CH
2O)
n-part can mix or be preferably formed-(R
6O)
m-and-(CH
2CH
2O)
nThe block of-group.R
6C preferably
3H
6(propylidene); M preferably 0-is about 5, and most preferably 0, promptly polyalkylene oxide groups is all by-(CH
2CH
2O)
n-group is formed.Group-(CH
2CH
2O)
n-preferably account for by weight described polyalkylene oxide groups at least about 85%; 100% (m is 0) by weight most preferably.
In above-mentioned chemical formula, for cationic diamine and polyamine, M
1With each M
2N+ group preferably.
Preferred ethoxylation positively charged ion monoamine and diamines have following formula:
Wherein X and n as defined above, a is 0-20, preferred 0-4 (for example ethylidene, propylidene, hexa-methylene), b is 1 or 0.For preferred cation monoamine (b=0), n preferably at least 16, and general range is about 20-about 35.For preferred cation diamines (b=1), n is about 12 at least, and general range is about 12-about 42.
In the chemical formula of above-mentioned ethoxylation cationic polyamine, 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, and general range is about 12-about 42; P is 3-6 preferably.Work as R
4When being the aryl that replaces or alkaryl, q preferably 1 and R
5C preferably
2-C
3Alkylidene group.Work as R
4When being the alkyl that replaces, hydroxyalkyl or thiazolinyl and when q is 0, R
5C preferably
2-C
3Oxyalkylene group; When q is 1, R
5C preferably
2-C
3Alkylidene group.
These ethoxylation cationic polyamines can be obtained by polyaminoamide, for example:
Or
These ethoxylation polyamine also can be obtained by poly-amino propylene oxide derivative, for example
Wherein each c is the numerical value of 2-about 20.
Carrier substance
Another main ingredient of particulate of the present invention is one or more powder carrier materials.
In the particle according to first aspect present invention, cation compound and powder carrier material preferably are by weight 1 with the ratio of aluminosilicate carrier material: 15-2: 1, more preferably 1: 7-1: 1, most preferably by weight 1: 4-1: 1.5.
Carrier substance is the free-pouring material of white preferably, and it has low water content, preferably is lower than 25% by carrier substance weight, more preferably less than 15%, most preferably is lower than 10%.
Carrier substance preferably has porous or crystalline texture, thereby the carrier substance that has with the better interactional high surface area of water-soluble cationic compound (with other detergent component optionally) is provided.
Preferred carrier substance is some inorganic and organic dust or salt, and more preferably some water-soluble and part or major part are not dissolved in the builder material of water.
Suitable organic dust comprises alkyl or alkylidene group vitriol, borate or phosphoric acid salt, preferred alkyl vitriol.
Preferred inorganic powder carrier material comprises carbonate, supercarbonate, silicate, vitriol and phosphoric acid salt.
Suitable water soluble detergency promoter material comprises water-soluble monomer multi-carboxylate or their sour form.
Highly preferred carrier substance is Citrate trianion or citric acid.
Major part be not dissolved in the builder material of water and in a second aspect of the present invention the example of other main highly preferred carrier substance comprise silico-aluminate, preferably aluminosilicate sodium.Zeolite is highly preferred.
Suitable aluminosilicate zeolite has unit structure cell formula Na
z[(AlO
2)
z(SiO
2)
y] .xH
2O, 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, and preferred feasible the existence is no more than 25% by aluminosilicate zeolite weight, more preferably no more than 10%, is most preferably not exceeding 5% structure bonded water.
Aluminosilicate zeolite can be naturally occurring material, but preferably synthetic obtaining.Being used for synthetic crystallization silico-aluminate ion exchange material of the present invention obtains with title zeolite A, zeolite B, zeolite P, X zeolite, zeolite HS and their mixture.
Another preferred aluminosilicate zeolite carrier substance is a zeolite MAP builder.
Zeolite MAP is described in EP384070A (Unilever).It is defined as the alkali metal aluminosilicate of P type zeolite, and its silica alumina ratio is not more than 1.33, is preferably 0.9-1.33, more preferably 0.9-1.2.
What cherish a special interest is zeolite MAP, and it has and is not more than 1.15, the silica alumina ratio more preferably no more than 1.07.
Aspect preferred, silico-aluminate, especially zeolite MAP has with d
50The 1.0-10.0 micron of value representation, more preferably 2.0-7.0 micron, the most preferably particle size of 2.5-5.0 micron.
d
50Value representation 50% particle by weight has diameter less than this numerical value.Particle size particularly can be by the routine analysis technology, and it is fixed for example to use the measurement microscope method of scanning electronic microscope or pass through the laser particle size instrumentation.Determine d
50Other method of value is described in EP384070.
The carrier substance that is contained in the particle of the present invention can contain single carrier substance.Preferred carrier substance mentioned above.The silico-aluminate material is especially preferred.Account at least 50% by the preferred a kind of preferred carrier substance of carrier substance weight in the particle, more preferably surpass 70%, most preferably surpass 80%.
Preparation particulate method
Particle can be by mixing or spray-drying carrier material and cation compound and optionally other component preparation.
Aspect preferred, the cation compound of before forming particle, purifying.Especially preferred purification step is by using the steam stripped method to remove the volatile compound that can cause stink from cation compound, cation compound can being added in the particle of the present invention subsequently.A kind of example is disclosed in EP111965A.
Particle of the present invention preferably prepares by agglomeration method.
This preferred agglomeration method comprises the steps:
(a) the heating water-soluble cationic compound is to obtain melting compound;
The melting compound of (b) agglomeration (a) becomes agglomerant particle with carrier substance;
(c) agglomerated particle of cooling (b).
The suitable agglomeration technique that is used for step (B) is described in detail at applicant's common unsettled European application EP-A-643130.In highly preferred agglomeration method, melting compound of the present invention and powder carrier material for example closely mix in the Loedige CB device at high-shear mixer.Agglomerate granule can be at other mixing device, for example ornamenting in Loedige KM device or the fluidized-bed.
In step (c), agglomerate granule preferably passes through the input chilled air cools in fluidized bed cooler.
In addition, can in step (b), add above a kind of carrier substance.
Also can be in step (b) detergent component of bringing Selection In property.Yet the selectivity detergent component preferably adds in the melting compound before in step (b).
Optionally in step (c) before cooling the dry agglomerates particle, the preferred fluidized bed dryer that adopts the input warm air.
Obtain the another kind of technology of particulate of the present invention and be to use spray drying technology.The appropriate technology that is used on the powder carrier material spraying melting compound on March 17th, 1994 disclosed co-pending patent application WO9405761 be described.
Optional ingredient in the particle
Optionally component can be included in the particle of the present invention, and it can be selected from other detergent component of hereinafter describing.In the time of in being included in particle, by particle weight they preferably with 0.05%-30%, more preferably 0.5%-20%, most preferably the content of 1.0%-15% exists.
The preferred selectivity detergent component that exists in particle of the present invention is an anion surfactant, preferred alkyl vitriol, alkylbenzene sulfonate or with the alkyl-sulphate of oxyethane and polyoxyethylene glycol condensation, preferably have the molecular weight of 5000-10000.
Another preferred ingredient in particle of the present invention is a cationic polymers, and described in next chapters and sections, it has clay soil removal/anti deposit properties again.
Detergent composition or its component
Particle of the present invention can add in the detergent composition (or mix with its component).
If particle of the present invention is present in the detergent composition, this will carry out in such a manner, make water-soluble cationic compound preferably in by detergent composition weight 0.01%-30%, more preferably 0.1%-15%, most preferably the content of 0.2%-3.0% is present in the detergent composition.
Definite character of other detergent component of these detergent composition or its component (wherein some also can be used as optional ingredient be included in the particle of the present invention) and their add-on will depend on the physical form of composition or its component and the definite character of the washing operation that adopted.
Detergent composition or its component preferably contain one or more other detergent components, and it is selected from (other) tensio-active agent, (other) washing assistant, sequestrant, SYNTHETIC OPTICAL WHITNER, bleach precursor, bleaching catalyst, organic polymer, other enzyme, suds suppressor, lime soap dispersing agent, other dirt suspension and anti redeposition agent, stain remover, spices and sanitas.
(other) tensio-active agent
Detergent composition or its component preferably contain (other) tensio-active agent, and it is selected from negatively charged ion, nonionic, positively charged ion, both sexes (ampholytic), both sexes (amphoteric) and zwitterionics and its mixture.
Classification and its 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 provides in the US4259217 of the Murphy of promulgation on March 31st, 1981.
If exist, both sexes (ampholytic), both sexes (amphoteric) and zwitterionics are used in combination with one or more negatively charged ion and/or nonionogenic tenside usually.
Anion surfactant
Detergent composition of the present invention or its component preferably contain other anion surfactant.Basically any anion surfactant that is used for washing purposes can be included in detergent composition.They can comprise anion sulfate, sulfonate, carboxylate salt and sarcosinate surfactant salt (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 the fatty acid amide of acyl isethinate, N-acyl taurine salt, methyl taurate, alkyl succinic acid ester salt and alkyl sulfosuccinate, 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, for example rosin, staybelite and the resinous acid and the hydrogenated resin acid that are present in or are obtained by Yatall MA.
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, alkylphenol oxyethane ether sulfate, C
5-C
17Acyl group-N-(C
1-C
4Alkyl) and-N-(C
1-C
2Hydroxyalkyl) vitriol of glucosamine sulfate and alkyl polysaccharide, 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, it is by per molecule 0.5 to 20 moles of ethylene oxide ethoxylation.Alkyl ethoxy sulfate surfactant is more preferably C
11-C
18, most preferably be C
11-C
15Alkyl-sulphate, it is by per molecule 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 number of 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 fit to comprises alkyl ethoxy carboxylate, alkyl polyethoxye multi-carboxylate's tensio-active agent and soap (' alkyl carboxyl '), especially some secondary soap of describing 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 based on weight basis, 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, methyl acidic group, amber acidic group, hydroxy succinic acid base and their mixture, and R
3Be selected from hydrogen, contain replacement or the unsubstituted alkyl and their mixture of 1 to 8 carbon atom.
Suitable soap surfactant is 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 material, 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
17The straight or branched alkyl or alkenyl, R
1Be C
1-C
4Alkyl, M are alkalimetal ions.Preferred embodiment is the tetradecyl 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 is applicable to the present invention.Preferred ethoxylation and propoxylation nonionogenic tenside.
The preferred alkoxylated tensio-active agent can be selected from the nonionic ethoxylate/propoxylated glycerine condenses of alkylphenol nonionic condenses, nonionic ethoxylated alcohol, nonionic ethoxylated/propoxylated fatty alcohol, propylene glycol and the nonionic ethoxylate condensation product of propylene oxide/ethylenediamine adduct.
Nonionic alcohol alcoxylates tensio-active agent
The condensation product of the alkylene oxide of fatty alcohol and 1-25 mole, especially oxyethane and/or propylene oxide is applicable to the present invention.The alkyl chain of fatty alcohol can be a straight or branched, and uncle or secondary alcohol contain 6-22 carbon atom usually.Especially preferred is to have the alcohol of the alkyl that contains 8-20 carbon atom and the condensation product of every mol of alcohol 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
1Those compounds 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
31Hydrocarbyl portion, 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 is polyhydroxy alkyl or its alkoxy derivative (preferred ethoxylation or propoxylation) with the linear hydrocarbyl chain that is connected directly to few three hydroxyls.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)
2Those compounds, 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.
The nonionic alkyl polysaccharide surfactant
It is open at the US4565647 of the Llenado of promulgation on January 22nd, 1986 to be used for suitable alkyl polysaccharide of the present invention, the polysaccharide that it has the hydrophobic grouping that contains 6-30 carbon atom and contains 1.3-10 sugar unit, for example many glycosides hydrophilic radical.
Preferred alkyl polyglycoside 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 that 0-10 and x are 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)
2Those compounds, R wherein
3Be selected from alkyl, hydroxyalkyl, acyl group amido propyl group and the alkyl phenyl or their mixture that contain 8-26 carbon atom; 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
18Acyl group amidoalkyl dimethyl oxidation amine.
The suitable example of alkyl both sexes dicarboxylic 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 its 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
-Those compounds, 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
10-18Acyl group amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.The beet alkali surface activator that cooperates also is applicable among the present invention.
Cats product
The suitable cation tensio-active agent that is used for detergent composition of the present invention or its component comprises quaternary ammonium surfactant, and it is selected from single C
6-C
16, preferred C
6-C
10N-alkyl or alkenyl ammonium surfactant, wherein all the other N positions are replaced by methyl, hydroxyethyl or hydroxypropyl.
The another kind of suitable cation tensio-active agent that is used for detergent composition of the present invention or its component is the cationic ester tensio-active agent.
The cationic ester tensio-active agent preferably has the dispersible compound of water of surfactant properties, and it contains at least one ester (promptly-COO-) key and at least one positively charged group.
Suitable cationic ester tensio-active agent comprises the cholinesterase tensio-active agent, is for example disclosing among the US4228042,4239660 and 4260529.
One preferred aspect, ester bond and positive charge group are spaced apart group and separate each other in surfactant molecule, spacer groups is by containing at least three atoms (i.e. three atom chain lengths), preferred 3-8 atom, more preferably 3-5 atom, most preferably the chain of 3 atoms is formed.The atom that forms the spacer groups chain is selected from carbon, nitrogen and Sauerstoffatom and its any mixture, and its condition is that any nitrogen in described chain or Sauerstoffatom only are connected with carbon atom in the chain.Therefore get rid of for example have-O-O-(being superoxide) ,-N-N-and-those groups of N-O-key, and comprise for example having-CH
2-O-CH
2-and CH
2-NH-CH
2The spacer groups of-key.Aspect preferred, the spacer groups chain only contains carbon atom, and most preferably this chain is a hydrocarbyl chain.
Cationic polymers
Detergent composition or its component can contain and have particle/clay soil removal/anti other polymerizing cationically ethoxylation amine compound of deposit properties again, and it is selected from water-soluble cationic polymer.These polymkeric substance contain polymer backbone, 2M group and at least one L-X group at least, wherein M be connected in skeleton or with the integrant cation group of skeleton; X is selected from H, C
1-C
4The non-ionic group of alkyl or hydroxyalkyl acrylate or ether group and their mixture; L is linking group M and X or the hydrophilic chain that X is connected to polymer backbone.
Polymerizing cationically ethoxylation amine compound can be by detergent composition weight 0.01%-30%, more preferably 0.1%-15%, and most preferably the content of 0.2%-3% is present in the detergent composition.
Be used for term " polymer " skeleton herein " be meant connected group M and L-X or with they integrant polymer-based groups.Be included in this term is oligopolymer skeleton (2-4 unit) and true polymers skeleton (5 or more multiple-unit).
Be used for herein term and " be connected in " and be meant that this group is the side chain of polymer backbone, the example is represented with following general structure A and B:
Term used herein " with ... constitute whole " be meant that group constitutes the part of polymer backbone, the example is represented by following general structure C and D:
Can use any polymer backbone, as long as the cationic polymers that forms is water miscible and has clay soil removal/anti deposit properties again.The suitable polymers skeleton can be obtained by poly-alkarylene such as polyolefine such as urethane, polyester, polyethers, polymeric amide, polyimide etc., polyacrylate, polyacrylamide, polyvingl ether, polyethylene, polypropylene, polystyrene, polyalkylene amine, polyalkyleneimine, polyvinylamine, PAH, polydiene propyl group amine, polyvinylpyridine, polyaminotriazole, polyvinyl alcohol, amino poly-ureylene and their mixture.
M can be any compatible cation group, and it contains N+ (quaternary ammonium) center of positive charge.The quaternary ammonium center of positive charge can be represented by following formula E and F:
Especially preferred M group is to contain those of the quaternary ammonium center represented by general formula E.Cation group preferably places near the polymer backbone or constitutes whole with polymer backbone.
The positive charge at N+ center is offset by the counter anion of suitable number.Suitable counter anion comprises Cl
-, Br
-, SO
3 2-, PO
4 2-, MeOSO
3 -Deng.Especially preferred counter anion is Cl
-And Br
-
X is selected from H, C
1-C
4The non-ionic group of alkyl or hydroxyalkyl acrylate or ether group or their mixture.Preferred ester or ether group are respectively acetic ester and methyl ether, and especially preferred non-ionic group is H and methyl ether.
Be applicable to that the cation group M of cationic polymers of granular detergent composition of the present invention and the ratio of non-ionic group X are generally about 1: about 1: 2 of 1-.Yet, for example (promptly contain group L-X) and blended cationic/nonionic monomer, can change the ratio of cation group M and non-ionic group X by suitable copolymerizable positively charged ion, nonionic.The ratio of group M and radicals X can be generally about 2: about 1: 10 of 1-.In the preferred cationic polymkeric substance, ratio is about 1: about 1: 5 of 1-.Normally random by the polymkeric substance that this interpolymerization forms, promptly positively charged ion, nonionic and mixed-cation/non-ionic monomer are with non-repetitive sequence copolymerization.
The unit that contains group M and group L-X can account for 100% of cationic polymers of the present invention.Yet, in polymkeric substance, comprise other unit (preferred nonionic) and also allow.Other unitary example comprises acrylamide, vinyl ether and contains the not quaternised tertiary amine group (M at N center
1) those unit.(polymkeric substance of about 10%-100% is the unit that contains M and L-X group to the 0%-that these other unit can account for polymkeric substance about 90%, comprises M
1-L-X group).Usually, these other unit about 50% (polymkeric substance of about 50%-100% is the unit that contains M and L-X group) of 0%-of accounting for polymkeric substance.
The number of each group M and L-X is generally about 2-about 200.The number of group M and the L-X about 3-about 100 that generally respectively does for oneself.The number of group M and the L-X about 3-about 40 that preferably respectively does for oneself.
Except linking group M and X or be connected in the group of polymer backbone, hydrophilic chain L is usually all by polyalkylene oxide groups-[(R ' O)
m(CH
2CH
2O)
n]-form.Polyalkylene oxide groups-(R ' O)
m-and-(CH
2CH
2O)
n-partly can mix or be preferably formed-(R ' O)
m-and-(CH
2CH
2O)
nThe block of-group.R ' is C preferably
3H
6(propylidene); M preferably 0-is about 5, and most preferably 0, promptly polyalkylene oxide groups is all by-(CH
2CH
2O)
n-group is formed.Group-(CH
2CH
2O)
n-preferably account for by weight described polyalkylene oxide groups at least about 85%; 100% (m is 0) by weight most preferably.For group-(CH
2CH
2O)
n-, the normally about 3-about 100 of n.Preferred n is about 12-about 42.
Many (2 or more) group-L-X also can link together and be connected on group M or the polymer backbone, and the example is represented by following general structure G and H:
Structure such as G and H can by for example with Racemic glycidol and group M or with polymer backbone reaction, the hydroxyl formation that ethoxylation subsequently forms.
The representation type of cationic polymers of the present invention is as follows: A. urethane, polyester, polyethers, polymeric amide or similar polymkeric substance.
One class suitable cationic polymers is obtained by urethane, polyester, polyethers, polymeric amide etc., and these polymkeric substance contain those unit that are selected from formula I, II and III:
Wherein A ' is:
Or
X is 0 or 1; R is H or C
1-C
4Alkyl or hydroxyalkyl; R
1Be C
2-C
12Alkylidene group, hydroxy alkylidene, alkenylene, cycloalkylidene, arylidene or alkarylene, or C with about 20 oxyalkylene units of 2-
2-C
3Oxyalkylene group, its condition be not with A
1Form O-O or O-N key; When x is 1, R
2Be-R
5-, except when A
1Be-C (=O)-or-(OR
8)
y-or-OR
5-outside, its condition be not with A
1Form O-O or N-O key, and R
3Be-R
5-, except when A
1Be-C (=O)-or-(R
8O)
y-or-R
5Outside the O-, its condition be not with A
1Form O-O or N-O key; R when x is 0
2Be-(OR
8)
y-.-OR
5-,
Or
And R
3Be-R
5-; R
4Be C
1-C
4Alkyl or hydroxyalkyl, or group-(R
5)
k-[(C
3H
6O)
m(CH
2CH
2O)
n]-X; R
5Be C
1-C
12Alkylidene group, hydroxy alkylidene, alkenylene, arylidene or alkarylene; Each R
6Be C
1-C
4Alkyl or hydroxyalkyl or group-(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,
-R
9Or their mixture, wherein R
9Be C
1-C
4Alkyl or hydroxyalkyl; K is 0 or 1; M and n make group-(CH
2CH
2O)
n-account for group-[(C by weight
3H
6O)
m(CH
2CH
2O)
n]-at least about 85% numerical value; M is 0-about 5; N is at least about 3; R is 1 or 2, and s is 1 or 2; With r+s be 3 or 4, y is 2-about 20; The numerical value of u, v and w makes at least 2 N+ centers and at least 2 X groups.
In above-mentioned formula, A
1Preferably
Or
A
2Preferably-O-; X preferably 1; With R H preferably.R
1But straight chain (for example-CH
2-CH
2-CH
2-,
) or side chain is (for example
) alkylidene group, hydroxy alkylidene, alkenylene, cycloalkylidene, arylidene or oxyalkylene; Work as R
1Be C
2-C
3During oxyalkylene group, the preferably about 2-about 12 of the number of oxyalkylene units; R
1C preferably
2-C
6Alkylidene group or phenylene, most preferably 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.Picture 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, and r and s respectively preferably 2; Y is 2-about 12 preferably.
In above-mentioned chemical formula, work as N
+Center and X group are 2 or 3 o'clock, and n is preferably at least about 6; N most preferably is at least about 12, and for the u+v+w of all scopes, general range is about 12-about 42.For homopolymer (v and w are 0), the preferably about 3-about 20 of u.For random copolymers (u is 1 or preferred 0 at least), v and w be preferably about 3-about 40 respectively.B. polyacrylate, polyacrylamide, polyvingl ether or similar polymkeric substance
Another kind of suitable cationic polymers is obtained by polyacrylate, polyacrylamide, polyvingl ether etc.These polymkeric substance contain the unit that is selected from formula IV, V and VI.
Wherein A ' is
Or
R is H or C
1-C
4Alkyl or hydroxyalkyl; R
1Be the C that replaces
2-C
12Alkylidene group, hydroxy alkylidene, alkenylene, arylidene or alkarylene, or C
2-C
3Oxyalkylene; Each R
2Be C
1-C
12Alkylidene group, hydroxy alkylidene, alkenylene, arylidene or alkarylene; Each R
3Be C
1-C
4Alkyl or hydroxyalkyl, or group-(R
2)
k-[(C
3H
6O)
m(CH
2CH
2O)
n]-X; Or form group-(CH together
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
4Form group-(CH together
2)
r-A
2-(CH
2)
s-; X is H,
-R
5Or their mixture, wherein R
5Be C
1-C
4Alkyl or hydroxyalkyl; J is 1 or 0; K is 1 or 0; M and n make group-(CH
2CH
2O)
n-account for group-[(C by weight
3H
6O)
m(CH
2CH
2O)
n]-at least about 85% numerical value; M is that 0-is about 5, and n is at least about 3; R is 1 or 2, and s is 1 or 2; With r+s be 3 or 4; The numerical value of u, v and w makes at least 2 N
+Center and at least 2 X groups.
In above-mentioned chemical formula, A
1Preferably
Or-O-; A
2Preferably-O-; R is H preferably.R
1It can be straight chain
(for example-CH
2-CH
2-CH
2-,
) or
Side chain (for example
The alkylidene group, hydroxy alkylidene, alkenylene, alkarylene 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 is
Or
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 respectively preferably 2.
In above-mentioned formula, n, u, v and w can change according to n, u for urethane and similar polymkeric substance, v and w.C. polyalkylene amine, polyalkyleneimine or similar polymkeric substance.
Another kind of suitable cationic polymers is to be obtained by polyalkylene amine, polyalkyleneimine etc.These polymkeric substance contain the unit that is selected from formula VII and VIII and IX.
R wherein
1Be C
2-C
12Alkylidene group, hydroxy alkylidene, alkenylene, cycloalkylidene, arylidene or alkarylene, or C with about 20 oxyalkylene units of 2-
2-C
3Oxyalkylene group, its prerequisite are not form the O-N key; Each R
2Be C
1-C
4Alkyl or hydroxyalkyl, or group-(R
2)
k-[(C
3H
6O)
m(CH
2CH
2O)
n]-X; R
3Be C
1-C
12Alkylidene group, hydroxy alkylidene, alkenylene, arylidene or alkarylene; M ' is N+ or N center; X is H,
-R
4Or their mixture, wherein R
4Be C
1-C
4Alkyl or hydroxyalkyl; When M ' is N+ d be 1 and when M ' is N d be 0; When M ' is N+, e be 2 and when M ' is N e be 1; K is 1 or 0; M and n make group-(CH
2CH
2O)
n-account for group-[(C by weight
3H
6O)
m(CH
2CH
2O)
n]-at least about 85% numerical value; M is that 0-is about 5, and n is at least about 3; The numerical value of x, y and z makes 2M ' group at least, 2N+ center and 2X group at least at least.
In above-mentioned formula, R
1Can be as the R in urethane and the similar polymkeric substance
1Change; Each R
2Methyl or group-(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 above-mentioned 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, and for the x+y+z of all scopes, scope is about 12-about 42 usually.X+y+z generally is that 2-is about 40, preferred 2-about 20.For short chain polymer, x+y+z can be 2-9, contains 2-9 N+ center, 2-11 X group.For long chain polymer, x+y+z is at least 10, and preferable range is 10-about 42.For short chain and long chain polymer, the mixture at M ' group normally about 50-100%N+ center and the about 50%N of 0-center.
Preferred cationic polymkeric substance in this class is by C
2-C
3Polyalkylene amine (x+y+z is 2-9) and polyalkyleneimine (x+y+z is at least 10, preferred 10-about 42) obtain.Especially preferred positively charged ion polyalkylene amine and polyalkyleneimine are cationic polyvinyl amine (PEA) and poly-ethyleneimine (PEI).These preferred cation polymkeric substance contain the unit with following general formula:
R wherein
2(preferable methyl), M ', X, d, x, y, z and n are as defined above; A is 1 or 0.
Before ethoxylation, the PEA that is used to prepare cationic polymers of the present invention has following general formula:
Wherein x+y+z is that 2-9 and a are 0 or 1 (the about 100-of molecular weight about 400).Each hydrogen atom that is connected in each nitrogen-atoms is represented the activity site of an ethoxylation subsequently.For preferred PEA, x+y+z is about 7 (the about 140-of molecular weight about 310) of about 3-.These PEA can be by comprising ammonia and Ethylene Dichloride reaction and fractionation subsequently obtain.Usually the PEA that obtains is Triethylenetetramine (TETA) (TETA) and tetren (TEPA).Surpass five amine, i.e. hexamine, seven amine, eight amine and nine possible amine, produced simultaneously mixture obviously can not pass through fractionation by distillation, can comprise other material, for example cyclammonium and especially piperazine.The cyclammonium that also may have the side chain that has nitrogen-atoms.Referring to the US2792372 of the Dickson that issues May 14 nineteen fifty-seven, it has described the preparation of PEA.
The minimum degree of the required ethoxylation of deposition properties can be according to unitary number of variations among the PEA again for preferred clay soil removal/anti.Wherein y+z is 2 or 3, and n is preferably at least about 6.Wherein y+z is 4-9, when n is at least about 3 the time, obtains suitable effect.For preferred cation PEA, n is at least about 12, and general range is about 12-about 42.
The PEI that is used to prepare polymkeric substance of the present invention had the molecular weight at least about 440 before ethoxylation, this represents at least about 10 unit.The preferred PEI that is used to prepare these polymkeric substance has the molecular weight of about 600-about 1800.The polymer backbone of these PEI can be represented by following general formula:
Wherein x, y and z's has the above polymkeric substance of the molecular weight of explanation with the enough big or small numerical value of expression with generation.Though the straight-chain polymer skeleton is possible, also may there be side chain.In polymkeric substance, exist primary, the relative proportion of the second month in a season and tertiary amine can change according to the mode of preparation.The distribution of amine groups is as follows usually:
-CH
2CH
2-NH
2 30％
-CH
2CH
2-NH- 40％
-CH
2CH
2-N- 30％
Each hydrogen atom that is connected to each nitrogen-atoms of PEI represents to be used for the activity site of ethoxylation subsequently.These PEI can be for example prepare by polymerization ethyleneimine in the presence of catalyzer such as carbonic acid gas, S-WAT, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetate etc.Be disclosed among the US2533696 (all being incorporated herein by reference) of the US2806839 of the US2208095 of the Esselmann of the US3033746 of the Mayle of the US2182306 of the Ulrich that the concrete grammar of preparation PEI was issued in December 5 nineteen thirty-nine etc., promulgation on May 8th, 1962 etc., promulgation on July 6th, 1940 etc., the Crowther of promulgation on September 17 nineteen fifty-seven and the Wilson of promulgation on May 21 nineteen fifty-one.
Such as in the above-mentioned formula definition, for positively charged ion PEI, n is at least about 3.Yet it should be noted, for suitable clay soil removal/anti the more required ethoxylation minimum degree of deposition properties can increase along with the increase of PEI molecular weight, especially surpass about 1800 when a lot.Equally, along with the increase of PEI molecular weight, for the ethoxylation degree increase of preferred polymers.For the PEI at least about 600 molecular weight, n is preferably at least about 12, and general range is about 12-about 42.For molecular weight is at least 1800 PEI, and n is preferably at least about 24, and general range is about 24-about 42.D. diallyl amine polymer
Another kind of suitable cationic polymers is the material that is obtained by diallyl amine.These polymkeric substance contain those materials that are selected from formula X and XI:
R wherein
1Be C
1-C
4Alkyl or hydroxyalkyl, or group-(R
2)
k-[(C
3H
6O)
m(CH
2CH
2O)
n]-X; R
2Be C
1-C
12Alkylidene group, hydroxy alkylidene, alkenylene, arylidene or alkarylene; Each R
3Be C
1-C
4Alkyl or hydroxyalkyl or form group-(CH together
2)
r-A-(CH
2)
s-; Wherein A be-O-or-CH
2-; X is H,
-R
4Or their mixture, wherein R
4Be C
1-C
4Alkyl or hydroxyalkyl; K is 1 or 0; M and n make group-(CH
2CH
2O)
n-account for group-[(C by weight
3H
6O)
m(CH
2CH
2O)
nThe numerical value of]-Yue at least 85%; M is that 0-is about 5, and n is at least about 3; R is 1 or 2, and s is 1 or 2; With r+s be 3 or 4, x is 1 or 0; Y is 1 when x is 0; With y when x is 1 be 0; The numerical value of u and v makes at least 2 N+ centers and at least 2 X groups.
In above-mentioned 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 respectively preferably 2.
In above-mentioned formula, when the number of N+ center and X group was respectively 2 or 3, n was preferably at least about 6, and n preferably at least 12, and for the u+v of all scopes, general range is about 12-about 42.Usually, v is 0, and u is that 2-is about 40, preferred 2-about 20.
(other) water soluble detergency promoter compound
Detergent composition or its component preferably contain the water soluble detergency promoter compound, and it is usually to press composition weight meter 1%-80%, preferred 10%-70% by weight, and most preferably the content of 20%-60% is present in the detergent composition by weight.
Suitable water soluble detergency promoter compound comprises water-soluble monomer multi-carboxylate or the poly carboxylic acid of their sour form, homopolymerization or copolymerization or their salt, and wherein poly carboxylic acid contains the mixture that at least two quilts are no more than hydroxy-acid group, borate, phosphoric acid salt and any above-mentioned substance that two carbon atoms separate.
Carboxylate salt or multi-carboxy acid salt washing agent can be monomer or oligopolymer type, although because cost and performance, monomeric multi-carboxylate is normally preferred.
The suitable carboxylate salt that contains a carboxyl comprises the water-soluble salt of lactic acid, oxyacetic acid and their ether derivant.The multi-carboxylate of containing two carboxyls comprises water-soluble salt and the ether carboxylate and the sulfinyl carboxylate salt of succsinic acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid.The multi-carboxylate of containing three carboxyls especially comprises water-soluble citrate, aconitate and citraconate and succinate derivative, for example the carboxy methoxy-succinic acid salt of in English Patent 1379241, describing, the newborn 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 multi-carboxylate of containing 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 multi-carboxylate of sulfo group be included in English Patent 1398421 and 1398422 and in US3936448 disclosed sulfo-succinic acid salt derivative and the sulfonation pyrolysis Citrate trianion in English Patent 1439000, described.Preferred multi-carboxylate is that each molecule contains hydroxycarboxylate, the most particularly Citrate trianion of three carboxyls at the most.
The mixture of the parent acid of monomer or oligomerisation multi-carboxylate sequestrant or they and salt, for example citric acid or Citrate trianion/citric acid mixture also can be considered as builder component.
The borate washing assistant and contain washing composition store or wash conditions under can to produce the washing assistant that boratory borate forms material be the useful water soluble detergency promoter of the present invention.
The suitable example of water-soluble phosphate washing assistant is that tripolyphosphate an alkali metal salt, trisodium phosphate, potassium and ammonium, trisodium phosphate, potassium and ammonium, sodium orthophosphate and potassium, the polymerization degree are the partially poly-/sodium phosphate of about 6-21 and the salt of phytinic acid.
Part solubility or insoluble washing-aid compound
Detergent composition of the present invention or its component can contain part solubility or insoluble washing-aid compound, it is usually to count 1%-80% by composition weight, preferred 10%-70% by weight, most preferably the content of 20%-60% is present in the detergent composition by weight.
Preferably insoluble basically washing-aid compound is the silico-aluminate ion exchange material, preferably aforesaid zeolite A and zeolite MAP.
Heavy metal ion chelating agent
Detergent composition or its component preferably contain the heavy metal ion chelating agent as optional ingredient.Heavy metal ion chelating agent has in this article referred to the component of chelating heavy metal ion effect.These components can also have calcium and magnesium sequestering power, but preferably show in conjunction with heavy metal ion, for example the 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 polyamino carboxylic acid, for example second diamino tetraacethyl, 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.The iminodiethanoic acid of describing in EP-A-516102-N-2-hydroxy-propanesulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrant also are suitable in the present invention.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 fit to.
EP-A-476257 has described suitable amino based 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.Dinicotinic acid and 2-phosphono-containing butane-1,2,4-tricarboxylic acid also are 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 system
The preferred property of detergent composition or its component is the organic peroxide acid bleach system.Bleach system contains hydrogen peroxide cource and organic peroxide acid bleach precursor compound in a preferred embodiment.Carry out the preparation of organic peroxide acid by the situ reaction of precursor and hydrogen peroxide cource.Preferred hydrogen peroxide cource comprises inorganic perhydrate SYNTHETIC OPTICAL WHITNER.In another preferred embodiment, preformed organic peroxide acid is directly added in the composition.Also can imagine the composition that contains with the mixture of preformed 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% by weight, most preferably 5%-25% by weight.
The example of inorganic perhydrate salt comprises perborate, percarbonate, superphosphate, persulphate and persilicate.Inorganic perhydrate salt is an alkali metal salt normally.In inorganic perhydrate salt can be comprised in the crystalline solid forms of no supplementary protection.Yet for some perhydrate salt, the preferred embodiment of this particulate composition is used the material of coated form, and it is 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 nominal formula NaBO
2H
2O
2Monohydrate or formula NaBO
2H
2O
23H
2The tetrahydrate 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
2The addition compound of the chemical formula of O obtains with crystalline solid commercial.
The peroxide Potassium peroxysulfate is another the inorganic perhydrate salt that is used for detergent composition of the present invention.
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, and the structure of the peroxy acid that was generated when making hydrolysis is:
The peroxyacid bleach precursor compound is preferably in by detergent composition weight 0.5%-20%, more preferably 1%-15% by weight, and most preferably the content of 1.5%-10% adds by weight.
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, imide, lactan and imidazoles and oxime.The example of useful material is disclosed in GB-A-1586789 in this class.Suitable ester GB-A-836988,864798,1147871,2143231 and EP-A-0170386 in be disclosed.
Leavings group
Leavings group, hereinafter referred to as the L group must be enough reactive so that cross hydrolysis reaction (for example wash(ing)cycle) generation in the time range of the best.Yet if L is too active, this activator is used for bleaching composition and will be difficult to stablize.
Preferred L group is selected from:
With
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 alkenylene chain and the Y that contains 1-8 carbon atom is H or solubilization radical.Any R
1, R
3And R
4Can be by any functional group basically, for example comprise that alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical, acid amides and ammonium or alkyl ammonium group replace.
Preferred solubilization radical 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 chain that contains 1-4 carbon atom, M provides water miscible positively charged ion to bleach-activating agent, and X provides water-soluble anionic to bleach-activating agent.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 when crossing hydrolysis.The preferred precursor of this class provides peracetic acid when crossing hydrolysis.
The alkyl peroxycarboxylic acid precursors compound of preferred imide-type comprises N-N, N ', and tetra-acetylatedization of N ' Alkylenediamine, wherein alkylidene group contains 1-6 carbon atom, and especially wherein alkylidene group contains the compound of 1,2 and 6 carbon atom.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 suitable for the present invention, and it comprises those compounds of following general formula:
Or
R wherein
1For having 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 bleach activating 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 when crossing hydrolysis.Suitable O-acylations peroxybenzoic acid precursors compound comprises the benzoyl product of replacement and unsubstituted benzoyloxy benzene sulfonate and Sorbitol Powder, glucose and all carbohydrates and benzoylation reagent, and those imide-type compounds comprise 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 produces the positively charged ion peroxy acid when crossing hydrolysis.
The positively charged ion peroxyacid precursor is usually by with positively charged functional group, for example ammonium or alkyl ammonium group, and the peroxy acid of the peroxyacid precursor compound that preferred ethyl or the replacement of ammonium methyl group are suitable partly forms.The positively charged ion peroxyacid precursor is conduct and suitable negatively charged ion usually, and for example halogen ionic salt is present in the solid detergent composition.
So the peroxyacid precursor compound that is replaced by positively charged ion can be the precursor compound of the derivative of peroxybenzoic acid as indicated above 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 US4904406,4751015,4988451,4397757,5269962,5127852,5039022,5106528, UK1382594, EP475512,458396 and 284292 and JP87-318332 in be described.
The example of preferred cation peroxyacid precursor is described in GB Patent Application No. 9407944.9 and US number of patent application 08/298903,08/298650,08/298904 and 08/298906.
Suitable positively charged ion peroxyacid precursor comprises alkyl or the tetra-acetylated glucose benzoyl peroxide of benzoyloxy benzene sulfonate, N-acylations hexanolactam and 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 benzoxazine class precursor compound in for example EP-A-332294 and EP-A-482807, especially has those compounds of following formula:
R wherein
1Be H, alkyl, alkaryl, aryl or aralkyl.
Preformed organic peroxide acid
Except that organic peroxide acid bleach precursor compound or as its surrogate, the organic peroxide acid bleach system can contain preformed organic peroxide acid, and common content is for pressing composition weight meter 1%-15%, more preferably 1%-10% by weight.
The organic peroxy acid compound of preferred class is the compound that the acid amides of following general formula replaces:
Or
R wherein
1Be alkyl, aryl or the alkaryl that contains 1-14 carbon atom, R
2Be alkylidene group, arylidene and the alkarylene that contains 1-14 carbon atom, R
5For H or contain alkyl, aryl or the alkaryl of 1-10 carbon atom.The organic peroxy acid compound 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.Single-and two cross nonane diacid, list-and two cross brazilic acid and N-phthaloyl amino oxy hexanoic acid also be applicable among the present invention.Enzyme
Another preferred ingredient that is used for detergent composition or its component is one or more additional enzymes.
Preferred additional enzymes material comprises commercial available cellulase, endolase, at, amylase, lipase, neutrality and Sumizyme MP, esterase, polygalacturonase, laccase and the peroxidase that is routinely added in the detergent composition.Suitable enzyme comes into question 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 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 in GB-1269839 (NoVo).Preferred commercial 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 composition of the present invention by the content of composition weight meter 0.0001%-2% organized enzyme.
(other) organic polymer
Organic polymer is the preferred annexing ingredient of detergent composition or its component, and preferred component existence as any grain fraction that plays the effect that grain fraction is bonded together.Organic polymer in this article refers to any basically polymerizable organic compound that is used as dispersion agent, anti redeposition agent and soil-suspending agent in detergent composition, it is included in any high molecular organic polymer of describing as the clay flocculating agent herein, but is not quaternized ethoxylation of the present invention (gathering) amine clay soil removal/anti deposition agent again.
Organic polymer is usually pressing composition weight meter 0.1%-30%, preferred 0.5%-15%, and most preferably the content of 1%-10% adds in the detergent composition of the present invention.
The example of organic polymer comprises poly carboxylic acid or its salt of water-soluble organic homopolymerization or copolymerization, and wherein poly carboxylic acid comprises that at least two quilts are no more than the hydroxy-acid group that two carbon atoms separate.The polymkeric substance of back one type is disclosed in GB-A-1596756.The example of this salt is the multipolymer of the polyacrylate of MWt1000-5000 and they and maleic anhydride, and this multipolymer has 2000-100000, especially the molecular weight of 40000-80000.
Being used for polyamino compound of the present invention comprises as EP-A-305282, EP-A-305283 and the disclosed compound that is obtained by aspartic acid of EP-A-351629.
The terpolymer that contains the monomeric unit that is selected from toxilic acid, vinylformic acid, poly aspartic acid and vinyl alcohol, the compound that especially has the molecular weight of 5000-10000 also is fit in the present invention.
Other organic polymer that is suitable for adding in the detergent composition of the present invention comprises derivatived cellulose, for example methylcellulose gum, carboxymethyl cellulose, Vltra tears and Natvosol.
Other useful organic polymers are (other) polyoxyethylene glycol, molecular weight 1000-10000 especially, more preferably 2000-8000 and most preferably from about 4000 compound.
Press down foam system
When preparation was used for the machine-washing composition, detergent composition preferably contained by composition weight meter with 0.01%-15%, preferred 0.05%-10%, and most preferably the content of 0.1%-5% exists presses down foam system.
Being used for the suitable foam that presses down of the present invention is to contain any basically known defoaming compounds, comprises for example polysiloxane defoaming compounds and 2-alkyl chain triacontanol defoaming compounds.
Defoaming compounds is meant and plays the solution that for example suppresses detergent composition herein, especially has the mixture that foams under the situation of solution stirring or produce any compound of foamy or compound.
Be used for especially preferred defoaming compounds of the present invention and be the polysiloxane defoaming compounds of any defoaming compounds that comprises the polysiloxane component that defines herein.This polysiloxane defoaming compounds 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 various types of alkyl.Preferred polysiloxane defoaming compounds is a siloxanes, especially contains the unitary polydimethylsiloxane of trimethyl silyl end-blocking.
Other suitable defoaming compounds comprises mono carboxylic lipid acid and its 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 as suds suppressor contains 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 fatty ester (for example fatty acid 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 phosphoric acid ester.
The preferred foam system that presses down is contained
(a) defoaming compounds, preferred polysiloxane defoaming compounds most preferably contains the polysiloxane defoaming compounds of following combination
(i) by polysiloxane defoaming compounds weight, content is 50%-99%, the polydimethylsiloxane of preferred 75%-95%; With
(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, most preferably contain the compound of silicone glycol rake formula multipolymer, wherein the content of polyoxyalkylene is 72-78%, and 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%; Especially preferred this class silicone glycol rake formula multipolymer is the commercial DCO544 that can be obtained with trade(brand)name DCO544 by DOW Corning;
(c) inert support fluid compound, most preferably containing ethoxylation degree is 5-50, the C of preferred 8-15
16-C
18The compound of ethoxylated alcohol; Its content is 5%-80% by weight, preferred 10%-70%.
Highly preferred granular suds suppressing system is described in EP-A-0210731, it contains polysiloxane defoaming compounds and fusing point is 50 ℃-85 ℃ organic carrier material, and wherein the organic carrier material contains glycerine and has the monoesters of the lipid acid of the carbochain that contains 12-20 carbon atom.EP-A-0210721 discloses other preferred granular suds suppressing system, and wherein the organic carrier material 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 composition of the present invention also can 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, thereby these polymkeric substance can be cross-linked polymers.
A) polyamine N-oxide pllymers
Be applicable to that polyamine N-oxide pllymers of the present invention contains the unit with following structural formula:
Wherein P is that polymerisable unit and A are
-O-,-S-,-N-; X is 0 or 1; R is aliphatic series, aliphatic, the aromatic series of ethoxylation, heterocycle or alicyclic 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 alicyclic 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 or both with polymeric skeleton.
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, alicyclic ring or heterocyclic group.The described 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 pyridine, pyrroles, imidazoles, tetramethyleneimine, 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 class are the polyamine N-oxide with general formula (I), and wherein R is aromatic series, heterocycle or alicyclic 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 can almost obtain with any polymerization degree.The polymerization degree 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-vinyl pyrrolidone polymer 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 composition of the present invention can also use the Polyvinylpyrolidone (PVP) (" PVP ") of molecular-weight average as 2500-400000.Suitable Polyvinylpyrolidone (PVP) commercial by ISPCorporation, New York, NY and Montreal, Canada is with ProductName PVP K-15 (viscosity molecular weight is 10000), PVP K-30 (molecular-weight average 40000), and PVP K-60 (molecular-weight average 160000) and PVP K-90 (molecular-weight average 360000) obtain.PVP K-15 also can be obtained by ISPCorporation.Comprise Sokalan HP 165 and Sokalan HP 12 at commercial other suitable Polyvinylpyrolidone (PVP) that obtains by BASF Cooperation.
D) Ju Yi Xi oxazolidinone
Detergent composition of the present invention also can use Ju Yi Xi oxazolidinone as the polymeric dye transfer inhibitor.Described Ju Yi Xi oxazolidinone has the molecular-weight average of 2500-400000.
E) polyvinyl imidazol
Detergent composition of the present invention also can use polyvinyl imidazol as the polymeric dye transfer inhibitor.Described polyvinyl imidazol preferably has the molecular-weight average of 2500-400000.
White dyes
Detergent composition of the present invention also optionally contains the hydrophilic white dyes of about by weight some type of 0.005% to 5%.
The hydrophilic white dyes of available has 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, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid and disodium salt.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, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl) amino]-2,2 '-the stilbene disulfonic acid disodium salt.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, whitening agent is 4,4 '-two [(4-anilino-6-morpholino-s-triazine-2-yl) amino] 2,2 '-stilbene disulfonic acid sodium salt.Concrete whitening agent is sold with trade(brand)name TinopalAMS-GX by Ciba-Geigy company commercial.
The polymerization stain remover
Known polymerization stain remover, hereinafter referred to as " SRA " optionally is used for detergent composition of the present invention.If use, SRA is generally the 0.01%-10.0% that accounts for composition by weight, is generally 0.1%-5%, preferred 0.2%-3.0%.
Preferred SRA generally contains hydrophilic segment makes hydrophobic fiber, as the surface hydrophilic of polyester and nylon; SRA also contain hydrophobic part with the surface that is deposited on hydrophobic fiber and in whole washing and rinse cycle all the time attached to fiber surface on, therefore hydrophilic segment is played fixed action.Easier cleaning in this feasible spot washing process afterwards that after SRA handles, produces.
Preferred SRA comprises the oligomerisation terephthalate, by comprising the method preparation of at least a transesterification/oligomerisation, uses metal catalyst usually, for example titanium alkoxide (IV) usually.This ester can use and can add in the ester structure by one, two, three, four or a plurality of position, and does not form closely crosslinked integrally-built other monomer preparation certainly.
Suitable SRA comprises the sulfonated products of linear ester oligopolymer basically; it is formed by the multiple unitary oligomer ester skeleton of terephthaloyl and oxyalkylene oxygen basic weight with the covalently bound sulfonation end group that is obtained by allyl group of skeleton, for example describes among the US4968451 of J.J.Scheibel that issues in November 6 nineteen ninety and E.P.Gosselink.This ester oligomer can prepare by the following method: (a) ethoxylation allyl alcohol; (b) make product and dimethyl terephthalate (DMT) (" DMT ") and 1 of (a), 2-propylene glycol (" PG ") reacts in two step transesterification/oligomerisation processes; The product of (b) is reacted with sodium metabisulfite in water.Other SRA comprises the end capped terephthalic acid 1 of nonionic of the US4711730 of the Gosselink of on December 8th, 1987 promulgation etc., 2-propylene glycol/polyoxyethylene ester polyester is for example by those of transesterification/oligomerisation preparation of poly-(ethylene glycol) methyl ether, DMT, PG and poly-(ethylene glycol) (" PEG ").Other example of SRA comprises the end capped oligomer ester of part or all of negatively charged ion of the US4721580 of the Gosselink that on January 26th, 1988 issued, for example by ethylene glycol (" EG "), PG, DMT and 3, and the oligopolymer that the hot sodium sulfonate of 6-two oxa-s-8-hydroxyl obtains; The end capped block polyester oligopolymer of nonionic among the US4702857 of the Gosselink of promulgation on October 27th, 1987; for example by DMT; the end capped PEG of methyl (Me) and EG and/or PG; or DMT; EG and/PG; the compound of the mixture preparation of end capped PEG of Me and 5-sodium sulfonate dimethyl isophthalate; Maldonado with promulgation on October 31st, 1989; the negatively charged ion of people's such as Gosselink US4877896; especially the end capped terephthalate of sulphur aroyl; the latter is the SRA that generally is used to wash with the fabric-conditioning product; the example is by a sulfosalicylic acid list sodium salt; the ester composition of PG and DMT preparation; optionally but preferably also contain the PEG of adding, PEG3400 for example.
SRA also comprises the simple copolymer block of terephthalic acid ethylidene ester or trimethylene terephthalate and polyethylene oxide or poly(propylene oxide) terephthalate, referring to the US3959230 of the Hays on May 25th, 1976 and the US3893929 of the Basadur on July 18th, 1975; Derivatived cellulose, for example the hydroxy ethers cellulose polymer compound that obtains with METHOCEL by Dow; C
1-4Alkylcellulose and C
4Hydroxy alkyl cellulose; US4000093 referring to the Nicol on December 28th, 1976 etc.; Be about 1.6 to about 2.3 and be about 80 methyl cellulose ethers at 20 ℃ of soltion viscosities of measuring down with average replacement (methyl) degree of every dehydrated glucose unit to about 120 centipoises as 2% aqueous solution.This material obtains as METOLOSE SM100 and METOLOSE SM200, and they are the trade(brand)names by the methyl cellulose ether of Shin-etsu Kagaku Kogyo KK preparation.
Another kind of SRA comprises: (I) use two isocyanuric acid ester couplers being connected to the nonionic terephthalate of polyester construction, referring to the US4240918 of the US4201824 of Violland etc. and Lagasse etc.; (II) by trimellitic acid 1,2-anhydride being added to the SRA that has the carboxylicesters end group that among the known SRA end hydroxyl is changed into the trimellitate preparation.By selecting catalyst suitably, trimellitic anhydride is by the isolated carboxylicesters of trimellitic anhydride and the end Cheng Jian of polymkeric substance, rather than opens the acid anhydride key.Nonionic or negatively charged ion SRA all can be used as starting material, as long as have can esterified hydroxyl end groups for they.US4525524 referring to Tung etc.Other class comprises: (III) urethane connects the SRA of the negatively charged ion terephthalic acid ester group of kind, referring to the US4201824 of Violland etc.
The form of composition
Particle of the present invention can pass through the whole bag of tricks, comprises that all cpds contained in the dry blend agglomerate detergent component adds in the detergent component.
Detergent composition or its component can have various physical form, comprise particle, tablet, thin slice, cream and bulk form.The especially so-called concentrated granular detergent composition of composition, it is adapted to pass through the diverting device that is placed in the machine roll that dirty fabric load is housed and adds in the washing machine.
The bulk density of granular detergent composition of the present invention has 600g/l at least usually, more preferably the bulk density of 650g/l-1200g/l.Bulk density is measured by simple funnel and cup device, and described device is made up of the conical funnel that is molded in rigidly on the pedestal, and funnel bottom is equipped with clack valve makes the material in the funnel enter in the cylinder cup of coaxial placement under funnel.Funnel is 130 millimeters high, and the internal 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 pedestal upper surface.The height overall of cup is 90 millimeters, and internal height is 87 millimeters, and internal diameter is 84 millimeters, and nominal volume is 500 milliliters.
For measuring, in funnel, incline to the powder of packing into hand, open clack valve, make powder overflow cup.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 limb and was removed excessive powder.The cup of weighing then and filling obtains bulk density g/l with 2 with the powder weight that obtains is on duty.Carry out replicate measurement on demand.
Compact solid can be used any suitable method for densifying, for example compressing tablet, granulation or extruding, preferred compressing tablet preparation.The tablet that is used for dishware washing method preferably uses the standard rotary tablet machine, adopts 5-13KN/cm
2, more preferably 5-11KN/cm
2Pressure preparation, make compact solid have 176N-275N, the minimum hardness of preferred 195N-245N, the C100 determination of hardness test that hardness is provided by the I.Holland instrument.This method can be used for preparing virtually any size or shape all or the stratiform tablet.Tablet is preferably symmetric to guarantee tablet uniform dissolution in washing soln.
The abbreviation of using among the embodiment
In detergent composition, the component of abbreviation sign has following implication: LAS: straight chain C
12Sodium 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 C of average z moles of ethylene oxide condensation
1x-C
1yMain linear primary
Alcohol QAS: R
2N
+(CH
3)
2(C
2H
4OH), R
2=C
12-C
14Soap: straight-chain alkyl carboxylic acid's sodium, mixed by 80/20 of butter and Oleum Cocois
Thing obtains CFAA: C
12-C
14(coconut) alkyl N-methyl glucose amide TFAA: C
16-C
18Alkyl N-methyl glucose amide TPKFA: C
12-C
14Dial the full cut lipid acid STPP on top: anhydrous sodium tripolyphosphate TSPP: tetrasodium pyrophosphate zeolite A: formula Na
12(AlO
2SiO
2)
12.27H
2The hydrated sodium aluminosilicate of O, just
Grade particles is of a size of 0.1-10 micron zeolite A (doing): zeolite A, moisture content is lower than 10% zeolite MAP by weight: silica alumina ratio is 1.07 hydrated sodium aluminosilicate zeolite MAP 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 a 200-900 micron anhydrous sodium carbonate supercarbonate: particle size distribution is the anhydrous sodium bicarbonate silicate of 400-1200 micron: amorphous sodium silicate (SiO
2: Na
2O ratio=2.0: 1) sodium sulfate: anhydrous slufuric acid na citrate: citrate trisodium dihydrate, activity 86.4%, particle size branch
Cloth is 425-850 micron MA/AA: 1: 4 toxilic acid/acrylic copolymer, the about 70000AA of molecular-weight average: polyacrylic acid sodium polymer, molecular-weight average 4500CMC: the plain ether of sodium carboxyme-thylcellulose fibre: the polymerization degree is 650 methyl cellulose ether, and is commercial by Shin Etsu
Chemicals obtains proteolytic enzyme: sold with trade(brand)name Savinase by NOVO Industries A/S
Proteolytic enzyme, active 4KNPU/gAlcalase:, live by the proteolytic ferment that NOVO Industries A/S sells
Property 3AU/g cellulase: sell with trade(brand)name Carezyme by NOVO Industries A/S
Cellulase, active 1000CEVUU/g amylase: by NOVO Industries A/S with trade(brand)name Termamyl 120T
The amylase of selling, active 120KNU/g lipase: sell with trade(brand)name Lipolase by NOVO Industries A/S
Lipase, active 100KLU/gEndolase: endoglucanase, sell by NOVO Industries A/S,
Active 3000CEVU/gPB4: nominal formula NaBO
2.3H
2O.H
2O
2Sodium perborate tetrahydrate PB1: nominal formula NaBO
2.H
2O
2Anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER percarbonate: nominal formula 2Na
2CO
33H
2O
2SPC-D NOBS: nonanoly acyloxy benzene sulfonate, sodium-salt form TAED: tetra acetyl ethylene diamine Mn catalyst: as the Mn that describes in US5246621 and 5244594
IV 2(m-
O)
3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2(PF
6)
2DTPA: ethylidene pentaacetic acid DTPMP: diethylenetriamine five (methylene phosphonic acid salt), by Meng Shan all with merchant
Name of an article Dequest 2060 sells the photoactivation SYNTHETIC OPTICAL WHITNER: use the capsular sulfonation zinc phthalocyanine phthalocyanine whitening agent of dextrin polymer soluble bag 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: 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid EDDS: quadrol-N, N '-disuccinic acid QEA1: two ((C
2H
5O) (C
2H
4O)
n) (CH
3)-N
+-C
6H
12-N
+-(CH
3) in pairs
((C
2H
5O)-(C
2H
4O)
n), n=20-30QEA2 wherein: two ((C
2H
5O)-(C
2H
4O)
n) (CH
3) N
+R
1, R wherein
1Be C
4-C
12
Alkyl, n=20-30QEA3: three { (two ((C
2H
5O)-(C
2H
4O)
n) (CH
3)-N
+)-(CONC
3H
6)-
C
3H
6O; n=20-26PEGX wherein: polyoxyethylene glycol; molecular weight XPEO: polyethylene oxide, molecular weight 50000TEPAE: tetren ethoxylate PVP: polyvinylpyrrolidonepolymers polymers PVNO: polyvinylpyridine N-oxide compound PVPVI: the multipolymer SRP1 of Polyvinylpyrolidone (PVP) and vinyl imidazole: sulfo group benzoyl end group is end capped to have ethylene oxide oxygen base and right
The ester SRP2 of phenyl-diformyl base skeleton: the short block of diethoxyization poly-(terephthalic acid 1,2 propylidene ester)
Multipolymer polysiloxane froth breaking: the polydimethylsiloxane foam control agent with as the siloxanes-oxygen thinner alkene copolymer of dispersion agent, the weight ratio of described foam control agent and described dispersion agent
Be 10: 1-100: 1 wax: paraffin
In following embodiment, all content are to represent by composition weight meter %:
Embodiment 1
Be prepared as follows the detergent formulations that is particularly useful for European washing machine wash conditions.
Embodiment 2
| A | B | C | D | |
| The blowing powder | ||||
| 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/AA | 2.0 | 4.0 | 6.0 | 4.0 |
| Silicate | 7.0 | 3.0 | 3.0 | 3.0 |
| CMC | 1.0 | 1.0 | 0.5 | 0.6 |
| Whitening agent | 0.2 | 0.2 | 0.2 | 0.2 |
| The polysiloxane suds suppressor | 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 suds suppressor | 0.3 | 0.3 | 0.3 | - |
| Agglomerate | ||||
| QEA1 | 0.8 | 1.0 | 1.4 | 0.5 |
| QEA2 | - | - | - | 0.5 |
| Zeolite A (doing) | 2.5 | 2.5 | 3.0 | 2.0 |
| 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 | 0.5 | 0.4 | 0.2 |
| Amylase | 0.2 | 0.2 | 0.2 | 0.4 |
| The photoactivation SYNTHETIC OPTICAL WHITNER | - | - | - | 0.15 |
| Altogether | 100.0 | 100.0 | 100.0 | 100.0 |
Be prepared as follows the granulated detergent preparation.
Embodiment 3
| E | F | G | H | I | J | ||
| The blowing powder | |||||||
| LAS | 22.0 | 5.0 | 4.0 | 9.0 | 8.0 | 7.0 | |
| C45AS | 7.0 | 7.0 | 6.0 | - | - | - | |
| C46AS | - | 4.0 | 3.0 | - | - | - | |
| C45E35 | - | 3.0 | 2.0 | 8.0 | 5.0 | 4.0 | |
| Zeolite A | 6.0 | 16.0 | 14.0 | 19.0 | 16.0 | 14.0 | |
| MA/AA | 6.0 | 3.0 | 3.0 | - | - | - | |
| AA | - | 3.0 | 3.0 | 2.0 | 3.0 | 3.0 | |
| Sodium sulfate | 7.0 | 18.3 | 11.3 | 24.0 | 19.3 | 19.3 | |
| Silicate | 5.0 | 1.0 | 1.0 | 2.0 | 1.0 | 1.0 | |
| Carbonate | 28.3 | 9.0 | 7.0 | 25.7 | 8.0 | 6.0 | |
| PEG4000 | 0.5 | 1.5 | 1.5 | 1.0 | 1.5 | 1.0 | |
| Sodium oleate | 2.0 | - | - | - | - | - | |
| DTPA | 0.4 | - | 0.5 | - | - | 0.5 | |
| Whitening agent | 0.2 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | |
| Spraying | |||||||
| C25E9 | 1.0 | - | - | - | - | - | |
| C45E7 | - | 2.0 | 2.0 | 0.5 | 2.0 | 2.0 | |
| Spices | 1.0 | 0.3 | 0.3 | 1.0 | 0.3 | 0.3 | |
| Agglomerate | |||||||
| C45AS | - | 5.0 | 5.0 | - | 5.0 | 5.0 | |
| LAS | - | 2.0 | 2.0 | - | 2.0 | 2.0 | |
| QEA1 | 0.9 | 0.9 | - | - | 0.5 | 1.1 | |
| QEA2 | - | - | 0.8 | 1.0 | - | - | |
| QEA3 | - | - | 0.4 | - | - | - | |
| Zeolite A (doing) | 4.5 | 7.5 | 7.5 | 2.0 | 7.5 | 7.5 | |
| HEDP | - | 1.0 | - | - | 2.0 | - | |
| Carbonate | - | 4.0 | 4.0 | - | 4.0 | 4.0 | |
| PEG6000 | - | - | - | 0.5 | 0.5 | - |
| PEG8000 | - | 0.5 | 0.5 | - | - | 0.5 |
| Minor component (water etc.) | - | 2.0 | 2.0 | - | 2.0 | 2.0 |
| Dried additive | ||||||
| TEAD | 1.0 | 2.0 | 3.0 | 1.0 | 3.0 | 2.0 |
| PB4 | - | 1.0 | 4.0 | - | 5.0 | 0.5 |
| PB1 | 6.0 | - | - | - | - | - |
| Percarbonate | - | 5.0 | 12.5 | - | - | - |
| Carbonate | - | 5.3 | 1.8 | - | 4.0 | 4.0 |
| NOBS | 4.5 | - | 6.0 | - | - | 0.6 |
| Cumene sulfonic acid | - | 2.0 | 2.0 | - | 2.0 | 2.0 |
| Lipase | 0.4 | 0.4 | 0.4 | 0.06 | 0.05 | 0.2 |
| Cellulase | 0.1 | 0.2 | 0.2 | - | 0.2 | 0.2 |
| Amylase | 0.1 | 0.3 | 0.3 | - | - | - |
| Proteolytic enzyme | 1.0 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| PVPVI | - | 0.5 | 0.5 | - | - | - |
| PVP | 0.5 | 0.5 | 0.5 | - | - | - |
| PVNO | - | 0.5 | 0.5 | - | - | - |
| SRP1 | - | 0.5 | 0.5 | - | - | - |
| The polysiloxane suds suppressor | - | 0.2 | 0.2 | - | 0.2 | 0.2 |
| Altogether | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 |
Be prepared as follows the granulated detergent preparation:
Embodiment 4
| K | L | M | |
| The blowing powder | |||
| Zeolite A | 30.0 | 22.0 | 6.0 |
| Sodium sulfate | 19.0 | 5.0 | 7.0 |
| MA/AA | 3.0 | 3.0 | 6.0 |
| LAS | 14.0 | 12.0 | 22.0 |
| C45AS | 8.0 | 7.0 | 7.0 |
| Silicate | - | 1.0 | 5.0 |
| Soap | - | - | 2.0 |
| Whitening agent 1 | 0.2 | 0.2 | 0.2 |
| Carbonate | 8.0 | 16.0 | 20.0 |
| DTPMP | - | 0.4 | 0.4 |
| Spraying | - | 1.0 | 5.0 |
| C45E7 | 1.0 | 1.0 | 1.0 |
| Agglomerate | |||
| QEA1 | 0.6 | 2.0 | 1.0 |
| Zeolite A (doing) | 2.0 | 4.0 | 2.2 |
| Dried additive | |||
| HEDP | 1.0 | - | - |
| PVPVI/PVNO | 0.5 | 0.5 | 0.5 |
| Proteolytic enzyme | 1.0 | 1.0 | 1.0 |
| Lipase | 0.4 | 0.1 | 0.2 |
| Amylase | 0.1 | 0.1 | 0.1 |
| Cellulase | 0.1 | 0.1 | 0.1 |
| TEAD | - | 6.1 | 4.5 |
| PB1 | 11.0 | 5.0 | 6.0 |
| Sodium sulfate | - | 6.0 | - |
| Equipoise (moisture and minor component) |
Following granular detergent composition.
Embodiment 5
| N | O | |
| The blowing powder | ||
| Zeolite A | 20.0 | - |
| STPP | - | 20.0 |
| LAS | 7.0 | 6.0 |
| C68AS | 6.0 | 2.0 |
| Silicate | 3.0 | 8.0 |
| MA/AA | 5.0 | 2.0 |
| CMC | 3.0 | 0.6 |
| QEA3 | 0.1 | - |
| Whitening agent 1 | - | 0.2 |
| DTPMP | 0.1 | 0.4 |
| Spraying | ||
| C45E7 | 6.5 | 5.0 |
| The polysiloxane suds suppressor | 0.3 | 0.3 |
| Spices | 0.2 | 0.2 |
| Dried additive | ||
| Citric acid | - | 2.0 |
| Carbonate | 10.0 | 9.0 |
| PB1 | 1.5 | 2.0 |
| PB4 | - | 13.0 |
| TAED | 7.0 | 2.0 |
| The photoactivation SYNTHETIC OPTICAL WHITNER | 15ppm | 15ppm |
| Proteolytic enzyme | 10.5 | 1.0 |
| Lipase | 0.1 | 0.08 |
| Amylase | 0.3 | 0.4 |
| Cellulase | 0.4 | 0.1 |
| Vitriol | 8.0 | 20.0 |
| Agglomerate | ||
| QEA1 | 0.9 | 0.6 |
| Zeolite A (doing) | 2.0 | 1.4 |
| LAS | 1.0 | 1.5 |
| Equipoise (moisture and minor component) | ||
| Density (g/l) | 700 | 700 |
Be prepared as follows detergent composition:
| P | Q | R | S | |
| The blowing powder | ||||
| Zeolite MAP | - | - | - | 20.0 |
| Zeolite A | 15.0 | 15.0 | 17.0 | - |
| Sodium sulfate | 0.0 | 5.0 | 0.0 | - |
| LAS | 3.0 | 3.0 | 5.0 | 5.0 |
| QAS | - | 1.5 | 0.5 | - |
| DTPMP | 0.4 | 0.2 | 0.0 | - |
| CMC | 0.4 | 0.4 | 0.4 | 1.0 |
| MA/AA | 4.0 | 2.0 | 2.0 | 1.0 |
| Agglomerate | ||||
| LAS | 5.0 | 5.0 | 1.0 | 6.0 |
| TAS | 2.0 | 2.0 | 0.4 | 2.0 |
| Silicate | 3.0 | 3.0 | 0.5 | 2.5 |
| QEA1 | 1.0 | 2.5 | 1.0 | 1.0 |
| Zeolite A (doing) | 8.0 | 8.0 | 5.0 | 5.0 |
| Carbonate | 8.0 | 8.0 | 10.0 | - |
| PEG8000 | - | 2.0 | 1.0 | 0.2 |
| Spraying | ||||
| Spices | 0.3 | 0.3 | 0.4 | 0.4 |
| C25E5 | 2.0 | 2.0 | 6.0 | 5.0 |
| C25E3 | 2.0 | - | - | 1.5 |
| Dried additive | ||||
| Citric acid | - | 2.0 | 2.0 | 2.0 |
| Citrate trianion | 3.0 | 3.5 | 2.0 | 1.5 |
| Supercarbonate | - | 3.0 | - | - |
| Carbonate | 8.0 | 15.0 | 14.0 | 10.0 |
| Percarbonate | - | 7.0 | 10.0 | 20.0 |
| TAED | 6.0 | 2.0 | 4.0 | 4.0 |
| PB1 | 14.0 | 7.0 | - | - |
| EDDS | - | 2.0 | 0.5 | - |
| Polyethylene oxide MW5000000 | - | - | 0.2 | - |
| Wilkinite | - | 8.0 | - | - |
| Proteolytic enzyme | 1.0 | 1.0 | 1.3 | 0.8 |
| Lipase | 0.4 | 0.1 | 0.5 | 0.3 |
| Amylase | 0.6 | 0.6 | 0.6 | 0.2 |
| Cellulase | 0.6 | 0.6 | 0.3 | - |
| The polysiloxane suds suppressor | 5.0 | 3.0 | 1.0 | 0.7 |
| Dried additive | ||||
| Sodium sulfate | 0.0 | 3.0 | 0.3 | - |
| Equipoise (moisture and minor component) | 100.0 | 100.0 | 100.0 | 100 |
| Density (g/l) | 850 | 850 | 850 | 850 |
Claims (18)
1. detergent particles, it contains:
(a) have the clay soil removal/anti water-soluble cationic compound of deposit properties again, it is selected from:
1) have the ethoxylation positively charged ion monoamine of following formula:
2) have the ethoxylation cationic diamine of following formula:
Or
Or
M wherein
1Be N+ or N group; Each M
2Be N+ or N group and at least one M
2It is the N+ group;
3) have the ethoxylation cationic polyamine of following formula:
4) and their mixture;
A wherein
1Be
Or-O-, R is H or C
1-C
4Alkyl or hydroxyalkyl, R
1Be C
2-C
12Alkylidene group, hydroxy alkylidene, alkenylene, arylidene or alkarylene, or C with 2-20 oxyalkylene units
2-C
3Oxyalkylene part, its prerequisite are not form the O-N key; Each R
2Be C
1-C
4Alkyl or hydroxyalkyl, group-L-X, or two R
2Form group-(CH together
2)
r-A
2-(CH
2)
s-, A wherein
2Be-O-or-CH
2-, r is 1 or 2, s be 1 or 2 and r+s be 3 or 4; Each R
3Be C
1-C
8Alkyl or hydroxyalkyl, benzyl, group-L-X, or two R
3Or R
2With a R
3Form group-(CH together
2)
r-A
2-(CH
2)
s-; R
4Be the C that replaces
3-C
12Alkyl, hydroxyalkyl, thiazolinyl, aryl or have the alkaryl of p the position of substitution; R
5Be C
1-C
12Thiazolinyl, hydroxy alkylidene, alkenylene, arylidene or alkarylene or C with 2-20 oxyalkylene units
2-C
3Oxyalkylene part, its prerequisite are not form O-O or O-N key; X is selected from H, C
1-C
4The non-ionic group of alkyl or hydroxyalkyl acrylate or ether group and their mixture; L contains polyalkylene oxide groups-[(R
6O)
m(CH
2CH
2O)
n]-hydrophilic chain; R wherein
6Be C
3-C
4The numerical value of alkylidene group or hydroxy alkylidene and m and n makes group-(CH
2CH
2O)
n-account for by weight described polyalkylene oxide groups at least about 50%; Work as M
2D is 1 and works as M when being N+
2D is 0 when being N; For described positively charged ion monoamine n is at least about 16, is at least about 6 and be at least about 3 for described cationic polyamine n for described cationic diamine n; P is 3-8; Q is 1 or 0; T is 1 or 0, and its prerequisite is that q is that 1 o'clock t is 1; With
(b) powder carrier material,
Wherein (a) and ratio (b) are by weight 1: 15-4: 1.
2. according to the particle of claim 1, wherein said powder carrier material is the aluminosilicate carrier material.
3. according to the particle of claim 1 or 2, wherein said cation compound contains ethoxylation positively charged ion monoamine, one of them R
2Be methyl, two R
2Group is group L-X, m be 0 and n be about 20 at least.
4. according to the particle of claim 1 or 2, wherein said cation compound contains ethoxylation cationic diamine, wherein R
1Be C
2-C
6Alkylidene group.
5. according to the particle of claim 4, the R in the wherein said ethoxylation cationic diamine
1It is hexa-methylene.
6. according to the particle of claim 1 or 2, wherein said cation compound contains ethoxylation cationic polyamine, wherein R
4Be the C that replaces
3-C
6Alkyl, hydroxyalkyl or aryl;
A1 is
With p be 3-6.
7. according to the particle of claim 4, each R of cation compound wherein
2Group is methyl or group-L-X, each R of cation compound
3Group is a methyl, and M
1With each M
2Be N
+Group.
8. according to the particle of claim 4, wherein m be 0 and n be at least 12.
9. according to the particle of claim 4, wherein m is 0, and n is at least 20.
10. according to the particle of claim 1 or 2, wherein said carrier substance has the water content that is lower than by carrier substance weight 15%.
11. according to the particle of claim 1 or 2, wherein said carrier substance contains the sodium silicoaluminate zeolite.
12. according to the particle of claim 1 or 2, wherein the ratio of water-soluble cationic compound and carrier substance is 1: 7-1: 1.
13., wherein have anion surfactant according to the particle of claim 1 or 2.
14. according to the particle of claim 13, wherein said anion surfactant be selected from alkyl-sulphate, alkylbenzene sulfonate and with the alkyl-sulphate of ethylene oxide condensation.
15., wherein have polyoxyethylene glycol according to the particle of claim 1 or 2.
16. according to the purposes of particle in granular detergent composition of claim 1 or 2, wherein said cation compound exists in the amount by described detergent composition weight 0.01%-30%.
17. according to the purposes of claim 16, wherein cation compound exists with the amount of 0.2%-3%.
18. a particulate agglomeration method for preparing according to claim 1 or 2, it comprises step:
(a) the heating water-soluble cationic compound is to obtain melting compound;
The melting compound of (b) agglomeration (a) becomes agglomerate granule with carrier substance;
(c) agglomerate granule of cooling (b).
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9619921A GB2317392A (en) | 1996-09-24 | 1996-09-24 | Detergent compositions |
| GB9619921.1 | 1996-09-24 | ||
| GB9623067.7 | 1996-11-06 | ||
| GB9623067A GB2319038A (en) | 1996-11-06 | 1996-11-06 | Detergent particle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1237999A CN1237999A (en) | 1999-12-08 |
| CN1113953C true CN1113953C (en) | 2003-07-09 |
Family
ID=26310092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97199894A Expired - Fee Related CN1113953C (en) | 1996-09-24 | 1997-09-22 | Detergent particle |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0929627A4 (en) |
| JP (1) | JP3773542B2 (en) |
| CN (1) | CN1113953C (en) |
| AR (1) | AR010223A1 (en) |
| AU (1) | AU4488397A (en) |
| BR (1) | BR9714343A (en) |
| CA (1) | CA2265891A1 (en) |
| CZ (1) | CZ102199A3 (en) |
| TR (1) | TR199900653T2 (en) |
| WO (1) | WO1998013453A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999011749A1 (en) * | 1997-08-28 | 1999-03-11 | The Procter & Gamble Company | Agglomeration process for producing a particulate modifier polyamine detergent admix |
| EP0971030A1 (en) * | 1998-07-10 | 2000-01-12 | The Procter & Gamble Company | Surfactant agglomerates |
| US6627596B1 (en) | 1999-02-01 | 2003-09-30 | The Procter & Gamble Company | Cationic particle and a process for making thereof |
| CA2359319C (en) * | 1999-02-01 | 2005-06-14 | The Procter & Gamble Company | Cationic particle and a process for making thereof |
| GB0002749D0 (en) | 2000-02-07 | 2000-03-29 | Unilever Plc | Detergent compositions |
| DE10044472A1 (en) * | 2000-09-08 | 2002-03-21 | Cognis Deutschland Gmbh | laundry detergent |
| DE10044471A1 (en) * | 2000-09-08 | 2002-03-21 | Cognis Deutschland Gmbh | Fabric-conditioning detergent composition comprising an anionic surfactant, a nonionic and amphoteric surfactant, a cationic polymer and a phosphate |
| DE10128894A1 (en) * | 2001-06-15 | 2002-12-19 | Basf Ag | Cationically surface-modified hydrophilic crosslinked polymer nanoparticles are used as an aqueous dispersion in stain-release treatment of textile or non-textile surfaces |
| ES2391263T3 (en) | 2002-12-04 | 2012-11-22 | Clariant Finance (Bvi) Limited | Procedure for preparing a quaternary ammonium composition |
| JP5903340B2 (en) * | 2012-06-25 | 2016-04-13 | ライオン株式会社 | Granular detergent |
| EP3743494A1 (en) | 2018-01-26 | 2020-12-02 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier |
| EP3743493A1 (en) * | 2018-01-26 | 2020-12-02 | Ecolab Usa Inc. | Solidifying liquid anionic surfactants |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4664848A (en) * | 1982-12-23 | 1987-05-12 | The Procter & Gamble Company | Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5880398A (en) * | 1981-11-09 | 1983-05-14 | 小林製薬株式会社 | Carpet treatment composition |
| US5211870A (en) * | 1992-03-11 | 1993-05-18 | The Procter & Gamble Company | Malodor-free cleansing bar composition containing zeolite odor controlling agent |
| EP0906382A4 (en) * | 1996-05-17 | 1999-11-24 | Procter & Gamble | Detergent composition |
-
1997
- 1997-09-22 JP JP51574798A patent/JP3773542B2/en not_active Expired - Fee Related
- 1997-09-22 CN CN97199894A patent/CN1113953C/en not_active Expired - Fee Related
- 1997-09-22 BR BR9714343-0A patent/BR9714343A/en not_active IP Right Cessation
- 1997-09-22 CA CA002265891A patent/CA2265891A1/en not_active Abandoned
- 1997-09-22 AU AU44883/97A patent/AU4488397A/en not_active Abandoned
- 1997-09-22 CZ CZ991021A patent/CZ102199A3/en unknown
- 1997-09-22 TR TR1999/00653T patent/TR199900653T2/en unknown
- 1997-09-22 EP EP97943401A patent/EP0929627A4/en not_active Withdrawn
- 1997-09-22 WO PCT/US1997/016706 patent/WO1998013453A1/en not_active Application Discontinuation
- 1997-09-24 AR ARP970104401A patent/AR010223A1/en not_active Application Discontinuation
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4664848A (en) * | 1982-12-23 | 1987-05-12 | The Procter & Gamble Company | Detergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1998013453A1 (en) | 1998-04-02 |
| EP0929627A1 (en) | 1999-07-21 |
| EP0929627A4 (en) | 2000-01-05 |
| CZ102199A3 (en) | 1999-07-14 |
| JP2000506936A (en) | 2000-06-06 |
| AR010223A1 (en) | 2000-06-07 |
| BR9714343A (en) | 2000-04-11 |
| AU4488397A (en) | 1998-04-17 |
| CA2265891A1 (en) | 1998-04-02 |
| TR199900653T2 (en) | 1999-06-21 |
| CN1237999A (en) | 1999-12-08 |
| JP3773542B2 (en) | 2006-05-10 |
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Legal Events
| Date | Code | Title | Description |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |