CN1040656C - Surfactant-containing dye transfer inhibiting compositions - Google Patents
Surfactant-containing dye transfer inhibiting compositions Download PDFInfo
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- CN1040656C CN1040656C CN93116491A CN93116491A CN1040656C CN 1040656 C CN1040656 C CN 1040656C CN 93116491 A CN93116491 A CN 93116491A CN 93116491 A CN93116491 A CN 93116491A CN 1040656 C CN1040656 C CN 1040656C
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3792—Amine oxide containing polymers
-
- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
Abstract
The present invention relates to dye transfer inhibiting compositions comprising: a) a polymer selected from polyamine N-oxide containing polymers which contain units having structure formula, wherein P is a polymerisable unit, whereto the N-O group can be attached to or wherein the N-O group forms part of the polymerisable unit or a combination of both; A is -O-, -S-, x is 0 or 1; R are aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups; b) a polymeric surfactant including surfactant selected from non-ion and/or anion and/or cation and/or amphoteric and/or zwitterion and/or half-polarity surfactant.
Description
The present invention relates to be used for suppressing dyestuff transfer compositions and method between the fabric of washing process.More particularly, the present invention relates to the dye transfer inhibiting composition that constitutes by polymkeric substance that contains polyamine N-oxide and tensio-active agent.
Be used to clean purpose, as the washing of fabric, detergent composition has generally all adopted various tensio-active agents.
The various dirts that detergent composition has on the removal fabric in common washing is loaded and the ability of spot are crucial for the evaluation of washing composition performance.But each tensio-active agent all has its strength and weak place.
So, all use the preparation of not only a kind of tensio-active agent farthest bringing into play its advantage in the detergent composition, and the influence of its shortcoming be reduced to minimum.
The relative capacity that each tensio-active agent satisfies various performance requriementss also depends on the existence of other additive component in the detergent composition.
One of type of adding the additive component in the detergent composition to is a dye transfer inhibiting polymers.
It is to transfer on other fabric that washs together with it from painted fabric in order to suppress dyestuff that said polymkeric substance is added in the detergent composition.These polymkeric substance have with select from painted fabric the fugitive dye washed off on they have an opportunity attached to other article of together washing before the ability of complexing or absorption.
Polymkeric substance has been used in the detergent composition to suppress the transfer of dyestuff.Do not introducing the polymkeric substance that contains polyamine N-oxide in No. the 92202168.8th, the european patent application of authorization as yet, it is very effective eliminating by dye transfer solubilising or that suspend.
Have been found that polymkeric substance and the tensio-active agent system of containing polyamine N-oxide are very compatible.In addition, find that also the dye transfer rejection has been enhanced when containing some tensio-active agent.
This discovery makes us can prepare a kind of like this detergent composition, and it promptly has excellent dye metastasis inhibition characteristic, has all washing composition performances again.
According to another embodiment of the invention, also provide a kind of method of washing DYED FABRICS.
The present invention relates to by a kind of polymkeric substance of selecting from the polymkeric substance that contains polyamine N-oxide and the dye transfer inhibiting composition that tensio-active agent system constitutes, said polymkeric substance contains the unit of following structural (1):
Wherein P is a polymerisable unit, and the N-O group can be incorporated on it, and perhaps this N-O group constitutes the part of polymerizable unit or the combination of two kinds of situations.A is
-O-,-S-,
X is 0 or 1;
R is an aliphatic group, the ethoxylation aliphatic group, and the nitrogen that aromatic group, heterocyclic radical or alicyclic radical, or their arbitrary combination, the nitrogen in the N-O group can be incorporated in top or the N-O group constitutes these basic parts.
Composition of the present invention comprises the polymkeric substance that contains polyamine N-oxide as main component, and said polymkeric substance contains the unit of following structural (I):
Wherein P is a polymerizable unit, and the R-N-O group can be incorporated on it, and perhaps this R-N-O group constitutes the part of polymerizable unit or the combination of two kinds of situations.A is
-O-,-S-,
X is 0 or 1;
R is an aliphatic group, the ethoxylation aliphatic group, and the nitrogen that aromatic group, heterocyclic radical or alicyclic radical, or their arbitrary combination, the nitrogen in the N-O group can be incorporated in top or the N-O group constitutes these basic parts.
This N-O group can be represented with following general structural formula:
R1 wherein, R2, R3 are aliphatic groups, aromatic group, heterocyclic radical or alicyclic radical or their combination, x or/and y or/and z is 0 or 1, wherein the nitrogen in the N-O group can be incorporated into that base is gone up or this N-O group in nitrogen constitute the part of these groups.
This N-O base can be the part of polymerizable unit (P) or can be incorporated on the polymer main chain or the combination of two kinds of situations.
The polyamine N-oxide that is suitable for that N-O group wherein constitutes the part of polymerizable unit comprises that wherein the R base is selected from aliphatic group, aromatic group, the polyamine N-oxide of alicyclic radical or heterocyclic radical.
Class in the said polyamine N-oxide comprises such one group, and wherein the nitrogen in the N-O group constitutes the part of R base.Best is those wherein the R base be heterocyclic radical, such as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, the polyamine N-oxide of acridine and derivative thereof.
The another kind of of said polyamine N-oxide comprises such one group, and wherein the nitrogen in the N-O group is attached on this R base.
Other polyamine N-oxide that is fit to be those wherein the N-O base be the polyamine N-oxide that is combined on the polymerizable unit.
A class best in these polyamine N-oxide is the polyamine N-oxide with general structural formula (I), and wherein R is an aromatic group, and heterocyclic radical or alicyclic radical, the nitrogen in the N-O functional group are the part of said R base.
The example of these classes has wherein that R is a heterogeneous ring compound such as pyridine, pyrroles, the polyamine oxide compound of imidazoles and derivative thereof.
The polyamine N-oxide of another kind of the best is the polyamine oxide compound with general molecular formula (I), and wherein R is an aromatic group, and heterocyclic radical or alicyclic radical, the nitrogen in the N-O functional group are attached on the said R base.
The example of these classes has wherein, and the R base is aromatic group, for example the polyamine oxide compound of phenyl.
Any main polymer chain all can use, as long as the amine oxide polymkeric substance that is constituted is water miscible and has the dye transfer rejection characteristic.The example of suitable polymers main chain is a polyvinyls, polyolefine, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and their mixture.
The ratio of amine and amine n-oxide was generally 10: 1 to 1: 1000000 in the amine n-oxide polymkeric substance of the present invention.Yet the amount of the amine oxide base in containing the polyamine N-oxide of polymkeric substance can change by suitable copolyreaction or suitable N-degree of oxidation.The preferred ratio of amine and amine n-oxide is 2: 3 to 1: 1000000.Preferable is from 1: 4 to 1: 1000000, the most preferably from 1: 7 to 1: 1000000.Polymkeric substance of the present invention is actual to be comprised random or segmented copolymer, and wherein one type monomer is an amine n-oxide, the monomer of another kind of type or amine n-oxide or be not.The amine oxide unit has PKa＜10 in the polyamine N-oxide, PKa＜7 preferably, and preferable is PKa＜6.
The polymkeric substance that contains polyamine N-oxide can be with almost any polymerization degree acquisition.To the requirement of the polymerization degree be and undemanding, as long as the material that is obtained has the ability of the water-soluble and suspension dyestuff of ideal.
The typical molecular-weight average of polymkeric substance that contains polyamine N-oxide is in 500 to 1000000 scope, preferably in 1000 to 50000 scope: preferable is in 2000 to 30000 scope, the most preferably in 3000 to 20000 scope.
The content that contains the polymkeric substance of polyamine N-oxide of the present invention is generally 0.001% to 10% of dye transfer inhibiting composition weight, and more preferably from 0.01% to 2%, the most preferably from 0.05% to 1%.
Composite inhibiting of the present invention can be added in the common detergent composition of laundry usefulness as additive easily.The present invention also comprises such dye transfer inhibiting composition, wherein comprises detergent ingredients, therefore can be used as detergent composition and uses.The preparation method of polyamine N-oxide:
The preparation that contains the polymkeric substance of polyamine N-oxide can perhaps can obtain polyamine N-oxide by amine oxide monomer self-polymerization by finishing with suitable oxygenant oxidation with the amine monomers polymerization with the polymkeric substance that obtains.
Contain polymkeric substance synthetic of polyamine N-oxide, for instance, can be undertaken by synthesizing of polyethylene-pyridine N-oxides.To be pre-dissolved in 50 milliliters of acetate available from poly--4-vinylpyridine (mw.50000,5.0g., 0.0475 mole) of Polysciences, (25 gram glacial acetic acids, 6.4 restrain the H of 30% volumetric concentration with peracetic acid solution by transfer pipet then
2O
2Solution and several H
2SO
4, make 0.0523 mole peracetic acid) and processed.Stirring the mixed solution of gained more than 30 minutes under 32 ℃ the envrionment temperature.This mixed solution will heat 3 hours in 80-85 ℃ oil bath before spending the night being placed.Then the polymers soln that obtains is under agitation mixed with 1 liter acetone.The yellowish brown mucilage liquid that the bottom is formed obtains the crystalline solid of light color at last with 1 liter acetone rinsing again.
The solid that obtains is utilized gravity filtration, use P then with acetone rinsing
2O
5Dry.
The amine of this polymkeric substance and the ratio of amine n-oxide are 1: 4 (measuring by nuclear magnetic resonance spectrometry).Tensio-active agent system:
Composite inhibiting of the present invention also comprises a tensio-active agent system except the polymkeric substance that contains polyamine N-oxide, tensio-active agent wherein can be selected from nonionic and/or negatively charged ion and/or positively charged ion and/or amphoteric and/or zwitterionic and/or semi-polar tensio-active agent.
The optimum surfactant system that the present invention adopts comprises one or more in the nonionogenic tenside as described herein.These nonionogenic tensides are found to be very useful, owing to added said tensio-active agent, the dye transfer rejection that comprises the polymkeric substance of polyamine N-oxide has strengthened.Nonionogenic tenside:
The nonionogenic tenside that alkylphenol and polyethylene, the condenses of polypropylene and polybutene oxide compound are suitable for use as tensio-active agent of the present invention system is polyethylene oxide condensate preferably wherein.These compounds comprise the condensation product of alkylphenol and alkylene oxide, and wherein alkylphenol contains an alkyl, and this alkyl comprises about 6 to 14 carbon atoms, and preferably about 8 to 14 carbon atoms perhaps become straight chain or become branched structure.In a most preferred embodiment, with respect to the alkylphenol of each mole, the amount of oxyethane is about 5 to 25 moles, more about 3 to 15 moles.Such nonionogenic tenside that can obtain from the market has the lgepal that is produced by GAF company
TMThe Triton that CO-630Rohm δ haas company produces
TMX-45, X-114, X-100 and X-102.These tensio-active agents are commonly referred to as alkylphenol alcoxylates (for example, alkyl phenol ethoxylate).
Uncle lipidol and secondary lipidol are suitable for use as the tensio-active agent that nonionogenic tenside of the present invention is with the condensation product of about 1 to 25 mole oxyethane.The alkyl chain of fatty alcohol can be a straight or branched, a generation or two generations, generally comprises about 8 to 22 carbon atoms.The condensation product of alcohol of each mole and about 2 to 10 moles oxyethane preferably, said alcohol comprises an alkyl, and alkyl wherein comprises about 8 to 20 carbon atoms, more about 10 to 18 carbon atoms.Such nonionogenic tenside available on the market has, for example the Tergitol that is produced by associating carbon products company
TM15-S-9 (C
11-C
15The condensation product of straight chain alcohol and 9 moles of ethylene oxide, Tergitor
TM24-L-6NMW (C
12-C
14Primary alconol and 6 moles of condensation products) with oxyethane of narrow molecular weight distribution; Neodol by shell chemical company product
TM45-9 (C
14-C
15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Neodol
TM23-6.5 (C
12-C
13The condensation product of straight chain alcohol and 6.5 moles of ethylene oxide).Neodol
TM45-7 (C
14-C
15The condensation product of straight chain alcohol and 7 moles of ethylene oxide), Neodol
TM45-4 (C
14-C
15The condensation product of the oxyethane of straight chain alcohol and 4 moles); And the Kyro of Procter δ Gamble company product
TMEOB (C
13-C
15Condensation product with 9 moles of ethylene oxide).
Can also also have U.S. Pat-4 as the nonionogenic tenside that tensio-active agent of the present invention is at the Llenado of promulgation on January 21st, 1986,565, disclosed alkyl polysaccharide in No. 647, said alkyl polysaccharide comprises a hydrophobic group and comprises about 6 to 30 carbon atoms, preferably about 10 to 16 carbon atoms; And glycan, as the glycan glycosides, hydrophilic group wherein comprises 1.3 to 10, and is preferably about 1.3 to 3, the most about 1.3 to 2.7 sugared units.Any reducing sugar that contains 5 or 6 carbon atoms can utilize, for example, glucose, semi-lactosi, wherein galactosyl part can partly be replaced that (hydrophobic group can at random be combined in 2-, 3-by glucosyl, 4-, Deng the position, what therefore draw is not glucoside or galactoside, but glucose or semi-lactosi).Combination between sugar can be, a position of for example other sugar unit and the 2-on the above-mentioned sugar unit, 3-, 4-, and/or 6-position.
Selectively, but seldom need, a polyalkylene epoxy chain that connects hydrophobic group part and glycan part can be arranged.Desirable alkylene oxide is an oxyethane.Typical hydrophobic group comprises alkyl, and is saturated or unsaturated, branched or not branched, contains 8 to 18 carbon atoms of having an appointment, preferably about 10 to 16 carbon atoms.Preferably this alkyl is an alkyl that straight chain is saturated.This alkyl can contain have an appointment 3 hydroxyls and/or polyalkylene epoxy chain can comprise about 10, most preferably less than 5 alkylene oxide parts.The alkyl polysaccharide that is fit to has octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and two, three, four, five, six glucosides, galactoside, lactoside, glucose, fructoside, fructose and/or semi-lactosi.The mixture that is fit to comprises the coconut alkyl, two-, three-, four-and five-glucoside, tallow alkyl four-, five-, six-glucoside.
Desirable alkyl polyglucoside has molecular formula
R
2O (C
nH
2nO)
t(glycosyl)
xR wherein
2Be to be selected to comprise alkyl, alkyl phenyl, hydroxyalkyl, in one group of base of hydroxyalkyl phenyl and composition thereof, wherein alkyl contains 10 to 18, preferably about 12 to 14 carbon atoms; N is 2 or 3, preferably 2; T is from 0 to 10, and preferably 0x is from about 1.3 to 10, preferably from about 1.3 to 3, the most preferably from about 1.3 to 2.7.This glycosyl is preferably derived from glucose.In order to prepare these compounds, form alcohol or alkyl polyethoxye alcohol earlier, then with glucose, or the source of glucose reaction, to form heteroside (being combined in the 1-position).The glycosyl units that adds is then by at their the 1-position and the 2-of above-mentioned glycosyl units, 3-, and 4-, and/or the combination of 6-position are preferably based on the 2-position.
Although inadvisable, the condensation product of oxyethane and the hydrophobic group that is formed by 1,2 epoxy prapane and propylene glycol condensation also is suitable for being used as the nonionogenic tenside of the interpolation that tensio-active agent of the present invention is.The hydrophobic group part of these compounds preferably has about molecular weight of 1500 to 1800 and demonstrates water-fast characteristic.Polyoxyethylene partly joins has increased as a whole water-soluble of molecule in this hydrophobic part, the characteristics of liquids of product is retained on such level, be polyoxyethylene content account for the condensation product gross weight 50%, be equivalent to and about 40 moles ethylene oxide condensation.The example of such compound comprises some the commercially available Pluronic that is produced by BASF
TMTensio-active agent.
The reaction product of 1,2 epoxy prapane and 1 and the condenses of oxyethane also are suitable for being used as the nonionogenic tenside that tensio-active agent of the present invention is.These product hydrophobic parts comprise the reaction product of 1 and excessive 1,2 epoxy prapane, and its molecular wt is generally from about 2500 to 3000.This hydrophobic part and ethylene oxide condensation be to such degree, promptly contains 40% to 80% the polyoxyethylene that accounts for weight in the condensation product, and its molecular weight is about 5,000 to 11,000.Some commercially available Tetronic that produces by BASF AG for example
TMCompound is exactly such nonionogenic tenside.
Uncle's fatty alcohol and secondary fatty alcohol and about 1 to 25 mole oxyethane, the condenses of condensation product of alkyl polysaccharide and composition thereof and alkylphenol and polyethylene oxide is preferably used as the nonionogenic tenside of tensio-active agent of the present invention.The C that the most preferably has 3 to 15 oxyethyl groups
8-C
14Alkyl phenol ethoxylate and C with 2 to 10 oxyethyl groups
8-C
18Alcohol ethoxylate (average out to C preferably
10), and their mixture.
Very desirable nonionogenic tenside is a polyhydroxy fatty acid amide surfactant.
Has molecular formula
Polyhydroxy fatty acid amide surfactant also be suitable for use as nonionogenic tenside.R wherein
1Be H, or R
1Be C
1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R
2Be C
5-31Alkyl, Z are one and have the polyhydroxy alkyl that directly is connected the straight-chain alkyl chain on the chain by at least 3 hydroxyls, or its alkoxy derivative.Preferably, R
1Be methyl, R
2Be a C
11-15Alkyl or alkenyl straight chain, as coconut alkyl or its mixture, Z is by reducing sugar such as glucose, fructose, maltose, lactose, derives out in a reductive amination process.
When nonionogenic tenside of the present invention is when being included in the detergent composition, can improve the performance that this detergent composition is removed fats/oils matter stain under very wide washing composition condition.Anion surfactant
The anion surfactant that is suitable for comprises alkyl alkoxylated sulfate surfactant, and said compound is for having molecular formula RO (A)
mSO
3The water-soluble salt of M or acid, wherein R is a unsubstituted C
10-C
24Alkyl or have C
10-C
24The hydroxyalkyl of alkyl, preferably C
12-C
20Alkyl or hydroxyalkyl, preferable is C
12-C
18Alkyl or hydroxyalkyl, A is an oxyethyl group or propoxy-unit, m is greater than zero, typical value is between about 0.5 to 6, more preferably between about 0.5 to 3, M is H or a positive ion, for example can be a metal positive ion (as sodium, potassium, lithium, calcium, magnesium or the like), ammonium or substituted ammonium ion.Alkyl ethoxylated sulfate is all the same here with the alkyl propoxylated sulphates to be considered.The specific example that replaces ammonium comprises the positively charged ion that methyl, dimethyl, trimethyl ammonium positively charged ion and quaternary ammonium cation such as tetramethyl-ammonium and dimethyl pyridine positively charged ion and those derive out from alkylamine such as ethamine, diethylamine, triethylamine and composition thereof, or the like.The example of tensio-active agent is C
12-C
18Alkyl polyethoxye (1.0) vitriol (C
12-C
18E (1.0M), C
12-C
18Alkyl polyethoxye (2.25) vitriol (C
12-C
18E (2.25) M), C
12-C
18Alkyl polyethoxye (3.0) vitriol (C
12-C
18E (3.0) M), C
12-C
18Alkyl polyethoxye (4.0) vitriol (C
12-C
18E (4.0) M), wherein M generally is selected from sodium and potassium.
According to " american petroleum chemistry association magazine ", 52 (1975), pp.323-329 is suitable for use as the alkyl sulfonate surfactants that has of anion surfactant, and it comprises uses gaseous state SO
3The sulfonated straight chain C
8-C
20Carboxylic acid (being lipid acid) ester.The initial substance that is fit to comprises from tallow plam oil, the natural fat material that extracts in waiting.
Desirable alkyl sulfonate surfactants especially for what wash, is made of the alkyl ester sulphur ester salt surfactant with following molecular formula:
R wherein
3Be C
8-C
20Alkyl, preferably an alkyl or its binding substances, R
4Be a C
1-C
6Alkyl, preferably alkyl, or its binding substances, M are positively charged ions, it constitutes water-soluble salt with alkyl ester sulfonate.Suitable salt-forming cation comprises metal such as sodium, potassium and lithium ion and replacement and unsubstituted ammonium ion, and as monoethanolamine, diethanolamine, and trolamine.Preferably, R
3Be C
10-C
18Alkyl, R
4Be methyl, ethyl or sec.-propyl.Especially preferably methyl ester sulfonate, wherein R
3Be C
10-C
18Alkyl.
Other anion surfactant that is fit to comprises alkyl sulfate surfactant, and this is that a kind of molecular formula is ROSO
3Insoluble salt or the acid of M, wherein R is a C
10-C
24Alkyl, preferably alkyl or have C
10-C
20The hydroxyalkyl of alkyl composition, preferable is C
12-C
18Alkyl or hydroxyalkyl, M are H or positively charged ion, for example, alkalimetal ion (as sodium, potassium, lithium), or ammonium or replace ammonium (as methyl, dimethyl and trimethyl ammonium ion and quaternary ammonium cation such as tetramethyl-ammonium, lupetidine father-in-law positively charged ion and from alkylamine, as ethamine, diethylamine, triethylamine, and composition thereof in the deutero-quaternary ammonium cation, or the like).Common C
12-C
16Alkyl chain be suitable for being used in lower wash temperature (as, be lower than 50 ℃), C
16-C
18Alkyl chain be suitable for being used in higher wash temperature (as, more than 50 ℃).
Other also can be included in the detergent composition of the present invention the useful anion surfactant of washing purpose.These comprise soap salt (as sodium salt, sylvite, ammonium salt and substituted ammonium salt, as list, two, triethanolamine salt), C
9-C
20Linear alkylbenzene sulfonate, C
8-C
22A generation and two generation sulfonated alkane, C
8-C
24Ethylenic sulfonate, the sulfonation poly carboxylic acid that is obtained by the pyrolysis product sulfonation of alkaline earth metal citrate for example, as in british patent specification the 1st, 082, is described C in 179
8-C
24Alkyl polyglycol ether sulfate (comprising oxyethane) up to 10 moles; Alkyl glycerol sulfonate; fatty acyl group glycerol sulfonate, fatty oil base glycerol vitriol, alkylphenol oxyethane ether sulfate; paraffin sulfonate; alkylphosphonic, isethionate is as acyl isethinate; the N-acyl taurine salt; amber alkyl amide salts, and sulfosuccinate, sulfosuccinate monoester (particularly saturated and undersaturated C
12-C
18Monoester) and sulfosuccinate two fat (particularly saturated and undersaturated C
6-C
12Two fat), acyl sarcosinate, alkyl polysaccharide vitriol such as alkyl polyglucoside vitriol (the non-sulfonated compound of nonionic is told about below), the generation alkyl-sulphate of side chain and alkyl polyethoxye carboxylate salt are as having molecular formula RO (CH
2CH
2O)
k-CH
2Those of COO-M+, wherein R is C
8-C
22Alkyl, k are integers of from 0 to 10, and M is soluble salt-forming cation.The resinous acid of resinous acid and hydrogenation also is fit to, as rosin, and staybelite and the resinous acid and the hydrogenation resin acid that are present in or from Yatall MA, derive.More example is documented in (first and second volumes, Schwartz, Perry and Berch work) in " tensio-active agent and washing composition " literary composition.Many this type of tensio-active agents also are disclosed in people's such as promulgation on December 30th, 1975 Laughlin the United States Patent (USP) the 3rd, 929,678, see that the 23rd hurdle 58 walks to 29 hurdles, 23 row (quoting as a reference) here.
In detergent composition of the present invention, the content of this analog anion surfactants accounts for 1% to 40% of gross weight, and preferably 3% to 20%.
Those that tell about except comprising here in the detergent composition of the present invention, also comprise positively charged ion, amphoteric, zwitter-ion and semi-polarity and nonionogenic tenside.
Desirable cats product system comprises nonionic and amphoterics.The cationic detergent tensio-active agent that is suitable for use as detergent composition of the present invention is those tensio-active agents that long chain hydrocarbon groups is arranged.Examples of such surfactants has ammonium surfactant, has molecular formula as alkyl dimethyl ammonium halogenide and those: [R
2(OR
3) y] [R
4(OR
3) y]
2R
5The tensio-active agent of N+X-, wherein R
2Be an alkyl or 8 the alkyl benzyls of on alkyl chain, having an appointment to 18 carbon atoms, each R
3Be selected from by-CH
2CH
2-,-CH
2CH (CH
3)-,-CH
2CH (CH
2OH)-,-CH
2CH
2CH
2-, and composition thereof one group of base constituting, each R
4Be selected from C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl connects two R
4The benzyl rings structure that base forms ,-CH
2CHOH-CHOHCOR
6CHOHCH
2OH, wherein R
6Be any hexose or molecular weight less than 1000 hexose polymkeric substance, and hydrogen, when y is not 0; R
5With R
4Identical or alkyl chain, wherein a R
2Add R
5The total number of carbon atoms be no more than 18; Each y is from 0 to 10, and the summation of y value is from 0 to 15; X is any compatible negatively charged ion.
For the useful desirable cats product of this composition is water miscible quaternary ammonium compound with following molecular formula:
R
1R
2R
3R
4N+X-(i)
R wherein
1Be C
8-C
18Alkyl, R
2, R
3And R
4In each all be C independently
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, benzyl and-(C
2H
40) the xH value from 2 to 5 of x wherein, x is a negatively charged ion.R
2, R
3And R
4In for benzyl should be no more than one.For R
1Desirable alkyl chain length is C
12-C
15, particularly alkyl wherein is from the mixture of the chain length of coconut or palm nuclear adipose-derived or synthetic or synthetic the deriving of oxo alcohol obtains by alkene.For R
2, R
3And R
4Desirable base is methyl and hydroxyethyl, and negatively charged ion x can be from halogenide, and methylsulfate is selected in acetate moiety and the phosphate anion.
The suitable example of the used here quaternary ammonium compound with molecular formula (i) has:
Coconut trimethyl ammonium muriate or bromide;
Coconut methyl dihydroxy ethyl ammonium muriate or bromide;
Decyl triethyl ammonium muriate;
Decyl dimethyl hydroxyethyl ammonium muriate or bromide;
C
12-C
15Dimethyl hydroxyethyl ammonium muriate or bromide:
Coconut dimethyl hydroxyethyl ammonium muriate or bromide;
Myristyl trimethyl ammonium Methylsulfate; Lauryl dimethyl hexadecyldimethyl benzyl ammonium muriate or bromide; Lauryl dimethyl (oxyethylene group)
4Ammonium muriate or bromide; Cholinesterase (compound of molecular formula (i), wherein R
1Be
Alkyl, R
2, R
3, R
4Be methyl)
The compound of dialkylimidazolium quinoline molecular formula (i)].
Here other useful cats product also is documented in the United States Patent (USP) the 4th, 228,044 of the Cambre that issued on October 14th, 1980.
In detergent composition of the present invention, the content of this type of cats product accounts for 0% to 25% of gross weight, and preferably 3% to 15%.
The amphoteric tensio-active agent also is applicable in the detergent composition of the present invention.These tensio-active agents can be described as the aliphatic derivatives of secondary amine or tertiary amine or the aliphatic derivatives of heterocyclic secondary or tertiary amine widely, and wherein the fat base can be a straight or branched.One of these aliphatic substituting groups comprise about 8 carbon atoms at least, generally are that at least one contains an anionic water lyotropy base to about 18 carbon atoms from about 8, for example, and carboxyl, sulfonate, vitriol.About the example of amphoterics, referring to No. the 3rd, 929,678, the people's such as Laughlin of on December 30th, 1975 promulgation United States Patent (USP), 19 hurdles 18 walk to 35 row.
In detergent composition of the present invention, the content of this type of amphoterics typically accounts for 0% to 15% of gross weight, and preferably 1% to 10%.
Zwitterionics also is suitable in the detergent composition.These tensio-active agents can be described as the derivative of secondary amine or tertiary amine widely, the derivative of heterocyclic secondary or tertiary amine, or quaternary ammonium, the derivative of quaternary phosphonium or uncle's sulfonium compound.About the example of zwitterionics, referring to No. the 3rd, 929,678, the people's such as Laughlin of on December 30th, 1975 promulgation United States Patent (USP), 19 hurdles 38 walk to 22 hurdles, 48 row.
In detergent composition of the present invention, containing of this type of bi ion active agent typically accounts for 0% to 15% of gross weight, and preferably 1% to 10%.
Semi-polar nonionic surfactants is a particular variety of nonionogenic tenside, it comprises water miscible amine oxide, wherein contains a moieties with about 10 to 18 carbon atoms and is selected from by alkyl and has two parts in one group of base that about 1 hydroxyalkyl to 3 carbon atoms constitutes; Water miscible phosphine oxide wherein contains a moieties with about 10 to 18 carbon atoms and is selected from by alkyl and has two parts in one group of base that about 1 hydroxyalkyl to 3 carbon atoms constitutes; With water-soluble sulfoxide, wherein contain one have about 10 to the moieties of 18 carbon atoms be selected from by alkyl and have a part in one group of base that about 1 hydroxyalkyl to 3 carbon atoms constitutes.
Semi-polar nonionic surfactants comprises the amine oxide tensio-active agent with following molecular formula:
R wherein
3Be an alkyl, hydroxyalkyl, or alkyl phenyl or its mixture wherein contain 8 to 22 carbon atoms of having an appointment; R
4Be an alkylidene group or hydroxyl alkylidene group, wherein contain have an appointment 2 to 3 carbon atoms or its mixture; X is from 0 to 3; Each R
5Be an alkyl or hydroxyalkyl, wherein contain have an appointment 1 to 3 carbon atom or a polyethylene oxide base, wherein contain 1 to 3 Oxyranyle of having an appointment.R
5Base can be bonded to each other, and for example, by oxygen or nitrogen-atoms, forms a ring texture.
These amine oxide tensio-active agents mainly are to comprise C
10-C
18Alkyl dimethyl amine oxide and C
8-C
12Alkoxyethyl dihydroxy ethyl amine oxide.
In detergent composition of the present invention, the content of this semi-polar nonionic surfactants generally is to account for 0% to 15% of gross weight, preferably about 1% to 10%.
The present invention also provides a kind of detergent composition, and wherein the total content of tensio-active agent accounts at least 1% of composition total weight, preferably accounts for about 3% to 65%, more about 10% to 25%.Detergent additives:
According to the present invention, in detergent composition, also comprise washing assistant system.The washing assistant system of any routine all is suitable for, comprise alumino-silicate materials, silicate, multi-carboxylate, and lipid acid, other material such as 1 tetraacetate, metal ion chelation agent, as aminopolyphosphonic acid fat, particularly 1 tetramethylene phosphonic acid and diethylenetriamine pentamethylene phosphonic acids.Although owing to the reason of environment protection is also inadvisable, phosphate builders also can use.
Inorganic ion exchange material, the synthetic zeolite of normally inorganic hydrated aluminosilicate material, particularly hydration such as hydrated zeolite A, X, B or HS also are suitable for use as washing assistant.
Other inorganic builders material that is fit to is a layered silicate, for example, and SKS-6 (Huo Xisite).SKS-6 is a kind of water glass (Na that contains
2Si
2O
5) layered crystal silicate.
The multi-carboxylate of containing a carboxyl who is fit to comprises lactic acid, and oxyacetic acid, and ether derivant are as in No. the 831st, 368, belgian patent document, disclosed in 821, No. 369 and 821, No. 370.The multi-carboxylate of containing two carboxyls comprises succsinic acid, propanedioic acid, (ethylenedioxy) diacetic acid; toxilic acid, diethyl alkyd, tartrate; the water-soluble salt of tartronic acid and fumaric acid, and at DS state prospectus 2,446; 686 and 2,446,687; with United States Patent (USP) the 3rd, 935, the ether carboxylate of record in 257; sulfinyl carboxylate salt with record in belgian patent the 840th, 623.The multi-carboxylate of containing three carboxyls comprises, particularly, and water miscible Citrate trianion, (suitable) aconitate, and citraconate, and succinate derivative, as in English Patent the 1st, the carboxy methoxy-succinic acid salt of record in 379, No. 241, the newborn oxygen base succinate of record in Netherlands patent applications 7205873, with oxidation multi-carboxylate material as in English Patent the 1st, the 2-oxa--1 of record in 387, No. 447,1-3-tricarballylic acid salt.
The multi-carboxylate of containing four carboxyls is included in English Patent the 1st, 261, the oxidation disuccinate of record in No. 829,1,1,2,2-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 and be included in English Patent the 1st, 398,421 and 1,398, the sulfo-succinic acid salt derivative of record in No. the 3rd, 936,448, No. 422 and the United States Patent (USP), in English Patent the 1st, the sulfonation pyrolysis Citrate trianion of record contains the substituent multi-carboxylate of phosphine and is disclosed in English Patent the 1st in 082, No. 179, in 439, No. 000.
Alicyclic ring and heterocycle multi-carboxylate comprise pentamethylene-cis, cis, cis-tetracarboxylic acid hydrochlorate, cyclopentadiene metallide pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-cis, cis, cis-tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-cis-dicarboxylate, 2,2,5,5-tetrahydrofuran (THF)-tetracarboxylic acid hydrochlorate, 1,2,3,4,5,6-hexane-hexacarboxylic acid salt and polyvalent alcohol such as Sorbitol Powder, the carboxymethyl derivant of mannitol and Xylitol.Aromatic multi-carboxy acid's salt comprises English Patent the 1st, 425, disclosed mellitic acid in No. 343,1,2,4,5-pyromellitic acid and phthalic acid derivative.
In above multi-carboxylate, preferably each molecule contains the hydroxycarboxylate of three carboxyls, particularly Citrate trianion.
The desirable washing assistant system that is used for composition of the present invention comprises the mixture of water-insoluble silico-aluminate washing assistant such as zeolite A or layered silicate (sks/6) and water-soluble carboxylate sequestrant such as citric acid.
The suitable integrated agent that is included in the detergent composition of the present invention is 1-N, N '-two Succinic Acid (EDDS) or its basic metal, alkaline-earth metal, ammonium, or the salt of replacement ammonium, or their mixture.Desirable EDDS compound is free acid form and their sodium salt or magnesium salts.The example of the EDDS sodium salt that this type of is desirable comprises Na
2EDDS and Na
4EDDS.The example of the EDDS magnesium salts that this type of is desirable comprises MgEDDS and Mg
2EDDS.It is the most desirable comprising magnesium salts according to the present invention in composition.
Particularly when compositions for use was liquid, suitable lipid acid washing assistant was saturated or unsaturated C
10-18Lipid acid is the same with corresponding soap class.Desirable saturation classes has 12 16 carbon atoms on alkyl chain.Desirable unsaturated fatty acids is an oleic acid.
Be used for the mixture that the desirable washing assistant system of granular composition comprises insoluble silico-aluminate washing assistant such as zeolite A and water-soluble carboxylate sequestrant such as citric acid.
Other washing assistant material that can be used as the part of the washing assistant system that is used for granular composition of the present invention comprises inorganic materials, as alkaline carbonate, and supercarbonate, silicate, and organic materials, as organic phosphonate, amino polyalkylene phosphonate and aminopolycanboxylic acid's salt.
Other water-soluble organic salt that is fit to is all-or co-polymeric acids or their salt, wherein poly carboxylic acid comprises that it is no more than at least two carboxyls of two carbon atoms at interval.
Such polymkeric substance is disclosed in English Patent GB-A-1, in 596,756.The example of this type of salt such as molecular weight are the multipolymer of the polyacrylate of 2000-5000 and they and maleic anhydride, and the molecular weight of this analog copolymer is 20,000 to 70,000, particularly about 40,000.
The content of builder salt accounts for 10% to 80% of composition weight usually in the washing composition, and preferably 20% to 70%, the most preferably from 30% to 60%.
The washing composition composition that can be included in the detergent composition of the present invention also comprises SYNTHETIC OPTICAL WHITNER.These bleach additive compositions can comprise one or more oxygen-bearing bleaching agents, and according to the selection of SYNTHETIC OPTICAL WHITNER, also have one or more bleach activators.Its typical content in detergent composition is about 1%-10% when having SYNTHETIC OPTICAL WHITNER.General bleaching compounds is at non-aqueous preparation, as being optional component in the granulated detergent.It if present, the amount of detergent active is generally 0.1% to 60% of bleaching composition, more typical is from 0.5% to 40%.
Here used bleach additive composition can be the known SYNTHETIC OPTICAL WHITNER useful to detergent composition that comprises oxygen-bearing bleaching agent in any prior art.
Aspect method, the present invention also provides a kind of and has been lower than 50 ℃, particularly be lower than the method for cleaning fabric, fiber, textiles under 40 ℃ the temperature, used detergent composition comprises the polymkeric substance that contains polyamine N-oxide, with denying random auxiliary detergent surfactant, available can no detergent additive composition and SYNTHETIC OPTICAL WHITNER.
Being suitable for SYNTHETIC OPTICAL WHITNER of the present invention can be active or inactive SYNTHETIC OPTICAL WHITNER.
There is a class available oxygen-bearing bleaching agent to comprise percarboxylic acids SYNTHETIC OPTICAL WHITNER and its esters.Example that this class SYNTHETIC OPTICAL WHITNER is suitable such as monoperphthalic acid magnesium hexahydrate, Jie's chloro peroxybenzoic acid, 4-amino in the ninth of the ten Heavenly Stems-4-oxygen are crossed the magnesium salts that (oxygen) butyric acid and two is crossed (oxygen) dodecandioic acid.This type of SYNTHETIC OPTICAL WHITNER is disclosed in U.S. Patent application 4483781,740, No. 446, in the european patent application 0,133, No. the 4th, 412,934, No. 354 and United States Patent (USP).Desirable especially SYNTHETIC OPTICAL WHITNER also is included in the United States Patent (USP) the 4634551st disclosed 6-amino in the ninth of the ten Heavenly Stems-6-oxygen and crosses (oxygen) caproic acid.。
Another kind of available SYNTHETIC OPTICAL WHITNER comprises the Halogen SYNTHETIC OPTICAL WHITNER.The example of hypohalite SYNTHETIC OPTICAL WHITNER comprises three chloro isocyanuric acids, dichloro-isocyanuric acid sodium and dichloro-isocyanuric acid potassium and N-chloro and N-bromo (chain) alkane sulfo group acid amides.This type of material adds 0.5-10%, preferably 1-5% weight percent usually in finished product.
The desirable SYNTHETIC OPTICAL WHITNER of the present invention that is suitable for comprises the peroxide bleaching agent.The water-soluble solid peroxygen bleach that is fit to comprises the hydrogen peroxide releasing agent, as hydrogen peroxide, perborate, and as the peroxyboric acid monohydrate, peroxyboric acid tetrahydrate, persulphate, percarbonate, peroxydisulfate, superphosphate and peroxyhydrate.Desirable SYNTHETIC OPTICAL WHITNER is percarbonate and perborate.
The hydrogen peroxide releasing agent can be used in combination with some bleach activators, as tetrem acyl 1 (TAED), nonanoyl hydroxy benzene sulfonate (NOBS, be disclosed in US-4,412,934), 3,5-trimethyl hexanol hydroxy benzene sulfonate (ISONOBS is disclosed in EP-120,591 in) or five acetyl glucose (PAG), they as activity bleaching class all be hydrolysis forming peracid, thereby improve bleaching effect.The promoting agent that is fit to also is included in disclosed acylated citrate esters in the european patent application of not authorizing as yet the 91870207.7th.
Also can there be (that is, enzyme and corresponding enzyme substrate) by adding enzyme-added system in hydrogen peroxide, and it can produce hydrogen peroxide in the washing process and/or in the rinse cycle when the washing beginning.This type of enzyme-added system is disclosed in No. 91202655.6, the european patent application of on October 9th, 1991 application.
Other is suitable for peroxygen bleach of the present invention and comprises organic peroxide acid, as percarboxylic acids.
Except oxygen-bearing bleaching agent also is utilizable with known other SYNTHETIC OPTICAL WHITNER in the external prior art.Make us an interested class oxygen-free SYNTHETIC OPTICAL WHITNER especially and comprise photoactivated SYNTHETIC OPTICAL WHITNER, as sulfonic acid zinc and/or sulfonic acid aluminium phthalocyanine.These materials can be deposited on the substrate in washing process.Under the irradiation of light and in the environment that exists of aerobic, when by day clothes being hung over the outside airing, sulfonic acid zinc phthalocyanine is activated, thereby substrate is bleached.Desirable zinc phthalocyanine and photosensitive bleaching method are disclosed in United States Patent (USP) the 4th, 033, in 718.In general, in detergent composition, comprise the sulfonic acid zinc phthalocyanine that accounts for gross weight 0.025% to 1.25%.
Other includable washing composition composition has detersive enzyme, and it is included in the detergent composition can be used for various purposes, for example remove proteinic, carbohydrate, or the dirt of triglyceride, prevent the dye transfer that fades away.The enzyme that adds comprises proteolytic enzyme, amylase, lipase, cellulase, peroxidase, and their mixture.The enzyme of other type is also includable.They can be any suitable bacterial classifications, such as plant, animal, bacterium, mould and zymic bacterial classification.
The amount that can add enzyme with respect to the composition of every gram can be heavy up to 5mg, be more typically about 0.05mg to 3mg.
The proteolytic enzyme that is fit to is subtilysin for example, and it is that bacterial strain by special withered grass B and lichens shape bacterium B obtains.The Alcalase that has Novo industrial (Denmark) to produce at the decomposition of protein enzyme that is suitable for removing the protein dirt available on the market, Savinase, with the enzyme of the Maxatase brand of the enzyme of Esperase brand and international Synbiotics AB (Holland), and the enzyme of the Optimase of the enzyme of the FNbase brand of Genencor company and MKC company and Opticlean brand.
Interesting in this decomposition of protein enzyme, especially for liquid detergent composition, be two kinds of enzymes that are referred to as Protease A and Protease B here.Protease A is disclosed in the european patent application 130,756.Protease B is disclosed in No. the 87303761.8th, the european patent application.
Amylase comprises that by the amylase that the special bacterial strain of lichens shape bacterium B is mentioned, detailed content is disclosed in british patent specification the 1st, 296, in 839 (Novo).Amylolytic enzymes comprises as Rapidase, Maxamyl board enzyme (international Synbiotics AB) and Termamyl board enzyme (Novo industrial).
The cellulase of Shi Yonging comprises bacteria cellulose enzyme and mould cellulase in the present invention.Preferably they have 5 to 9.5 pH value.Suitable cellulase is disclosed in people's such as Barbesgoard the United States Patent (USP) the 4th, 435,307, and it discloses the mould cellulase of producing from Humicola insolens.Suitable cellulase also is disclosed in GB-A-2, in 075,028 and GB-A-2,095,275 and DE-OS-2,247,832.
The useful Humicola insolens of the example of this cellulase (Humicolagrisea Var.thermoi dea) bacterial strain, the cellulase produced of Humicola strain DSM 1800 particularly, with with genus bacillus N or belonging to the cellulase 212-that Aeromomas belongs to produces the cellulase that mould produces, and the cellulase that from the liver pancreas of extra large mollush (Dolabella Auricula Solander), extracts.
It is about 50KDa that other cellulase that is fit to has the molecular weight that obtains from Humicola insulens, and iso-electric point is 5.5, contains 415 amino acid whose cellulases.This cellulase is disclosed in the co-pending European application the 93200811.3rd of application on March 19th, 1993.
Specially suitable cellulase is the cellulase with protection color characteristics.The cellulase Carezyme (Novo) that No. the 91202879.2nd, the european patent application of the example application on November 6th, 1 of the plain enzyme of this fibrid.
Be suitable for lipase in the washing composition and comprise those lipase, as in English Patent 1,372, introduce in 034 by Rhodopseudomonas stutzeri ATCC19.154 microorganisms.The lipase that is suitable for comprise make with Rhodopseudomonas fluorescence IAM 1057 microorganisms be those lipase of complete positive immunological cross-reaction with lipase antibody.This lipase is produced by the Amano Medicine stock Co., Ltd of Japan Nagoya market, and trade mark is " Amano " lipase P, hereinafter is referred to as " Amano-P ".
The lipase of particularly suitable such as M1 lipase (Ibis) and Lipolase enzyme (Novo)
Peroxidase is and oxygen source, for example, percarbonate, perborate, persulphate, hydrogen peroxide, or the like be used in combination.They are used to " solution bleaching ", prevent that promptly the dyestuff that fades away in washing process from transferring on other substrate from substrate.Peroxidase is known in prior art, for example comprises, and horseradish peroxidase, ligninase and halo peroxidase such as chloro-and bromo-peroxidase.The detergent composition that comprises peroxidase is disclosed in No. the 91202882.6th, the european patent application of pct international patent application WO89/099813 and application on November 6th, 1991.
In liquid preparation, preferably use the enzyme stability series.The enzyme stabilization technique has been well-known in prior art.For example, a kind of aqueous solution enzyme stabilization technique just is to use the free calcium ions from calcium sources such as lime acetate, calcium formiate and calcium propionate.Calcium ion can with short chain carboxy acid's salt, preferably formate is used in combination.For example visible United States Patent (USP) the 4th, 318,818.Someone advises also can using polyvalent alcohol, resembles glycerol and Sorbitol Powder.And alkoxyl alcohol, dialkyl group alcohol ether, the mixture of multivalence alcohol and multifunctional aliphatic amine (for example, diethanolamine, trihydroxy ethylamine, diisopropanolamine (DIPA), etc.) boric acid or alkali metal borate.The enzyme stabilization technique is in U.S. Pat-4,261,868 and US-3,600,319 and European patent EP-A-0,199,405 and No.86200586.5 in be disclosed and example.Non-boric acid and borate stablizer are desirable.The enzyme stability series are in U.S. Pat-4,261,868, and US-3 is also on the books in 600,319 and US-3,519,570.Other detergent ingredients that is fit to that can add is the oxydasis scavenging agent, and it is on the books in the European patent N-92870018.6 of application on January 31st, 1992.The example of this kind of enzyme oxidation scavengers such as oxyethyl group four ethylidene polyamines.
Especially desirable detergent ingredients should combine with the composition with color safe energy.These compositions can be, for example are used for the cellulase that color is kept and recovered, and/or peroxidase and/or metal catalyst.This type of metal catalyst is disclosed among the european patent application No.92870181.2 that does not authorize as yet.
In addition, thus the polymkeric substance of also finding to contain polyamine N-oxide can eliminate or reduce the deposition of metal catalyst on fabric and improved bleachability.
Another kind of selectable composition is a suds suppressor, for example siloxanes, and silicon-dioxide-mixture of siloxanes.The general available alkylation polysiloxane material of siloxanes is represented, and silicon-dioxide uses as the form of aerosil, xerogel and various types of water drain silicas normally with fine shape.These materials can add with particle form, but suds suppressor be with the form that facility discharges be added in water miscible or the basically nonsurfactant impervious carrier of disperse in water in.Change a kind of method, suds suppressor can be dissolved in or disperse in a kind of liquid vehicle, and splash is on one or more other component.
A kind of desirable silicone suds suppressor is disclosed in people's such as Bartollota U.S. Pat-3,933, in 672.Other special useful suds suppressor has the German patent application DTOS-2 that announces on April 28th, 1977, disclosed self-emulsifying silicone suds suppressor in 646,126.An example of this compound is the DC-544 that can buy from DowCorning company, and this is a kind of siloxanes glycol multipolymer.Desirable especially suds suppressor is the suds suppressor system that comprises the mixture of silicone oil and 2-alkyl chain triacontanol.The 2-alkyl chain triacontanol that is fit to is the 2-butyl octanol of the Isofol 12R board bought on can market.
This suds suppressor is to be disclosed among the European patent N-92870174.7 of application on November 10th, 1992.
Especially desirable silicone suds suppressor is a disclosed suds suppressor in European patent N-92201649.8.Said composition can comprise siloxanes/silica mixture, and wherein silicon is atresia silicon-dioxide such as the Aerosi 1R that smokes.
The content of above-mentioned suds suppressor in composition generally accounts for 0.001% to 2% of composition weight, and preferably 0.01% to 1%.
Other composition that is used for detergent composition also can use, as soil-suspending agent, dirt remover, white dyes, abrasive, sterilant, tarnish inhibitor, color brightening agent, and/or with capsulated or need not capsulated spices.
The antiredeposition and the soil-suspending agent that are fit to comprise the poly carboxylic acid of derivatived cellulose such as methylcellulose gum, carboxymethyl cellulose, Natvosol, homopolymerization or copolymerization or their salt.Such polymkeric substance comprises above-mentioned polyacrylic ester and maleic anhydride acrylic copolymer as washing assistant, and maleic anhydride and ethene, the multipolymer of ethylene methacrylic ether or methacrylic acid, wherein maleic anhydride constitutes at least 20 molecular fractions of this multipolymer.The weight of these materials in composition is generally 0.5% to 10%.More preferably from 0.75% to 8%, the most preferably from 1% to 6%.
Desirable whitening agent is that negatively charged ion is the thing feature, for example 4,4 '-two-(2-diethanolamine-4-anilino-s-triazine-6-base is amino) stilbene 2:2 ' disulfonic acid disodium, 4,4 '-two-(2-morpholino-4-anilino-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(2,4-hexichol amido-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 4 ', 4 " two-(2; 4-hexichol amido-s-triazine-6-base is amino) stilbene-2-sodium sulfonate, 4,4 '-two-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium; 4; 4 '-two-(4-phenyl-2,1,3-triazole-2-yl) stilbene-2:2 ' disulfonic acid disodium; 4,4 '-two-(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium.2 (stilbene radicals-4 " (naphtho--1 ', 2 ': 4,5)-1,2,3-triazoles-2 " sodium sulfonate.
Other useful polymeric material is that those molecular weight are 1000-10000, more preferably is 2000-8000, the most preferably is 4000 polyoxyethylene glycol.Used content accounts for 0.20% to 5% of composition weight, and more preferably 0.25% to 2.5%.These polymkeric substance and above-mentioned all-or the multi-carboxylate of copolymerization under the situation that has transition metal impurity to exist, improving bleachability, fabric ash-deposition and to remove soil property, protein and oxidable dirt be valuable.
The dirt remover that is used for composition of the present invention mainly is terephthalic acid and 1,2 ethylidene glycol and/or multipolymer or the terpolymer of propylene glycol under various structures.The example of this polymkeric substance is disclosed in the U.S. Pat of together transferring the possession of 4116885 and US-4711730 and European publication N-0272033.A kind of polymkeric substance desirable especially according to European patent EP-A-0-0272033 has molecular formula
(CH
3(PEG)
43)
0.75(POH)
0.25[(T-PO)
2.8(T-PEG)
0.4] T (PO-H)
0.25(PEG)
43CH
3)
0.75Wherein PEG is-(OC
2H
4) O-, PO is (OC
3H
6O), T is (pcOC
6H
4CO).
Modified poly ester such as dimethyl terephthalate, dimethyl sulfo group isophthalic ester, 1, the random copolymers of 2-ethylidene glycol and 1-2 propylene glycol also is very useful, and end group comprises the sulfosalicylic acid salt of one-level, 1,2 ethylidene glycol and/or propylene glycol monoester with secondary.Purpose obtains at two ends exactly by the end capped polymkeric substance of sulfosalicylic acid base, and " one-level " under the meaning of said multipolymer, is meant that end group is covered by the sulfosalicylic acid base.But some multipolymer is not capped entirely, so their end group may comprise the monoesters of 2-ethylidene glycol and/or 1-2 propylene glycol, thereby formation " secondary " class.
Here selected polyester comprises the dimethyl terephthalic acid of about 46% weight, 1 of about 16% weight, 2-propylene glycol, 1 of about 10% weight, the 2-ethylidene glycol, the dimethyl methyl yl benzoic acid of about 13% weight and about 15% weight sulfoisophthalic acid, molecular weight is about 3000.These polyester and their preparation method see EPA-311342 for details.
According to the present invention, detergent composition can be liquid, pasty state, gel, or particulate state.According to the present invention, granular composition also can be referred to as " concentrated shape ", and promptly they have higher density than common detergent granules, i.e. the 550-950 grams per liter; In this case, compare, will contain more a spot of " inorganic filling salt " in the granular detergent composition of the present invention with common granulated detergent.Typical filling salt has the vitriol and the muriate of alkaline-earth metal, and is typical in sodium sulfate; The filling salt that " concentrated shape " washing composition contains generally is no more than 10%.According to the present invention, liquid composition also can be " concentrated type ", in this case, compares with common liquid washing agent, and liquid washing agent of the present invention will contain a spot of water.Typically, the content of water generally is less than 30% of detergent composition weight in this concentrated liquid detergent, and preferable is to be less than 20%, the most preferably is less than 10%.The other example of liquid composition is the anhydrous composition that is substantially free of water.Have water or anhydrous liquid composition can be setting or unbodied.
The present invention also relates in the fabric washing operation that includes yarn dyed fabric, to suppress dissolved suspension dyestuff and transfer to method on the another kind of fabric of being run into from a kind of fabric.
This method comprises the washing soln contact fabric of introducing with the front.
Method of the present invention can be implemented in the program of washing methods expediently.Washing process preferably at 5 ℃ to 75 ℃, particularly carries out under 20 ℃ to 60 ℃ temperature, but these polymkeric substance are up to 95 ℃ or all be effective under the higher temperature.The pH value of washings preferably from 7 to 11, especially from 7.5 to 10.5.
Method and composition of the present invention also can be used as the washing composition additive.
This type of additive can be used for replenishing or strengthening the performance of common washing composition.
Also can comprise in the detergent composition of the present invention and be used for article-cleaning, as the composition of fabric, fiber, crust, skin etc., as hard-surface cleaning composition (being with or without abrasive), washing powder composition, automatic or non-automatic dish washing agent composition.
The following examples are intended to illustrate composition of the present invention, but do not mean and limit or define scope of the present invention with this, and said scope is determined by the accompanying Claim book.
A liquid detergent composition prepared in accordance with the present invention, it comprises following ingredients:
% is in gross weight lipid acid 10 oleic acid 4 citric acids 1 sodium hydroxide 3.4 propylene glycol 1.5 ethanol 10 of detergent composition
Table 1 example I
The degree that dyestuff shifts between different yarn dyed fabrics is studied with the cycles of washing meter that can simulate 30 minutes washing process.200 milliliters washings is arranged in the beaker of cycles of washing meter, 10 centimetres of one 10 cm x the cloth that constitutes as the multiple fiber of the sensing tracer of the dyestuff of separating out of yarn dyed fabric and.The multiple fiber cloth of this root is made of six (respectively being 5 centimetres of sizes of 1.5 cm x) differing materials (peracetic acid fat, cotton, polymeric amide, polyester, wool and polyacrylonitrile silk) stitched together.
The degree of dye transfer is measured to determine with Hunter color.The Hunter color system assesses the colourity of a fabric sample with Δ E value, the Hunter that Δ E value representation is determined by reflecting spectrograph:.L, a, b, the variation of value.This Δ E value is defined by following formula: Δ E={ (a
f-a
i)
2+ (b
f-b
i)
2+ (L
f-L
i)
2}
1/2Wherein subscript i and f are illustrated respectively in the Hunter value before and after the washing in the diffusion of coloring matter fabric.Effective difference of minimum is 1 when 95% confidence level.
Embodiment 1 shows that nonionogenic tenside combines with the polymkeric substance that contains polyamine N-oxide, makes the dye transfer rejection obtain enhancing.
Used tensio-active agent is the Dobanol board nonionogenic tenside of being produced and being sold by Shell Co. Ltd.
The dye transfer rejection is by measuring with containing nonionogenic tenside and/or containing the whiteness of the textiles that the composition of the polymkeric substance of polyamine N-oxide washs and definite.Experiment condition:
PH value=7.8
Wash temperature is 40 ℃
A. according to the detergent composition of Table I, wherein do not contain nonionogenic tenside and PVNO (poly--4-vinylpyridine-N-oxide compound).
B. according to the detergent composition of Table I, wherein contain nonionogenic tenside (Dobanol 45/11) (270ppm), but do not contain PVNO (poly--4-vinylpyridine-N-oxide compound).
C. according to the detergent composition of Table I, wherein contain the PVNO (poly--4-vinylpyridine-N-oxide compound) of 6ppm, its molecular-weight average is about 10,000, amine is 1: 10 (using nmr for the determination) with the ratio of amine n-oxide.
D. according to the detergent composition of Table I, wherein contain 6ppm PVNO (poly--4-vinylpyridine-N-oxide compound), its molecular-weight average is about 10,000, and amine is 1: 10 with the ratio of amine n-oxide: and the nonionogenic tenside of 270ppm (Dobanol45/11).
Result: the Δ E value of cotton tracer.Cotton sun blue 90 13.1 12 9.4 5.1 example II (A/B/C) of diffusion of coloring matter fabric composition diffusion of coloring matter fabric color A B C D100% a liquid detergent composition prepared in accordance with the present invention, it comprises following ingredients: % is in the gross weight of detergent composition
A B C linear alkylbenzene sulfonate 10--alkyl alkoxylated suifate-9-polyhydrony fatty acid--9 trimethyl ammonium muriate C
12-C
14--4 alkyl-sulphates 444 Fatty Alcohol(C12-C14 and C12-C18) C
12-C
15) ethoxylate 12 12 12 aliphatic acid 10 10 10 oleic acid 444 citric acids 111 diethylenetriamines 1,5-1.5 1.5 1.5 pentylidene phosphonic acids NaOH 3.4 3.4 3.4 propane diols 1.5 1.5 1.5 ethanol 10 10 10 ethoxylation tetrens 0.7 0.7 0.7 poly--4-vinylpyridine-N-oxide 0-1 0-1 0-1Thermamyl 0.13 0.13 0.13Carezyme 0.014 0.014 0.014FN-alkali (FN-Base) 1.8 1.8 1.8 lipase (Lipolase) 0.14 0.14 0.14 interior glucolase (Endoglucanase) 0.53 0.53 0.53 foam inhibitors (ISOFOLr) 2.5 2.5 2.5 submembers reach as high as 100 EXAMPLE III (A/B/C)
A kind of concentrated type granular detergent composition prepared in accordance with the present invention, it comprises following ingredients:
% is in the gross weight of detergent composition:
A B C linear alkylbenzene sulfonate 11.40--alkyl alkoxy sulfate-10-polyhydroxy fatty hydrochlorate--9 trimethyl ammonium muriate C
12-C
14--4 tallow alkyl sulfates 1.80 1.80 1.80C
45Alkyl-sulphate 3.00 3.00 3.00C
45Alcohol 7 ethoxylates 4.00 4.00 4.00 tallow alcohols 11 ethoxylates 1.80 1.80 1.80 dispersants 0.07 0.07 0.07 silicone liquid 0.80 0.80 0.80 trisodium citrate 14.00 14.00 14.00 citric acids 3.00 3.00 3.00 zeolites 32.50 32.50 32.50 maleic acid acrylic copolymers 5.00 5.00 5.00 cellulases (activated protein) 0.03 0.03 0.03Alkalase/BAN 0.60 0.60 0.60 lipase 0.36 0.36 0.36 sodium metasilicate 2.00 2.00 2.00 sodium sulphate 3.50 3.50 3.50 are poly--and (example I (A/B/C) and II (A/B/C) show good scourability during with fabric mixing, washing white and to the color safe energy of colored fabric coloured and coloured to 4-vinylpyridine-N-oxide 0-1 0-1 0-1 submember to 100 above-mentioned compositions.
Claims (8)
1. detergent composition that suppresses dye transfer, it comprises
A) amine is 2: 3 to 1: 1 with the amine n-oxide ratio, 000,000 poly-(4-vinylpridine-N-oxide compound); With
B) the tensio-active agent system of cleaning significant quantity, it is selected from nonionic, negatively charged ion, positively charged ion, amphoteric, zwitter-ion and semi-polarity tensio-active agent or its mixture,
Wherein said composition is granular or liquid, aqueous form detergent composition.
2. inhibition dye transfer composition according to claim 1, wherein the average molecular weight range of poly-(4-vinylpridine-N-oxide compound) polymkeric substance is 500 to 1,000,000.
3. inhibition dye transfer composition according to claim 1, wherein the content of poly-(4-vinylpridine-N-oxide compound) accounts for 0.001% to 10% of composition weight.
4. inhibition dye transfer composition according to claim 1, wherein said tensio-active agent are to comprise nonionogenic tenside.
5. inhibition dye transfer composition according to claim 4 also comprises the tensio-active agent that is selected from anion surfactant or positively charged ion or amphoterics or its mixture.
6. inhibition dye transfer composition according to claim 1, it is a kind of non-dust granules or liquid scrubbing agent addition agent.
7. one kind contains the detergent composition that right requires 6 described inhibition dye transfer compositions, also comprise washing assistant, sequestrant, SYNTHETIC OPTICAL WHITNER, suds suppressor, soil releasing agent, anti redeposition agent, optional whitening agent, abrasive, sterilant, tarnish inhibitor, tinting material, spices, or its mixture.
8. one kind contains the detergent composition that right requires 1 described inhibition dye transfer composition, also comprise washing assistant, sequestrant, SYNTHETIC OPTICAL WHITNER, suds suppressor, soil releasing agent, anti redeposition agent, optional whitening agent, abrasive, sterilant, tarnish inhibitor, tinting material, spices, or its mixture.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92202168 | 1992-07-15 | ||
| EP92202168.8 | 1992-07-15 | ||
| EP92870182A EP0596185A1 (en) | 1992-11-06 | 1992-11-06 | Stable liquid detergent compositions inhibiting dye transfer |
| EP92870182.0 | 1992-11-06 | ||
| EP93201198A EP0579295B1 (en) | 1992-07-15 | 1993-04-26 | Detergent compositions inhibiting dye transfer |
| EP93201198.4 | 1993-04-26 | ||
| EP19930870105 EP0587549B1 (en) | 1992-07-15 | 1993-06-09 | Dye transfer inhibiting compositions comprising bleaching agents |
| EP93870106.7 | 1993-06-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1084211A CN1084211A (en) | 1994-03-23 |
| CN1040656C true CN1040656C (en) | 1998-11-11 |
Family
ID=40427517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93116491A Expired - Lifetime CN1040656C (en) | 1992-07-15 | 1993-07-15 | Surfactant-containing dye transfer inhibiting compositions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1040656C (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0135217A1 (en) * | 1983-07-22 | 1985-03-27 | THE PROCTER & GAMBLE COMPANY | Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions |
| EP0327927A2 (en) * | 1988-02-06 | 1989-08-16 | Henkel Kommanditgesellschaft auf Aktien | Detergent additive |
-
1993
- 1993-07-15 CN CN93116491A patent/CN1040656C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0135217A1 (en) * | 1983-07-22 | 1985-03-27 | THE PROCTER & GAMBLE COMPANY | Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions |
| EP0327927A2 (en) * | 1988-02-06 | 1989-08-16 | Henkel Kommanditgesellschaft auf Aktien | Detergent additive |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1084211A (en) | 1994-03-23 |
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