CN1047623C - Dye transfer inhibiting compositions comprising bleaching agents - Google Patents
Dye transfer inhibiting compositions comprising bleaching agents Download PDFInfo
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- CN1047623C CN1047623C CN 93116770 CN93116770A CN1047623C CN 1047623 C CN1047623 C CN 1047623C CN 93116770 CN93116770 CN 93116770 CN 93116770 A CN93116770 A CN 93116770A CN 1047623 C CN1047623 C CN 1047623C
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- dye transfer
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- transfer compositions
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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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—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
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 the following 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 or 0 or 1; R are aliphatic, ethoxylated aliphatics, 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 form part of these groups. b) a bleacher.
Description
The present invention relates to a kind of dye transfer compositions and method thereof between fabric that suppress in cleaning process, inhibition dye transfer compositions particularly comprises polymkeric substance and the SYNTHETIC OPTICAL WHITNER that contains polyamine N-oxide.
The SYNTHETIC OPTICAL WHITNER that is usually used in detergent composition assists in removing stain, bleached woven fabric.Generally, SYNTHETIC OPTICAL WHITNER is removed dirt and color spot on the fabric by oxygenizement, and oxygenizement makes the easier dissolving that becomes of dirt and color spot, therefore removes also just much easier.SYNTHETIC OPTICAL WHITNER also is used to brighten along with time and use and the white fabrics of turning to be yellow.
The relative capacity that SYNTHETIC OPTICAL WHITNER satisfies various performance index especially depends on the existence of adding detergent ingredients.Therefore, the difficult problem that the makers-up faced of washing composition provides the detergent composition with various premium propertiess.
A kind of washing composition that adds in the detergent composition adds the polymkeric substance that composition is the inhibition dye transfer.These polymkeric substance are added in the detergent composition in order that suppress dyestuff transfer on other fabric of washing simultaneously from colored fabric.In the cleaning process, on dyestuff is had an opportunity attached to fabric before, these polymkeric substance can be compound or be absorbed from DYED FABRICS and wash the unsettled dyestuff that comes.
Polymkeric substance has been used for detergent composition to suppress dye transfer.Common pending European application No92202168.8 has put down in writing the polymkeric substance that contains polyamine N-oxide, and these polymkeric substance can be eliminated the transfer of dissolving or suspension dyestuff effectively.
It has been found that the polymkeric substance and the SYNTHETIC OPTICAL WHITNER that contain polyamine N-oxide are very compatible.Find also that when SYNTHETIC OPTICAL WHITNER exists the performance of inhibition dye transfer that contains the polymkeric substance of polyamine N-oxide increases.
This discovery makes us can prepare such detergent composition: they not only have the performance of all washing composition, also have the characteristic of good inhibition dye transfer.
According to another embodiment of the invention, also provide washing to include the working method of yarn dyed fabric.
The present invention relates to suppress dye transfer compositions, comprising:
A) a kind of polymkeric substance is selected from the polymkeric substance that contains polyamine N-oxide, and it contains the unit of following structural (I):
Wherein P is one and can gathers the unit, above the N-O group can be connected in, or constitute and can gather a unitary part, or both combinations;
A is
-O-,-S-,
X is 0 or 1;
R is aliphatic, ethoxylated fat family, aromatic, heterocycle family or alicyclic group, or their any combination, above wherein the nitrogen of N-O group can be connected in, or constitutes the part of these groups,
B) a kind of SYNTHETIC OPTICAL WHITNER.
It is the polymkeric substance that contains polyamine N-oxide that composition of the present invention comprises a kind of necessary composition, and it contains following structural formula unit:
Wherein P is one and can gathers the unit, and the R-N-O group can connect thereon, perhaps form this and can gather a unitary part, or both combinations;
A is
-O-,-S-,
X is 0 or 1;
R is aliphatic, ethoxylated fat family, aromatic, heterocycle family or alicyclic group, or their any combination, and wherein the nitrogen in the N-O group can connect thereon, or becomes the part of these groups.
The N-O group can be used following general formula:
R wherein
1, R
2, R
3Be aliphatic group, aromatic, heterocycle family or alicyclic group, or their combination, x and/or y and/or z are 0 or 1, and wherein the nitrogen in the N-O group can be connected on the group or constitute the part of these groups.
The N-O group can be the part that can gather unit (P), or links on the polymer main chain, or the two is mixed with it.
Wherein N-O group forms can gather a unitary part, and so suitable polyamine N-oxide comprises that R is selected from the polyamine N-oxide of aliphatics, aromatic series, alicyclic or heterocyclic group group.
The described polyamine N-oxide of one class comprises the wherein polyamine N-oxide class of the nitrogen formation R-base section of N-O group.Preferred polyamine N-oxide compound is that wherein R is a heterocyclic group, for example pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, those of quinoline, acridine and their derivative.
Another kind of described polyamine N-oxide comprises that the nitrogen of N-O group wherein links the polyamine N-ization thing class on the R-base.
Other suitable polyamine N-oxide is that wherein N-O group is linked the polyamine N-oxide that can gather on the unit.
These polyamine N-oxide preferably have the polyamine N-oxide of general formula (I), and wherein R is aromatic series, heterocycle family or alicyclic group, and the nitrogen of N-O functional group is the part of described R-base.
The example of these polyamine N-oxide is that wherein R is a heterogeneous ring compound, for example the polyamine N-oxide of pyridine, pyrroles, imidazoles and their derivative.
Another kind of preferred polyamine N-oxide compound is the polyamine N-oxide with general formula (I), and wherein R is aromatic series, heterocycle family or alicyclic group, and the nitrogen of N-O functional group is connected on the described R-base.
The example of these polyamine N-oxide is that wherein the R base is the polyamine N-oxide of aromatic series such as phenyl.
Any main polymer chain all can use, as long as the amine oxide polymers that forms is water miscible and has the characteristic that suppresses dye transfer.The example that polymer main chain is suitable is polyethylene, poly-alkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and their mixture.
The ratio of amine and amine n-oxide is generally 10 in the amine n-oxide polymkeric substance of the present invention: 1-1: 1000000.But being present in the amount that contains amine oxide group in the polyamine N-oxide pllymers can change with suitable co-polymerization or suitable N-degree of oxidation.The preferred ratio of amine and amine n-oxide is 2: 3-1: 1000000, and preferred ratio is 1: 4-1: 1000000 most preferred ratios are 1: 7-1: 1000000.In fact, polymkeric substance of the present invention comprises random or segmented copolymer, and wherein a kind of monomer is an amine n-oxide, and another kind of monomer can be amine n-oxide or not be.The unitary PKa of the amine oxide of polyamine N-oxide＜10, preferred PKa＜7, more preferably PKa＜6.
Almost in the polymerization of any degree, can obtain containing the polymkeric substance of polyamine N-oxide.As long as the ability of material water-soluble likely and suspension dyestuff, the polymerization degree is not strict.
Generally, the average molecular weight range of polymkeric substance that contains polyamine N-oxide is at 500-1, and 000,000; Preferably 1,000-50,000, more preferably 2,000-30,000, most preferably 3,000-20,000.
The present invention contains the amount of polymkeric substance of polyamine N-oxide to suppress the weight of dye transfer composition, is generally 0.001%-10%, 0.01%-2% more preferably, most preferably O.05%-1%.
Composition of the present invention is easily as the additive of conventional washing agent composition and be used for washing operation.The present invention also comprises the inhibition dye transfer compositions, and it contains detergent components, therefore can be used as detergent composition.The method for preparing polyamine N-oxide:
The preparation method who contains polyamine N-oxide pllymers can be: the polymeric amine monomer, and resulting polymers and a kind of suitable oxygenant carry out oxidation; Perhaps amine oxide monomer itself aggregates into polyamine N-oxide.
The synthetic method that contains the polymkeric substance of polyamine N-oxide can illustrate by synthesizing polyethylene-pyridine N-oxides.Poly--4-vinylpyridine ex Polysciences (mw.50,000,5.0g 0.0475mole) is dissolved in the 50ml acetate in advance, by volumetric pipette peracetic acid solution (25g Glacial acetic acid, the H of 6.4g30%vol.
2O
2Solution, several H
2SO
4, obtain the 0.0523mol peracetic acid) handle.Stirred this mixture 30 minutes down in envrionment temperature (32 ℃).Then, with oil bath mixture heating up is arrived 80-85 ℃, 3 hours, again standing over night.Tremble down stirring, polymers soln that obtains and the mixing of 1L acetone.Obtain being positioned at the yellowish brown mucilage of bottom, clean with 1L acetone again, produce a kind of grey look crystalline solid.
Utilize gravity filtration to go out solid, clean with acetone, again through P
2O
5Dry.
This polymeric amine: amine n-oxide is 1: 4 (being determined by NMR).SYNTHETIC OPTICAL WHITNER
Detergent composition of the present invention contains the oxygen bleaching agent component.These SYNTHETIC OPTICAL WHITNER components can comprise one or more oxygen bleaching agents, one or more bleach-activating agents, and this depends on the SYNTHETIC OPTICAL WHITNER of selection.When having SYNTHETIC OPTICAL WHITNER, general SYNTHETIC OPTICAL WHITNER compounds content is the about 1%-of detergent composition about 10%.Usually, the SYNTHETIC OPTICAL WHITNER compound is the selectivity component of non-liquid formulation such as granulated detergent.If there is activator of bleaching agent, it is about 60% that its amount is generally about 0.1%-of whitener composition, more common is about 0.5%-about 40%.
Here used SYNTHETIC OPTICAL WHITNER component can be any SYNTHETIC OPTICAL WHITNER that detergent composition is suitable for, and comprises other known SYNTHETIC OPTICAL WHITNER in oxygen bleaching agent and the prior art.
On the other hand, the present invention also provides with detergent composition and has been lower than about 50 ℃, especially is being lower than the method for cleaning fabric, fiber, textiles under about 40 ℃ temperature, and wherein detergent composition comprises the polymkeric substance that contains polyamine N-oxide, optionally auxiliary detergent surfactant, optionally attached composition of washing composition and SYNTHETIC OPTICAL WHITNER.
Being suitable for SYNTHETIC OPTICAL WHITNER of the present invention can be active or inactive SYNTHETIC OPTICAL WHITNER.
An available class oxygen bleaching agent comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The example that these SYNTHETIC OPTICAL WHITNER are suitable comprises that list is crossed O-phthalic enzyme magnesium hexahydrate, chlorine peroxybenzoic acid magnesium salts, 4-ammonia in the ninth of the ten Heavenly Stems-4-oxo perbutyric acid and two are crossed dodecandioic acid partially.These SYNTHETIC OPTICAL WHITNER are disclosed in United States Patent (USP) 4,483, and 781, U.S. Patent application 740,446, european patent application 0,133,354 and United States Patent (USP) 4,412,934.SYNTHETIC OPTICAL WHITNER very preferably comprises that also 6-chloro-in ninth of the ten Heavenly Stems 6-oxo crosses caproic acid, and it is disclosed in United States Patent (USP) 4,634, in 551.
Available another kind of SYNTHETIC OPTICAL WHITNER comprises the halogen SYNTHETIC OPTICAL WHITNER.The example of hypohalite (hypohalite) SYNTHETIC OPTICAL WHITNER comprises as trichloroisocyanuric acid, Surchlor GR 60 and potassium, N-chlorine and N-bromine alkane sulfonamide.The add-on of these materials is generally the 0.5-10% of final product weight, is preferably 1-5% (wt).
Be suitable for preferred SYNTHETIC OPTICAL WHITNER of the present invention and comprise peroxygen bleach.The example of suitable water-soluble solid peroxygen bleach comprises the hydrogen peroxide releasing agent, and as hydrogen peroxide, perborate is as a water perborate, four water perborate, persulphate, percarbonate, peroxydisulfate, superphosphate and peroxyhydrates.Preferred SYNTHETIC OPTICAL WHITNER is percarbonate and perborate.
The hydrogen peroxide releasing agent can mix use with bleach-activating agent, for example the tetrem acyl 1,2-quadrol (TAED), nonanoly acyloxy benzene sulfonate (NOBS is disclosed in US4, and 412, in 934), 3,5-trimethyl acetyl oxygen base benzene sulfonate (ISONOBS is disclosed in EP120,591 in) or five acetyl glucose (PAG), they cross the peracid of hydrolysis formation as active bleaching agent, and bleaching effect is improved.Suitable activator also can be an acylated citrate (ATC), for example is disclosed in common pending European application No.91870207.7.
Also can produce hydrogen peroxide by adding a kind of enzyme catalysis system (being enzyme and Substrate thereof), wherein the generation of hydrogen peroxide can be in beginning or the centre cleaned and/or rinsing is operated.Such enzyme system is disclosed in european patent application 91202655.6 (1991,10,9 application).
Other is suitable for peroxygen bleach of the present invention and comprises organic peroxide acid, as percarboxylic acids.
Except oxygen bleaching agent, can be SYNTHETIC OPTICAL WHITNER well known in the prior art also, and be used for the present invention.Interested especially a kind of non-oxygen bleaching agent comprises photosensitive SYNTHETIC OPTICAL WHITNER such as sulfonated Phthalocyanine Zinc and/or aluminium.In cleaning process, these materials can be deposited on the Substrate.Under the rayed, aerobic exists, and for example clothes is hung over and spills driedly under the daylight, and the sulfonated Phthalocyanine Zinc is activated, and Substrate obtains bleaching as a result.Preferred Phthalocyanine Zinc and photosensitive bleaching method are disclosed in United States Patent (USP) 4,033, in 718.Generally, detergent composition contains the sulfonation phthalocyanine phthalocyanine zinc of the 0.025%-that has an appointment about 1.25% (wt).Detergent additive
Detergent composition can utilize a lot of tensio-active agents.Generally be negatively charged ion, nonionic, amphoteric and zwitterionic tensio-active agent, the kind of these tensio-active agents is documented in Norris1972, in 5,23 United States Patent (USP)s of publishing 3,664,961.
The mixture of anion surfactant is particularly suitable for the present invention, the mixture of sulfonate and sulfate surfactant especially, and its weight ratio is 5: 1-1: 2, preferred 3: 1-2: 3, more preferably 3: 1-1: 1.Preferred sulfonate comprises alkylbenzene sulfonate, and the carbon atom on its alkyl is 9-15, especially 11-13; Also comprise α-sulfonated fatty acid methyl ester, wherein adipose-derived in C
12-C
18Fat is preferably from C
16-C
18Fat.In each example, positively charged ion is a basic metal, preferred sodium.Preferred sulfate surfactant is the alkyl-sulphate that 12-18 carbon atom arranged on the alkyl, optionally mixes with ethoxy vitriol, and the carbon atom on the ethoxy vitriol alkyl is 10-20, is preferably 10-16, and average degree of ethoxylation is 1-6.The example of preferred alkyl vitriol of the present invention is tallow alkyl sulfate, coconut alkyl-sulphate and C
14-C
15Alkyl-sulphate.Positively charged ion in each example also is an alkali metal cation, is preferably sodium.
Being used for a class nonionogenic tenside of the present invention is the condenses of oxyethane and hydrophobic part, and its average hydrophilic lipophilic balance value (HLB) of the tensio-active agent that obtains is 8-17, is preferably 9.5-13.5, more preferably 10-12.5.Hydrophobic (oleophylic) part can be an aliphatics or aromatic, can easily regulate with the length of the polyoxyethylene group of any specific hydrophobic group condensation, and the water-soluble cpds of generation has the equilibrium value between the hydrophilic and oleophylic unit of ideal.
This class nonionogenic tenside particularly preferably is the C that every mol alcohol contains 3-8mol oxyethane
9-C
14The primary alconol b-oxide, particularly every mol alcohol contains the C of 6-8mol oxyethane
14-C
15Primary alconol and every mol alcohol contain the C of 3-5mol oxyethane
12-C
14Primary alconol.
Another kind of ionic surfactant pack is drawn together the alkyl poly glucoside compound, and general formula is:
RO (C
nH
2nO)
tZ
xWherein Z is the part from glucose; R is the saturated hydrophobic alkyl that contains 12-18 carbon atom; T is 0-10, and n is 2 or 3; X is 1.3-4, and these compounds comprise and are less than 10% unreacted Fatty Alcohol(C12-C14 and C12-C18) and are less than 50% short-chain alkyl polyglucoside.This compounds and the purposes in washing medicated roll thereof are disclosed among the EP-B0070077,0075996 and 0094118.
Suitable nonionogenic tenside also can be a polyhydroxy fatty acid amide surfactant, and formula is:
Or its oxidation alkyl derivative, wherein R
1Be H, perhaps R
1Be C
1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixing; R
2Be C
5-31Alkyl; Z is the polyhydroxy alkyl with straight-chain alkyl, and at least 3 hydroxyls are directly linked on the alkyl straight chain.Preferably, R
1Be methyl, R
2It is straight chain C
11-15Alkyl or alkenyl such as coconut alkyl or its mixture, Z are from the reducing sugar in the reductive amination process such as glucose, fructose, maltose, lactose.
Can also comprise builder system according to composition of the present invention.Any common builder system all is applicable to the present invention, comprise silico-aluminate material, silicate, many carboxylates and lipid acid, material such as edetate, metal ion sequestering agent such as aminopolyphosphonic acid salt, particularly ethylenediamine tetramethylene phosphoric acid and diethylenetriamine pentamethylene phosphoric acid.The present invention can also use phosphate builders, although this is for various environmental factorss and not preferred.
Suitable washing assistant can be a mineral ion exchange material, zeolite A, X, B or the HS of the synthetic zeolite of normally inorganic hydrated aluminosilicate material, particularly hydration such as hydration.
Another kind of suitable inorganic builders material is lamellated silicate, as SKS-6 (Hoechst).SKS-6 is by water glass (Na
2Si
2O
5) the layered silicate crystal formed.
The suitable many carboxylates that contain a carboxyl comprise lactic acid, oxyacetic acid and its ether derivant, and they are disclosed in belgian patent 831,368,821,369 and 821,370.The multi-carboxylate of containing two carboxyls comprises the water-soluble salt of following acid: succsinic acid, propanedioic acid, (ethylenedioxy) diacetic acid, toxilic acid, diethyl alkyd, tartrate, tartronic acid, fumaric acid; be disclosed in German offenlegenschrift2 in addition; 446; 686,2; 446,687 and United States Patent (USP) 3,935; ether carboxylate in 257 (ether carboxy-late) and be disclosed in sulfinyl carboxylate salt in the belgian patent 840,623.Especially, the multi-carboxylate of containing three carboxyls comprises water miscible Citrate trianion, aconitate, citraconate, be disclosed in English Patent 1 in addition, succinate derivative such as carboxyl methoxy succinate in 379,241 are documented in the newborn acyloxy succinate (lactoxysuccinates) in Holland's application 7205873 and are documented in English Patent 1,387, oxidation multi-carboxylate material in 447 such as 2-dislike-1,1,3-tricarballylic acid salt.
The multi-carboxylate of containing four carboxyls comprises and is disclosed in English Patent 1,261, the oxygen di-succinate, 1,1,2 in 829,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Containing the substituent multi-carboxylate of sulphur comprises and is disclosed in English Patent 1,398,421,1,398,422 and United States Patent (USP) 3,936,448 in the thio succinate derivative, be disclosed in English Patent 1, sulfonated pyrolysis Citrate trianion in 082,179 contains the substituent multi-carboxylate of phosphine (Phosphone) and is disclosed in English Patent 1, in 439,000.
Alicyclic ring and heterocyclic multi-carboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene (cyclopentadienide) pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylate, 2,2,5,5-tetrahydrofuran (THF)-tetracarboxylic acid hydrochlorate, 1,2,3,4,5, the carboxymethyl derivant of 6-hexane-hexacarboxylic acid salt and polyvalent alcohol such as sorbyl alcohol, N.F,USP MANNITOL and Xylitol.Aromatic multi-carboxylate comprises and is disclosed in English Patent 1,425, mellitic acid, 1,2,4,5-pyromellitic acid and phthalic acid derivative in 343.
In above-mentioned multi-carboxylate, preferably per molecule contains the multi-carboxylate of no more than 3 carboxyls, particularly Citrate trianion.
Be used for the preferred builder system of the present composition and comprise water-insoluble silico-aluminate washing assistant such as zeolite A or lamellated silicate (SKS/6), also comprise the mixture of water miscible carboxylate sequestrant such as citric acid.
Being included in sequestrant suitable in the detergent composition of the present invention is quadrol-N, the ammonium salt of N '-disuccinic acid (EDDS) or its basic metal, alkaline-earth metal, ammonium or replacement, or their mixture.Form that preferred EDDS compound is a free acid and its sodium or magnesium salts.The example of preferred EDDS sodium salt comprises Na
2EDDS and Na
4EDDS.The example of preferred EDDS magnesium salts comprises MgEDDS and Mg
2ED-DS.This magnesium salts is that the present composition is most preferred.
For liquid composition of the present invention, the suitable fatty acids washing assistant of use is saturated or undersaturated C especially
10-18Lipid acid and corresponding soap.Preferred saturated fatty acid washing assistant has 12-16 carbon atom on alkyl chain.Preferred unsaturated fatty acids is an oleic acid.
Be used for the mixture that the preferred builder system of particulate composition comprises water-insoluble silico-aluminate washing assistant such as zeolite A and water miscible carboxylate sequestrant such as citric acid.
The part that other builder material also can become builder system is used for particulate composition, and they comprise inorganics such as alkaline carbonate, supercarbonate, silicate and organism such as organic phosphonate, amino poly-alkylene phosphonate and amino many carboxylates.
Other suitable water-soluble organic salt is equal polymeric acid or copolymerization acid or their salt, and wherein poly carboxylic acid contains at least two mutually by the carboxyl that is no more than two carbon atoms separate.
This polymkeric substance is disclosed in GB-A-1, in 596,756.
The example of these salt be MW2000-5000 polyacrylate and with the multipolymer of maleic anhydride, the molecular weight of these multipolymers is 20,000-70,000, particularly about 40,000.
Detergent builder compound salt accounts for the 10%-80% of composition weight usually, preferred 20-70%, the most frequently used 30-60% (wt) that accounts for.
Other washing composition composition can comprise the detergency enzymes that is used for detergent formulation, and they have been widely used, and comprises removing protein, carbohydrate or triglyceride level dirt, for example prevents dye transfer.Used enzyme comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase and their mixture.The enzyme that also can comprise other type.These enzymes can be any suitable sources, for example plant, animal, bacterium, fungi and yeast source.
Usually, the enzyme that adds enough content has the organized enzyme that is not higher than about 5mg (wt) to provide in every gram composition, is generally the about 3mg of about 0.05mg-.
The example that proteolytic enzyme is suitable is the subtilysin from B.Subtilis and the specific bacterial strain of B.licheniforms.The commercial decomposition of protein enzyme that is suitable for removing the albumen dirt that gets comprises to be sold with following trade mark, Alcalase, the Savinase and the Esperase that comprise Novo Industries A/S (Den-mark), International Bio-synthet-lcs, Inc. the Maxatase of (Holland), the FN-base of Genencor, the Opti-mase of Mke and opticlean.
In interesting decomposition of protein enzyme,, be the enzyme that is called protease A and proteolytic enzyme B herein especially for liquid detergent composition.Protease A is documented in the european patent application 130,756, and proteolytic enzyme B is documented in the european patent application sequence number 87303761.8.
Amylase comprises that as the amylase from the special bacterial strain of B.licheniforms its write up is in british patent specification 1,296, among 839 (Novo).Amylolytic protein comprise as Rapidase, Maxamyl (International Bio-Synthetics, Inc.) and Termamyl (Novo Industries).
Can be used for the cellulase that cellulase of the present invention comprises bacterium and fungi.Preferably, their best PH is between 5-9.5.Suitable cellulase is disclosed in people's such as Barbesgoard the United States Patent (USP) 4,435,307, and it has disclosed the fungal cellulase that is produced by Humico-la insolens.Suitable cellulase also is disclosed in GB-A-2, in 075,028, GB-A-2,095,275 and DE-OS-2,247,832.
The example of these cellulases is produced by Humicola insolens (Humicolagrisea var.thermoidea) bacterial strain, Humicola bacterial strain DSW1800 particularly is by the mycetogenetic cellulase of Bacillus N or by mycetogenetic cellulase 212 that belongs to Aeromonas (Aeromonas) and the cellulase (Dolabella Auricula Solander) that extracts from the hepatopancreas of sea mollusk.
Other suitable cellulase is the cellulase from Humicola Insulens, the about 50KPa of its molecular weight, and iso-electric point is 5.5, contains 415 amino acid.These cellulases are documented in the common unsettled European patent 93200811.3 of application on March 19th, 1993.
Especially, suitable cellulase has the effect of protecting color.The example of these cellulases is documented in the european patent application 91202879.2 that Carezyme (Novo) on November 6th, 1991 applied for.
The suitable lipase that is used for washing composition comprises the lipase that is produced by pseudomonas microorganism belonging to genus such as Pseu-domonas stutzeri ATCC19.154, and it is disclosed in English Patent 1,372, in 034.Suitable lipase comprise produce by microorganism fluorescence pseudomonas (Pseu-domonas fluorscent) IAM1057, show those lipase of positive immunological cross-reaction with the antibody of lipase.This lipase can be available from Amano pharmaceuticals company limited, and (Nagoya, Japan), trade mark is called (Lipase) lipase P " Amano ", is called " Amano-P " later on.
Specially suitable lipase is as M
1Lipase (Ibis) and Lipolase (Novo).
Peroxidase and oxygen source for example percarbonate, perborate, persulphate, hydrogen peroxide etc. are used in combination.They are used as " solution SYNTHETIC OPTICAL WHITNER ", prevent that promptly the coloring matter of removing from Substrate in the washing process from transferring to cleaning solution on other Substrate.Peroxidase is that prior art is known, comprises as horseradish peroxidase (horseradish peroxidase), lignoenzyme, halo peroxidase such as chloro and bromo peroxidase.The detergent composition that contains peroxidase is disclosed in for example PCT International Application No. WO 89/099813 and European patent application EP 91202882.6 (application on November 6th, 1991).
In liquid preparation, preferably utilize the enzyme stabilising system.The enzyme stabilization technique of aqueous detergent compositions is disclosed by prior art.For example, the enzyme stabilization technique relates to and utilizes free calcium ions, calcium source such as lime acetate, calcium formiate and calcium propionate in the aqueous solution.Calcium ion can with short chain carboxy acid's salt preferably formate mix to use.For example referring to US4,318,818.People also propose to utilize polyvalent alcohol such as glycerine and sorbyl alcohol.Can also utilize mixture, boric acid or the alkali metal borate of alkoxyl alcohol, dialkyl group glycol ether (dialkylghycoethers), polyvalent alcohol and polyfunctional group fatty amine (as diethanolamine, trolamine, two-Yi Bingchunan etc.).The enzyme stabilization technique also discloses and exemplifies at US4, and 261,868, US3,600,319, European patent application publication No. 0199405 and applying in 86200586.5.Non-boric acid and borate stablizer are preferred.The enzyme stabilising system also is documented in for example US4, in 261,868,3,600,319 and 3,519,570.
The washing composition composition that other that can add is suitable is the oxydasis scavenging agent, and it is documented among the co-pending European application N92870018.6 of application on January 31st, 1992.The example of these oxydasis scavenging agents is four ethylidene polyamines of ethoxylation.
Particularly preferred washing composition composition is the purging compound that has the effect of protection color simultaneously.These examples of substances are that polyvinyl pyrrolidone polymers has the polymkeric substance that suppresses the dye transfer characteristic with other.Other example is used to keep, recover cellulase and/or the peroxidase and/or the metal catalyst of color.These metal catalysts are documented in co-pending European application NO.92870181.2.
In addition, it has been found that the polymkeric substance that contains polyamine-N-oxide compound can eliminate or reduce the deposition of metal catalyst on fabric, therefore improved bleaching effect.
Another kind of selection composition is a froth suppressor, for example polysiloxane and silica-polysiloxane mixture.Polysiloxane can be expressed as alkylating polysiloxane material at large, and silica often uses with tiny form simultaneously, as the silica of silica aerogel and silica xerogel and various hydrophobic naturies.Be added to such particle froth suppressor water-soluble or water is diffusible, come down in the impermeable carrier of on-surface-active detergent these foam inhibition can the particulate form addings, and they have significant releasing effect.In addition, froth suppressor also can dissolve or be dispersed in the liquid vehicle, and is sprayed on one or more other components.
A kind of preferred polysiloxane Foam Control is disclosed among people's such as Bartollota the US3933672.The polysiloxane froth suppressor that other useful especially froth suppressor is a self-emulsifying, it is disclosed among the disclosed German patent application DTOS2646126 on April 28th, 1977.An example of this compounds is can be available from the DC-544 of DowCorning, and it is siloxanes-glycol multipolymer.Especially preferred Foam Control is the froth suppressor system that comprises polysiloxane oil and 2-alkyl-alcohol (alcanol) mixture.Suitable 2-alkyl-alcohol is 2-butyl-octanol, and it can be bought by trade name Isofol12R.
These froth suppressor systems are documented among the co-pending European application N92870174.7 of application on November 10th, 1992.
Particularly preferred polysiloxane Foam Control is documented among the co-pending European application No92201649.8.Described composition can contain imporosity silica such as the Aerosi/R blended polysiloxane/silica mixture with smoke-like.
Usually, the usage quantity of above-mentioned froth suppressor is the 0.001%-2% of composition weight, preferred 0.01%-1%wt.
Other the component that is used for detergent composition can be, for example dirt suspension agent, dirt releasing agent, white dyes, abrasive material, sterilant, tarnish inhibitor, tinting material and/or spices sealing or multiple sealing.
Be suitable for anti-redeposition agent of the present invention and dirt suspension agent and comprise derivatived cellulose such as methylcellulose gum, carboxymethyl cellulose, Natvosol, all or the poly carboxylic acid of copolymerization and salt thereof.This base polymer comprises polyacrylate and above-mentioned copolymer of maleic anhydride and acrylic acid as washing assistant, and the multipolymer of maleic anhydride and ethene, methylvinylether or methylacrylic acid, and maleic anhydride accounts for the 20%mol of multipolymer at least.Usually, the consumption of these materials is 0.5%-10%wt of composition weight, is 0.75%-8% more preferably, most preferably is 1%-6%.
Preferred white dyes is an anionic, for example 4,4 '-two-(2-diethanolamine-4-anilino-S-triazine-6-base ammonia) stilbene--2:2 '-disulfonic acid disodium, 4 ,-4 '-two-(2-morpholine-4-anilino-S-triazine-6-base ammonia) stilbene-2:2 '-disulfonic acid disodium, 4,4 '-two-(2,4-hexichol amido-S-triazine-6-base ammonia) stilbene-2:2 '-disulfonic acid disodium, 4 ', 4 " two-(2; 4-hexichol amido-S-triazine-6-base ammonia) stilbene-2-sulfonic acid one sodium; 4,4 '-two-(2-anilino-4-(N-methyl-N-2-hydroxyethyl ammonia)-S-triazine-6-base ammonia) stilbene-2,2 '-the disulfonic acid disodium; 4; 4 '-two-(4-phenyl-2,1,3-triazole-2-yl)-stilbene-2; 2 '-two sulphurs are to disodium, 4,4 '-two-(2-anilino-4-(1-methyl-2-hydroxyethyl ammonia)-S-triazine-6-base ammonia) stilbene-2,2 '-disulfonic acid disodium and 2 (stilbene radicals-4 " (naphtho--1 '; 2 ': 4; 5)-1,2,3-triazoles-2 " sodium sulfonate.
Other useful polymeric material is a polyoxyethylene glycol, and particularly molecular weight is 1000-10000, be 2000-3000 more preferably, most preferably is about 4000.The consumption of these polymkeric substance is 0.20%-5%wt, more preferably is 0.25%-2.5%wt.In the presence of transition metal impurity, the multi-carboxylate of these polymkeric substance and all above-mentioned or copolymerization helps improving the deposition of the maintenance of whiteness, fabric dirt and to the cleaning performance of clay, proteinic and oxidable dirt.
The soil releasing agent that is used for the present composition is common terephthalic acid and ethylene glycol and/or propylene glycol unit multipolymer or the terpolymer with various arrangements.The example of these polymkeric substance be disclosed in the common US4116885 that assigns and 4711730 and European disclosed patent application 0272033 in.According to EP-A-0272033, a kind of particularly preferred polymkeric substance has formula: (CH
3(PEG)
13)
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
5O), T is (PCOC
6H
4CO).
Modified poly ester is also very suitable, and as the random copolymers of following material: terephthalic acid dimethyl ester, sulfoisophthalic acid dimethyl ester, ethylene glycol, 1,2-propylene glycol, end group mainly are the sulfosalicylic acid esters, and inferior strategic point is the monoesters of ethylene glycol and/or propylene glycol.The purpose of modification be the polymkeric substance two ends that obtain by sulfosalicylic acid ester end-blocking, " mainly ", most of herein multipolymers are end capped by the sulfosalicylic acid ester group.But some polymkeric substance can not be by abundant end-blocking, so their end group can be ethylene glycol and/or 1, the 2-propylene glycol, and Here it is, and " inferior strategic point " is made up of this class.
Here the polyester of Xuan Zeing contains the about 16%wt.1 of 46%wt. terephthalic acid dimethyl ester that has an appointment, 2-propylene glycol, about 10%wt. ethylene glycol, about 13%wt. sulfosalicylic acid dimethyl ester, about 15%wt. sulfoisophthalic acid, molecular weight about 3,000.These polymkeric substance and their preparation method's write up are in EPA311342.
It can be liquid, pulpous state, gel or particulate form that the relevant washing composition of the present invention is combined into.Particulate composition of the present invention also can be " form closely ", and promptly their density is higher relatively than the density of plain particles washing composition, just 550-950g/l; In this case, compare with traditional granulated detergent, granular detergent composition of the present invention contains more a spot of " inorganic filling salt "; General filling salt is the vitriol and the muriate of alkaline-earth metal, is generally sodium sulfate; " closely " detergent composition generally contains no more than 10% filling salt.Liquid composition of the present invention can also be " a dense volume form ", in this case, compares with traditional liquid washing agent, and liquid detergent composition of the present invention contains more a spot of water.Generally, water-content less than 30%, more preferably is less than 20%, most preferably less than 10%wt in detergent composition weight in the spissated liquid washing agent.The example of other liquid composition is the anhydrous composition that is substantially free of water.
Moisture or water-free liquid composition can be structurizing or non-structured.
The invention still further relates to a kind of method, promptly include in the operating process of yarn dyed fabric, suppress dyestuff dissolved and that suspend and transfer on another fabric from a fabric in washing.
Present method comprises that fabric contacts with cleaning solution, and these cleaning solutions were described in front.
Method of the present invention is carried out in cleaning process easily.Cleaning process is preferably carried out under 5 ℃-75 ℃, and especially 20-60 ℃, but polymkeric substance is effective under height to 95 ℃ or higher temperature.The PH of treatment soln is preferably 7-11, particularly 7.5-10.5.
Method and composition of the present invention also can be used for doing washing composition and adds goods.
These add the performance that goods are used for replenishing or improving common detergent composition.
Detergent composition of the present invention comprises the composition that can be used for cleanup action thing such as fabric, fiber, crust, skin etc., for example cleans the composition (have or do not have abrasive material), laundry detergent composition of crust, the composition of motor-driven or non-moving cleaning tableware.
The following examples are used to illustrate composition of the present invention, but are not restriction or definition scope of invention, and described scope is determined according to claim.
Prepare a kind of granular detergent composition of the present invention, composition is as follows:
Table I
% is by the weight of whole detergent composition
Linear alkylbenzene sulfonate 11.40
Tallow alkyl sulfate 1.80
C
45Alkyl-sulphate 3.00
The C that contains 7 ethoxy units
45Ferment 4.00
The tallow alcohol 1.80 that contains 11 ethoxy units
Dispersion agent 0.07
Polysiloxane fluid 0.80
Trisodium citrate 14.00
Citric acid 3.00
Zeolite 32.50
Toxilic acid acrylic acid copolymer compound 5.00
Cellulase (activated protein) 0.03
Lipase 0.36
Water glass 2.00
Sodium sulfate 3.50 embodiment 1
With bottle formula detersive power meter 30 minute cleaning interval of test simulation, research is from the degree of the dyestuff of different colored fabrics transfers.This bottle formula detersive power meter beaker contains the colored fabric of 200ml washing soln, 10cm * 10cm and gathers the multifilament cloth specimen of tracer as the bleeding dyestuff.This multifilament cloth specimen is knitted together and is formed by 6 (every of 1.5cm * 5cm) different material (poly-acetic ester, cotton, polymeric amide, polyester, wool and polyacrylonitrile silk).
Usually measure the degree that Hunter color (Hunter Colour) is determined dye transfer.The Hunter color system uses Δ E value to estimate the colourity of fabric sample, the variation of Δ E value representation Hunter L, a, b value, and it utilizes reflective spectrophotometer to determine.Δ E value defines with following equation:
Δ E={ (a
f-a
i)
2+ (b
f-b
i)
2+ (L
f-L
i)
2}
1/2Wherein subscript i and f refer to the Hunter value before and after cleaning respectively in the presence of the bleeding fabric.Useful variable minimum under 95% confidence level is 1.
Polymkeric substance that embodiment 1 explanation and SYNTHETIC OPTICAL WHITNER blended contain polyamine N-oxide has the performance of the inhibition dye transfer that has improved.Used SYNTHETIC OPTICAL WHITNER is an active bleaching agent (perborate (PB)/TAED).
By with containing PB/TAED and/or poly-(4-vinylpyridine-N-oxide compound) composition cleaning fabric (PVNO), measure the whiteness of fabric, thereby determine the performance of described mixture.Test conditions:
PH＝10
Cleaning temperature: 40 ℃
A: a kind of detergent composition according to table 1 does not contain PB/TAED and PVNO[poly-(4-vinylpridine-N-oxide compound)].
B: a kind of detergent composition according to table 1 contains 16%PB and 5%TAED and does not contain PVNO[poly-(4-vinylpridine-N-oxide compound)].
C: a kind of detergent composition according to table 1 contains 10ppm PVNO[poly-(4-vinylpridine-N-oxide compound)], its molecular-weight average is about 30,000, amine: amine n-oxide is 1: 10 (being measured by NMR).
D: a kind of detergent composition according to table 1 contains 10ppm PVNO[poly-(4-vinylpridine-N-oxide compound)], its molecular-weight average is about 30,000, amine: amine n-oxide is 1: 10 (being measured by NMR), and 16%PB, 5%TAED are arranged.Result: the Δ E value of gathering tracer for cotton.
Example II (A/B/C)
| The bleeding fabric composition | The bleeding fabric composition | ?A | ?B | ?C | ?D |
| 100% cotton | Sun blue | ?23.1 | ?21.6 | ?6.9 | ?4.5 |
Prepare a kind of liquid detergent composition of the present invention, composition is as follows: % is by the weight of whole detergent composition
A B C linear alkylbenzene sulfonate 10--vitriol--9 alkyl-sulphate 444 Fatty Alcohol(C12-C14 and C12-C18) (C of polyhydroxy fatty acid amide-9-alkyl alkoxide
12-C
15) tetren 0.7 0.7 0.7 P4VPs-N-0-1 0-1 0-1 oxide Thermamyl 0.13 0.13 0.13Carezyme 0.014 0.014 0.014FN-Base 1.8 1.8 1.8Lipolase 0.14 0.14 0.14Endoglucanase A, 0.53 0.53 0.53 foams in hibitors (ISOFOL ') 2.5 2.5 2.5H of b-oxide 12 12 12 aliphatic acid 10 10 10 oleic acid 444 citric acids 111 diethylenetriamine pentamethylenophosphonic acids 1.5 1.5 1.5NaOH 3.4 3.4 3.4 propane diols 1.5 1.5 1.5 ethanol 10 10 10 ethoxylations2O
27.5 7.5 7.5ATC, 555 micro-components are added to 100 EXAMPLE III (A/B/C)
Prepare tight granular detergent composition of the present invention, composition is as follows: % is by the weight of whole detergent composition
A B C linear alkylbenzene sulfonate 11.40--vitriol--9 tallow alkyl sulfate 1.80 1.80 1.80C of polyhydroxy fatty acid amide-10-alkyl alkoxide
45Alkyl-sulphate 3.00 3.00 3.00 contains the C of 7 ethoxy units
45Tallow alcohol 1.80 1.80 1.80 dispersants 0.07 0.07 0.07 polysiloxane fluid 0.80 0.80 0.80 trisodium citrate 14.00 14.00 14.00 citric acids 3.00 3.00 3.00 zeolites 32.5 32.5 32.5 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 P4VPs that alcohol 4.00 4.00 4.00 contains 11 ethoxy units-N-oxide 0-1 0-1 0-1 perborate 15 15 15TAED 5-5ATC-5-Trace Components are added to 100
(example II (A/B/C) and EXAMPLE III (A/B/C) show the effect of good cleaning performance and significant protection color to top composition to the mixed goods of colored fabric and colored fabric and white fabrics.
Claims (12)
1. an inhibition dye transfer compositions of using in the water-based washing soln comprises
A) the dye transfer amount of suppression has 2: 3-1: poly-(4-vinylpridine-N-oxide compound) of the ratio of 1000000 amine and amine n-oxide and
B) SYNTHETIC OPTICAL WHITNER of cleaning significant quantity, described SYNTHETIC OPTICAL WHITNER is selected from percarboxylic acids, halogen bleaching agent, perborate, persulphate, percarbonate, peroxydisulfate, superphosphate, peroxyhydrate, hydrogen peroxide generates enzyme, non-oxygen type SYNTHETIC OPTICAL WHITNER, or their mixture;
The content of wherein said poly-(4-vinylpridine-N-oxide compound) polymkeric substance is the 0.001%-10% of composition weight, and its weight-average molecular weight is in the 500-1000000 scope.
2. according to the inhibition dye transfer compositions of claim 1, it also comprises bleach-activating agent.
3. according to the inhibition dye transfer compositions of claim 1, wherein said SYNTHETIC OPTICAL WHITNER is a peroxygen bleach, is selected from perborate, persulphate, percarbonate, peroxydisulfate, superphosphate and peroxyhydrate, or their mixture.
4. according to the inhibition dye transfer compositions of claim 2, wherein said SYNTHETIC OPTICAL WHITNER is a peroxygen bleach, is selected from perborate, persulphate, percarbonate, peroxydisulfate, superphosphate and peroxyhydrate, or their mixture.
5. according to the inhibition dye transfer compositions of claim 4, wherein said bleach-activating agent is selected from tetra acetyl ethylene diamine, nonanoly acyloxy benzene sulfonate; 3,5,5-trimethyl acetyl oxygen base benzene sulfonate; penta-acetyl glucose, the citrate of acidylate, or their mixture.
6. according to the inhibition dye transfer compositions of claim 1 or 2, it also contains metal catalyst as bleaching assistant.
7. according to the inhibition dye transfer compositions of claim 1 or 2, it is the detergent additives of dustless particle or liquid form.
8. according to the inhibition dye transfer compositions of claim 1 or 2, it also comprises
C) detergent surfactant of cleaning significant quantity.
9. inhibition dye transfer compositions according to Claim 8, wherein said bleach-activating agent is selected from tetra acetyl ethylene diamine, nonanoly acyloxy benzene sulfonate; 3,5,5-trimethyl acetyl oxygen base benzene sulfonate; penta-acetyl glucose, the citrate of acidylate, or their mixture.
10. according to the inhibition dye transfer compositions of claim 9, it also contains metal catalyst as bleaching assistant.
11. a detergent composition, the inhibition dye transfer composition that it contains claim 1 or 2 also contains one or more following ingredients: washing assistant, sequestrant, froth suppressor, soil releasing agent, anti redeposition agent, white dyes, abrasive material, sterilant, tarnish inhibitor, tinting material, spices, or their mixture.
12. according to the detergent composition of claim 11, wherein said inhibition dye transfer composition also comprises:
C) detergent surfactant of cleaning significant quantity.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92202168 | 1992-07-15 | ||
| EP92202168.8 | 1992-07-15 | ||
| EP19920870181 EP0596184B1 (en) | 1992-11-06 | 1992-11-06 | Detergent compositions inhibiting dye transfer |
| EP92870181.2 | 1992-11-06 | ||
| EP93201198.4 | 1993-04-26 | ||
| EP93201198A EP0579295B1 (en) | 1992-07-15 | 1993-04-26 | Detergent compositions inhibiting dye transfer |
| EP93870105.9 | 1993-06-09 | ||
| EP19930870105 EP0587549B1 (en) | 1992-07-15 | 1993-06-09 | Dye transfer inhibiting compositions comprising bleaching agents |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1084215A CN1084215A (en) | 1994-03-23 |
| CN1047623C true CN1047623C (en) | 1999-12-22 |
Family
ID=27442374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93116770 Expired - Fee Related CN1047623C (en) | 1992-07-15 | 1993-07-15 | Dye transfer inhibiting compositions comprising bleaching agents |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0587549B1 (en) |
| CN (1) | CN1047623C (en) |
| DE (2) | DE69322449T2 (en) |
| ES (2) | ES2125970T3 (en) |
| MX (1) | MX9304299A (en) |
| TR (1) | TR28340A (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1541576A (en) * | 1975-06-20 | 1979-03-07 | Procter & Gamble Ltd | Inhibiting dye ltransfer in washing |
| US4548744A (en) * | 1983-07-22 | 1985-10-22 | Connor Daniel S | Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions |
| DE3803630A1 (en) * | 1988-02-06 | 1989-08-17 | Henkel Kgaa | DETERGENT ADDITIVE |
| DE69117490T2 (en) * | 1991-04-12 | 1996-09-26 | Procter & Gamble | Compact detergent containing polyvinylpyrrolidone |
-
1993
- 1993-06-09 ES ES93870109T patent/ES2125970T3/en not_active Expired - Lifetime
- 1993-06-09 ES ES93870105T patent/ES2132210T3/en not_active Expired - Lifetime
- 1993-06-09 DE DE1993622449 patent/DE69322449T2/en not_active Expired - Lifetime
- 1993-06-09 EP EP19930870105 patent/EP0587549B1/en not_active Expired - Lifetime
- 1993-06-09 DE DE1993624422 patent/DE69324422T2/en not_active Expired - Lifetime
- 1993-07-15 CN CN 93116770 patent/CN1047623C/en not_active Expired - Fee Related
- 1993-07-15 MX MX9304299A patent/MX9304299A/en unknown
- 1993-07-15 TR TR00616/93A patent/TR28340A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0587549A1 (en) | 1994-03-16 |
| DE69324422T2 (en) | 1999-11-18 |
| DE69322449T2 (en) | 1999-07-08 |
| ES2132210T3 (en) | 1999-08-16 |
| MX9304299A (en) | 1994-05-31 |
| EP0587549B1 (en) | 1999-04-14 |
| TR28340A (en) | 1996-05-02 |
| DE69324422D1 (en) | 1999-05-20 |
| ES2125970T3 (en) | 1999-03-16 |
| CN1084215A (en) | 1994-03-23 |
| DE69322449D1 (en) | 1999-01-21 |
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