CN1154136A - Detergent composition containing oleoyl sarcosinate and anionic surfactants in optimum ratios - Google Patents
Detergent composition containing oleoyl sarcosinate and anionic surfactants in optimum ratios Download PDFInfo
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- CN1154136A CN1154136A CN 95194348 CN95194348A CN1154136A CN 1154136 A CN1154136 A CN 1154136A CN 95194348 CN95194348 CN 95194348 CN 95194348 A CN95194348 A CN 95194348A CN 1154136 A CN1154136 A CN 1154136A
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Abstract
A detergent composition surprisingly having improved cleaning performance and improved solubility in aqueous laundering solutions is provided. Specifically, the detergent composition comprises at least 1 % of a surfactant system containing at least one anionic surfactant selected from the group consisting of alkyl benzene sulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl ethoxy sulfates, secondary alkyl sulfates and mixtures thereof. Also included is at least about 0.1 % of oleoyl sarcosinate, wherein the ratio of oleoyl sarcosinate to the surfactant system is from about 1:20 to about 10:1.
Description
Invention field
Relate generally to of the present invention has the detergent composition of the cleaning performance of improvement.More particularly; what the present invention directly related to is the detergent composition that contains oleoyl sarcosinate and one or more anion surfactants, and wherein anion surfactant is selected from alkylbenzene sulfonate, alkyl ester sulfonate, alkyl-sulphate, alkyl ethoxy sulfate, secondary alkyl sulfate and its mixture.The anion surfactant of describing among the present invention mixes with oleoyl sarcosinate with optimum proportion.
Background of invention
General conventional detergent composition contains various surfactant mixtures to remove multiple dirt and spot from the surface.For example various anion surfactant, especially alkylbenzene sulfonates are used to remove particulate fouling and various nonionogenic tenside, and for example alkylethoxylate and alkylphenol ethoxylate are used to remove the lipid dirt.
Although, there is the kinds of surface promoting agent to use in this area for the technician in the washing composition formulation art, most of available tensio-active agents are special chemical, they are not suitable for daily low consumption product for example in the family expenses cleaning composition.In fact, many household laundry still comprise one or more conventional alkylbenzene sulfonates or primary alkyl sulphates tensio-active agent with washing composition.
Generally being used for low temperature (for example 5 ℃ to 30 ℃) washing soln and using for low dosage and be formulated into contemporary granular laundry for " concentrating " or " closely knit " shape and use the limited alkyl sulfate surfactant of solvability especially at large in washing composition, comprise the primary and secondary alkyl-sulphate.For consumers, the packing material that closely knit Betengent product is housed is less, is easy to store and handle.For manufacturers, unit carrying cost, trucking costs and Packing Fee have reduced.
Produce acceptable closely knit or concentrated granulated detergent its difficulty is arranged.In general closely knit detergent formulations, so-called 'inertia' composition for example sodium sulfate is deleted basically.Yet this composition but plays a part to strengthen conventional detergent dissolution degree.Therefore, usually there is solubility problem in closely knit washing composition, especially in cold washing solution.And conventional closely knit or low density detergent granule is normally used spray drying method for preparation, and this has obtained very being easy to extremely porous detergent particles of dissolved in wash water solution.On the contrary, closely knit washing composition generally is made up of the high density detergent granules in few hole, and it is not easy to dissolving.In a word, contain a large amount decontamination composition and have only the particle that on a small quantity or does not add solubilizing agent owing to the compact-type granulated detergent generally comprises, and because this particle is to have a mind to be made into high-bulk-density, therefore, net result is about deliquescent subject matter in using.
Also need in heavy duty liquid laundry detergent, to mix effectively some alkyl sulfate surfactant, with the comprehensive cleansing power that obtains.And the lower alkyl chains sulfate surfactant can easily be incorporated in the light dirt liquid detergent, but the prescription teacher in this area face with have 14 or the alkyl-sulphate of more a plurality of carbon atoms mix difficulty in the liquid laundry detergent.These generally are preferred for laundry and other fabric cleaning use than the long-chain tensio-active agent.
Therefore, need a kind of detergent composition, it particularly has the solvability of improvement and the cleaning performance that improves in cold washing solution.This demand is especially general in the used closely knit or high-density granulated detergent field of human consumer.Also need a kind of like this detergent composition, its also can be liquid form or and comprise be used to effectively to improve cleaning performance than the long chain alkyl sulfates tensio-active agent.
Background technology
Oleoyl sarcosinate is described in following patent and the open source literature: U.S.2,542,385; U.S.3,402,990; U.S.3,639,568; U.S.4,772,424; U.S.5,186,855; European patent discloses 505,129; English Patent discloses 1,211, and 545; Japanese Patent discloses 59/232194; Japanese Patent discloses 62/295997; Japanese Patent discloses 02/180811; With chemical abstracts No.61:3244q, 70:58865x and 83:181020p.
Summary of the invention
The present invention has satisfied the above needs by the deliquescent detergent composition that the cleaning performance with improvement is provided and has an improvement in wash water solution.The invention provides and can be particle or agglomerate, or be the detergent composition of liquid form, it can comprise than long chain alkyl sulfates.The oleoyl sarcosinate component has great contribution to beyond thought superior cleaning and the solvability result that the present invention realizes.Fortunately, found the available relatively inexpensive method acyl sarcosinate that produces oil, this method is illustrated in the present invention.In view of above-mentioned, detergent composition of the present invention is practical for current human consumer and can affords.Said composition also provides fabulous color nursing property for colored fabric, provides fabulous skin mildness for the hand washing operation.
Phrase used herein " solvability of the improvement " meaning be the anion surfactant of detergent composition when in the washing soln that uses in mode of the present invention, its solvability is compared enhancing at least 5% with the solvability of identical anion surfactant under same test conditions (being water temperature and pH value, stirring velocity and time, granularity, the water hardness etc.) itself.Term used herein " agglomerate " is meant by agglomeration generally have the particle that the particle of the average particle size littler than the agglomerate that forms forms.Except as otherwise noted, all percentage ratios used herein, ratio and ratio are by weight.All documents that this paper quotes comprise patent and open source literature, are hereby incorporated by.
According to an aspect of the present invention, the solvability that in wash water solution, has unexpected improvement and the detergent composition of cleaning performance are provided.Specifically, detergent composition comprises at least 1% surfactant system, contains at least a anion surfactant that is selected from alkylbenzene sulfonate, alkyl ester sulfonate, alkyl-sulphate, alkyl ethoxy sulfate, secondary alkyl sulfate and its mixture in this system.Comprise also that at least about 0.1% oleoyl sarcosinate wherein the ratio of oleoyl sarcosinate and surfactant system is about 1: 20 to about 10: 1.The comprehensive cleaning performance and the solvability in cold washing solution of this detergent composition are unexpectedly improved.
In other embodiment of the present invention, this detergent composition also comprises at least about 1% (weight) detergency washing assistant, and wherein washing assistant is selected from yellow soda ash, zeolite and its mixture.And another embodiment comprises that the additive component that will be selected from SYNTHETIC OPTICAL WHITNER, bleach-activating agent, suds suppressor, enzyme stabilizers, polymeric dispersant, dye transfer inhibitor and dirt release agent adds in the detergent composition.
Different with spray-dried granules, detergent composition of the present invention can be the form of agglomerate, and for commercial purpose, is at least about 600g/l as the total body density of closely knit Betengent product.Other preferred embodiment directly relates to and comprise about 45% (weight) alkyl-sulphate of about 0.1%-and alkyl sulfonate surfactants mixture in composition; And/or comprise about 20% polyhydroxy fatty acid amide surfactant of about 0.1%-.
In another embodiment, detergent composition also contains the 0.1%-that has an appointment about 20% at least a nonionogenic tenside, it is selected from alkylethoxylate, alkyl phenolic alkoxy thing, alkyl polyglucoside, with its mixture, wherein the ratio of nonionogenic tenside and surfactant system is about 1: 1 to about 1: 30.
This detergent composition can be the form of laundry soap bar or liquid detergent composition.The present invention also provides the method for the fabric of contamination with wash, comprises the step that fabric is contacted with the water-bearing media of the detergent composition of the present invention that contains significant quantity.
Therefore, an object of the present invention is to provide the cleaning performance that especially in cold washing solution, has improvement and the deliquescent detergent composition of improvement.Another object of the present invention provides this class detergent composition, and it also can be the form of liquid and comprise the long chain alkyl sulfates tensio-active agent that is used to improve cleaning performance effectively.After embodiment preferred of describing in detail below reading and the appended claim, to those skilled in the art, these and other objects of the present invention, feature will be more obvious with relevant advantage.
Description of Preferred Embodiments
The present invention relates to preferably comprise at least 1%, more preferably from about 10%-is about 55%, the detergent composition of 15%-about 40% (weight) surfactant system most preferably from about, and wherein surfactant system contains at least a anion surfactant of the present invention.Also be included as detergent composition weight at least about 0.1%, preferably about 0.1%-is about 90%, more preferably from about 1%-is about 50%, most preferably from about the oleoyl sarcosinate of 3%-about 30%.
In addition, the ratio of oleoyl sarcosinate and surfactant system is preferably about 1: 20 to about 10: 1, and more preferably from about 1: 20 to about 5: 1, most preferably from about 1: 20 to about 2: 1.By this way, the comprehensive cleaning performance of the solvability of surfactant system and composition improves." solvability of improvement " that this detergent composition reached be with surfactant system in the solvability of the tensio-active agent that contains strengthen relevant.Preferably, this improvement represents that the solvability of anion surfactant in washing soln is than the solvability increase at least 5% of dissolving or be not contained in the similar face promoting agent in the detergent composition defined herein separately.More preferably have improved solubility and be about 10%-about 50%.Those technician will appreciate that in this area, and the deliquescent any contrast of anion surfactant all should be in identical wash conditions, and for example water temperature, hardness and pH value, stirring velocity and time, granularity get off to finish.
Those technician in this area also should understand the content that can use several different methods to measure the surfactant system in the washing soln.For example use so-called " CatSO
3" relegate a high offi and decide technology; after 1 minute, get the wash water solution sample that contains detergent composition; and filter with 0.45 μ m nylon filter paper; cationic titrant titration filtrate in the presence of anionic dyestuff, used afterwards; this titrating solution can be bought; for example buy from Sigma Chemical Company, commodity are called Hyamine.From the above mentioned, can measure the amount that is dissolved in the anion surfactant in the washing soln.
Randomly, the present invention also can add one or more nonionogenic tensides in detergent composition.With regard to it, it is about 20% that the amount of nonionogenic tenside is preferably about 0.1%-, and more preferably from about 0.2%-is about 10%, and most preferably from about 0.4%-about 4%.The ratio of nonionogenic tenside and anion surfactant is preferably about 3: 1 to about 1: 30 in composition of the present invention, and more preferably from about 1: 2.5 to about 1: 20, most preferably from about 1: 5 to about 1: 20.
Oleoyl sarcosinate
The present composition comprises oleoyl sarcosinate, can select the form of its acid and/or salt by the present composition and purposes requirement, and it has following structural formula:
Wherein M is hydrogen or cationic moiety.Preferred M is hydrogen and basic metal, especially sodium and potassium.Oleoyl sarcosinate can be bought, for example by W.R.Grace ﹠amp; Co. the Hamposyl O that provides.
Except the commercial oleoyl sarcosinate of buying; the useful oleoyl sarcosinate of the present invention also preferably from oleic acid ester (preferred methyl esters) and sarcosinate (particular certain cancers) under the anhydrous response condition, be equal to or greater than in a kind of alkalescence to react in the presence of the alkaline catalysts of alkoxide catalysis (particular methanol sodium) and prepare.For example should react available following illustration:
This salt can randomly be neutralized the oleoyl sarcosinate that forms sour form.
The preferred method of preparation oleoyl sarcosinate is at about 80 ℃ to about 200 ℃, and especially about 120 ℃ are extremely carried out under about 200 ℃ temperature.Preferred reaction is carried out under solvent-free, although can use boiling point to be at least 100 ℃ and to the alcoholic solvent (being that glycerine is unacceptable) of stable reaction conditions.Mol ratio at methyl esters reactant and sarcosinate reactant and basic catalyst is about 1: 1: under the 0.05-0.2, the productive rate that reaction can about 85% carries out.
The mixtures of methyl esters that is obtained by the natural oils (preferably having at least about 60%, more preferably at least about 75%, most preferably at least about 90% oleic acid content) of high oleic acid content is especially preferably as starting raw material.Example comprises high oleic Sunflower Receptacle and vegetable seed/canola oil.In addition, the high oleic methyl esters cut that obtains from palm-kernel oil or butter also is acceptable.This oils generally contains the impurity of a tittle, comprises some lipid acid impurity, and it can be converted to the sarcosinate compound by this synthetic method.For example, canola/ rapeseed oil commodity can comprise for example mixture of palmitinic acid, stearic acid, linolic acid, linolenic acid and/or eicosenoic acid of a large amount of oleic acid and lipid acid impurity, and some or all in them are converted to sarcosinate by this reaction method.If by the requirement of preparation purpose, be used in preparation can removing some or all these class impurity from stock oil before the oleoyl sarcosinate of the present composition.
At last, by in reaction mixture, adding maleic anhydride or diacetyl oxide, sarkosine remaining in reaction mixture can be converted to acid amides, thereby makes the content of sarkosine reduce to minimum, and makes any potential possibility that forms undesirable nitrogenous impurity reduce to minimum.
The synthetic of oleoyl sarcosinate can be undertaken with preparation oleoylsarcosine sodium by following.
Synthetic one 2 liters 3 neck round-bottomed flasks of the oleylamide of Sodium sarcosinate, it is equipped with thermometer, has the dean stark trap of condenser, mechanical stirrer and gas inlet connection, and nitrogen is taken over through reaction mixture top by this.In reactor, add sarkosine (43.3g, 0.476mol), 25% in methyl alcohol sodium methylate (97.7g, 0.452mol) and methyl alcohol (400ml); To react and reflux 15 minutes, add common high oleyl sunflower oil (148.25g, the methyl esters that 0.5mol) obtains then by Cargill with the neutralizer propylhomoserin.After removing methyl alcohol with dean stark trap, with reaction mixture be heated to 170 ℃ through 1 hour to remove all water.(15.4g 0.0714mol) makes the reaction beginning to the sodium methylate of adding 25% in methyl alcohol.Be reflected at 170 ℃ and kept 2.5 hours down, during this period, methyl alcohol is collected in the dean stark trap.To react cooling a little, add methyl alcohol (200g) then.(9.43g 0.095mol) adds in the methanol solution, and this is reflected at 60 ℃ and stirred 0.5 hour down, through rotary evaporation most of methyl alcohol is removed then, adds acetone (2L) with precipitated product with maleic anhydride.Filter the collection product and obtain pale solid through suction through dry air.Analyze this reaction mixture with GC and show that most of products are oleoyl sarcosinates, a small amount of following impurity is arranged: sarkosine, oleic acid and the sarcosinate that produces by palmitinic acid, stearic acid and linolic acid.
Surfactant system
The limiting examples that is used for the preferred anionic surfactants tensio-active agent of surfactant system comprises conventional C
11-C
18Alkylbenzene sulfonate (" LAS "), primary, side chain and random C
10-C
20Alkyl-sulphate (" AS "), C
10-C
18Secondary (2,3) alkyl-sulphate, its chemical formula is CH
3(CH
2)
x(CHOSO
3 -M
+) CH
3And CH
3(CH
2)
y(CHOSO
3 -M
+) CH
2CH
3, wherein x and (y+1) be to be at least about 7 integer preferably is at least about 9 integer, and M is water solubilising positively charged ion, especially a sodium, undersaturated alkyl-sulphate such as oleyl vitriol, C
10-C
18Alkyl alkoxy sulfate (" AE
xS ", the about 7EO ethoxy sulfate of x as many as especially).
Optional other tensio-active agent example that is used for the present composition comprises C
10-C
18Alkyl alkoxy carboxylate salt (especially EO 1-5 ethoxy carboxylate), C
10-C
18Glyceryl ether, C
10-C
18Alkyl polyglycoside and the many glycosides of they corresponding sulfations, and C
12-C
18α-sulfonated fatty acid ester.If desired, also can comprise conventional nonionic and amphoterics in all compositions of the present invention, as C
12-C
18Alkylethoxylate (" AE "), it comprises the alkylethoxylate and the C at so-called narrow peak
6-C
12Alkyl phenolic alkoxy thing (especially ethoxylate and blended oxyethyl group/propoxy-), C
12-C
18Trimethyl-glycine and sultaine (" sultains "), C
10-C
18Amine oxide etc.Also can use C
10-C
18N-alkyl polyhydroxy fatty acid amide.Typical example comprises C
12-C
18The N-methyl glucose amide.Referring to WO 9,206,154.Other sugared deutero-tensio-active agent comprises N-alkoxyl group polyhydroxy fatty acid amide, for example C
10-C
18N-(3-methoxycarbonyl propyl) glucamide.The N-propyl group is to N-hexyl C
12-C
18Glucamide can be used for low foaming.Also can use C
10-C
20Conventional soap.High if desired foaming can be used side chain C
10-C
16Soap.The mixture of negatively charged ion and nonionogenic tenside is useful especially.Other conventional useful tensio-active agent standard of listing in is taught in the book.
Additive component
The present composition can randomly comprise one or more other detergent additives materials or other help or strengthen the cleaning performance of detergent composition, to the handling property of the basic thing that is cleaned or improve the material (for example pigment, dyestuff etc.) of aesthetic effect.It below is the illustrative example of these additive materials.Decontamination lotion promoter
Detergent builders can randomly be included in the composition of the present invention to help to control inorganic mineral hardness.Can use inorganic and organic washing-assisting detergent.Washing assistant generally is used for fabric cleaning composition to help to remove particulate fouling.
The content of washing assistant can change in wide region according to end-use and its required physical form of composition.When using washing assistant, generally contain washing assistant in the composition at least about 1%, granular preparation generally comprises about 10% to about 80%, more typically comprises about 15% detergent builders to about 50% (weight).But this does not also mean that the washing assistant content that eliminating is lower or higher.
Inorganic or phosphorus-containing detergent washing assistant comprises, but be not limited to basic metal, ammonium, the alkanol ammonium salts of poly-phosphate (for example tri-polyphosphate, pyrophosphate salt and glassy polymeric metaphosphate), phosphoric acid salt, phytinic acid, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and silico-aluminate.Yet, need nonphosphate builders in some place.Importantly, the present composition in addition have so-called " weak " washing assistant (with phosphate ratio) have unexpected effect under as Citrate trianion or so-called " owing composite (underbuilt) " situation of being produced with zeolite or layered silicate washing assistant.
The example of silicate-like builder is alkalimetal silicate, particularly SiO
2With Na
2The silicate of the ratio of O in 1.0: 1 to 3.2: 1 scopes, and layered silicate are as the lamina sodium silicate of describing in the United States Patent (USP) 4664839 that licenses to H.P.Rieck on May 12nd, 1987.NaSKS-6 is the trade mark (being abbreviated as " SKS-6 " in this article usually) by the crystalline layered silicate of Hoechst sale.Do not resemble zeolite builders, the NaSKS-6 silicate-like builder does not contain aluminium.NaSKS-6 has δ-Na
2SiO
5The layered silicate of morphology configuration.It can be by the method preparation as describing in DE-A-3417649 and DE-A-3742043.SKS-6 is a layered silicate very preferably used herein, but can use other layered silicate, as has general formula NaMSi
xO
2x+1YH
2O, wherein M is sodium or hydrogen, and x is 1.9 to 4 numerical value, is preferably 2, and y is 0 to 20 numerical value, is preferably 0 layered silicate.Various other layered silicates of buying from Hoechst comprise NaSKS-5, NaSKS-7 and NaSKS-11, are α, β and γ form.As indicated above, δ-Na
2SiO
5(NaSKS-6 form) most preferably used herein.Other silicate also is useful, Magnesium Silicate q-agent for example, and it can be used as in the granular preparation crisp dose, the stablizer of oxygen bleaching agent and the component of control foam system.
The example of carbonate builders is alkaline-earth metal and the alkaline carbonate on November 15th, 1973 disclosed German patent application 2321001.
The silico-aluminate washing assistant is useful in the present invention.The silico-aluminate washing assistant is extremely important in most popular commercially available heavy dirty granular detergent composition, and also is washing assistant composition important in the liquid detergent preparation.The silico-aluminate washing assistant comprises the washing assistant with following empirical formula:
M
Z/n[(AlO
2)
z(SiO
2)
y] xH
2O wherein z and y is at least 6 integer, and the mol ratio of z and y is 1.0 to 0, and x is 0 to about 264 integer, and M is the element of IA or IIA family, for example has Na, K, Mg, the Ca of n valence state.
Useful aluminosilicate ion exchange material is commercial the purchase.These silico-aluminates can be crystallization or amorphous structure, and can naturally occurring silico-aluminate or synthetic obtaining.A kind of method for preparing aluminosilicate ion exchange material is disclosed in the people's such as Krummel that authorized on October 12nd, 1976 the United States Patent (USP) 3985669.Being used for preferred synthetic crystallization aluminosilicate ion exchange material of the present invention is to buy for zeolite A, zeolite P (B), zeolite MAP and X zeolite by name.In an especially preferred embodiment, the crystal aluminosilicate ion-exchange material has following formula:
Na
12[(AlO
2)
12(SiO
2)
12] xH
2O wherein x is about 20 to about 30, especially is about 27.This material is called zeolite A.The present invention also can use dehydration zeolite (x=0-10).Preferred silico-aluminate has the granularity of diameter for about 0.1-10 micron.
The organic detergent washing assistant that is fit to purposes of the present invention includes, but are not limited to various polycarboxylic acid salt compounds." polycarboxylate " used herein is meant to have a plurality of carboxylate groups, the compound of preferred at least 3 carboxylate groups.The polycarboxylate washing assistant can add in the composition with sour form usually, but also can add with the form of neutralized salt.When using with the form of salt, basic metal, as sodium, potassium and lithium or alkanol ammonium salts are preferred.
In the polycarboxylate washing assistant, comprise polytype useful matter.An important class polycarboxylate washing assistant comprises the ether polycarboxylate, comprise the oxidation disuccinate, disclosed in the United States Patent (USP) 3635830 as the United States Patent (USP) 3128287 of the Berg that authorizes on April 7th, 1964 and the people such as Lamberti that authorized on January 18th, 1972.Also license to " TMS/TDS " washing assistant in people's such as Bush the United States Patent (USP) 4663071 referring on May 5th, 1987.The ether polycarboxylate who is fit to also comprises ring compound, particularly alicyclic compound, as at United States Patent (USP) 3923679; 3835163; 4158635; Describe in 4120874 and 4102903.
Other useful detergency washing assistants comprise the multipolymer, 1,3 of ether hydroxy-polycarboxylate, maleic anhydride and ethene or vinyl methyl ether, 5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyl oxosuccinic acid, various poly-acetate are as the basic metal of ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA), ammonium and substituted ammonium salt, and polycarboxylate such as mellitic acid, succsinic acid, oxidation disuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxy methoxy-succinic acid and its water-soluble salt.
The Citrate trianion washing assistant, for example citric acid and its water-soluble salt (particularly sodium salt) are the polycarboxylate washing assistants of particularly important in the heavy duty liquid laundry detergent preparation, reason is that they can be obtained and their biodegradability by renewable resource.Citrate trianion also can be used for particulate composition, especially can be used in combination with zeolite and/or layered silicate washing assistant.The oxidation disuccinate also is useful especially in these compositions and mixture.
Disclosed 3 in the United States Patent (USP) 4566984 that also has the Bush that authorizes on January 28th, 1986 that is adapted at using in the detergent composition of the present invention, 3-dicarboxyl-4-oxa--1, the compound that the 6-adipate is relevant with it.Useful succsinic acid washing assistant comprises C
5-C
20Alkyl and alkenyl succinic and its salt.Particularly preferred compound is the dodecenyl succinic succsinic acid in this type.The specific examples of succinate washing assistant comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates etc.The lauryl succinate is a preferred washing assistant in this group, and is described in the disclosed european patent application 86200690.5/0200263 on November 5th, 1986.
Other polycarboxylates that are fit to be disclosed in the people's such as Crutchfield that authorized on March 13rd, 1979 United States Patent (USP) 4144226 and the United States Patent (USP) 3308067 of the Diehl that authorized on March 7th, 1967 in.Also can be referring to the United States Patent (USP) 3723322 of Diehl.
Lipid acid, for example C
12-C
18Monocarboxylic acid as oleic acid and/or its salt, also can mix in the composition separately, or mixes composition so that additional washing assistant activity to be provided with aforesaid washing assistant, especially Citrate trianion and/or the combination of succinate washing assistant.So use lipid acid generally can cause reducing whipability, this prescription teacher should consider.
In the situation that can use phosphorus base washing assistant, especially, can use various alkali metal phosphates, as everyone knows tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate at the block preparation that is used for hand-washing operation.Phosphate builders such as ethane-1-hydroxyl-1,1-diphosphate and other known phosphate (referring to, US3159581 for example; 3213030; 3422021; 3400148 and 3422137) also can use.
Enzyme-for the purpose of multiple laundering of textile fabrics, comprise remove protein-based, spot carbohydrate-based or the triglyceride level base, and, in detergent formulations of the present invention, can comprise enzyme for the dye migration that suppresses to come off with for the recovery of fabric.The enzyme that can mix comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase, with and composition thereof.The enzyme that also can comprise other type, they can be from any suitable source, as plant, animal, bacterium, mould and yeast source.Yet their selection determines by Several Factors, as pH-activity and/or optimal stability point, thermostability, to stability of activated detergent and washing assistant etc., aspect this, bacterium or fungous enzyme are preferred, as bacterial amylase and proteolytic enzyme, and the mould cellulase.
Enzyme is impregnated in enough amounts usually so that as many as about 5 milligrams (weight) in every gram composition to be provided, be generally about 0.001 to about 3 milligrams organized enzyme, explanation is in addition, and the composition among the present invention generally comprises about 0.001% to about 5%, preferred 0.01% to 2% (weight) commercial enzyme preparation.The proteolytic enzyme amount in this commercial formulation usually is enough to guarantee that every gram composition has 0.005 to 0.1 Anson unit (AU) activity.
Suitable examples of proteases is a subtilisin, it is that special bacterial strain by Bacillus subtillis and bacillus licheniformis obtains, another kind of suitable proteolytic enzyme is obtained by bacterial strain of bacillus, it has maximum activity in pH 8-12 scope, by Novo Industries A/S exploitation and sale, the trade name of registration is ESPERASE.The preparation of this kind of enzyme and similar enzyme is described in the british patent specification 1243784 of Novo.The commercial commercially available suitable proteolytic ferment of removing protein-based spot comprises to be sold by Novo Industries A/S (Denmark), commodity ALCALASE by name and SAVINASE, with by International Bio-Synthetics, the MAXATASE that Inc. (Holland) sells.Other proteolytic enzyme comprises that protease A is (referring to european patent application 130756,1985.01.09 open) and proteolytic enzyme B (referring to european patent application No87303761.8,1987.04.28 people's such as application and Bott the disclosed european patent application 130756 of 1985.01.09); With according to one or more following patents by Genencor International, the proteolytic enzyme of Inc. preparation: people's such as Caldwell United States Patent (USP) 5,185,285,5,204,015 and 5,244,791.Alleged " the proteolytic enzyme C " of this paper most preferably, it is by genus bacillus, the mutation of the alkaline serine protease that particularly slow genus bacillus obtains, wherein arginine replaces the Methionin of 27 positions, tyrosine replaces the Xie Ansuan of 104 positions, the Threonine that l-asparagine that the Serine replacement is 123 and L-Ala replace 274 positions.Proteolytic enzyme C is described in EP 90915958:4; U.S.5 is in 185,250 and U.S.5,204,015.The preferred U.S. Patent Application Serial 08/136 that is described in pending trial in addition, 797, exercise question is the U.S. Patent Application Serial 08/136 of " cleaning combination (Protease-Containing CleaningCompositions) that contains proteolytic enzyme " and pending trial, 626, exercise question is the proteolytic enzyme in " bleaching composition (Bleaching Compositions Comprising ProteaseEnzymes) that comprises proteolytic enzyme ", and this two document is quoted as a reference at this paper.The present invention also comprises genetically altered mutation, particularly proteolytic enzyme C.
Amylase comprises α-Dian Fenmei, the International Bio-Synthetics that for example describes in british patent specification 1296839 (Novo), the TERMAMYL that RAPIDASE that Inc. sells and NovoIndustries sell.
The cellulase that can be used among the present invention comprises bacterium and mould cellulase.Preferably they have best pH scope 5-9.5.Suitable cellulase is disclosed in the United States Patent (USP) 4435307 of authorizing in 6 days March in 1984 of people such as Barbesgoard, it discloses the cellulase that extracts by in Humicola insolens and rotten cellulase 212 of planting mould cellulase that trichoderma strain DSM 1800 produces or being produced by the mould that belongs to Aeromonas and the hepatopancreas by extra large mollush (Dolabella AuriculaSolander).Suitable cellulase also is disclosed in GB-A-2075028; Among GB-A-2095275 and the DE-OS-2247832.CAREZYME (Novo) is useful especially.
The lipase that is applicable to the washing composition purposes comprises by the microorganism in the Rhodopseudomonas family, as is disclosed in those lipase that Situ Ci Shi (stutzeri) aeruginosa atcc 19.154 in the English Patent 1372034 produces.Also referring to the lipase in the Japanese patent application 53-20487 of open special permission on February 24th, 1978.This lipase can be by Amano Pharmaceutical Co.Ltd., Nagoya, and Japan has bought, and commodity are called lipase P " Amano ", hereinafter are referred to as " Amano-P ".Other commercial lipase comprises Amano-CES, from the lipase of Chromobacter viscosum, for example, pigment bacillus viscosum var.lipolyticum NRRLB 3673, commercial can be by Toyo Jozo Co., Tagata, Japan has bought; With also have by U.S.Biochemical Corp., (USA) and the pigment bacillus viscosum lipase bought of Disoynth Co. (Holland) and from the lipase of gladiolus pseudomonas (Pseudomonas gladioli).Plant that Pseudomonas fetal hair bacterium (Humicolalanuginosa) obtains and be the preferred fat enzyme that is used for herein by corruption at the commercial LIPOLASE enzyme that can buy by Novo (equally referring to EPO 341947).
Peroxidase is and oxygen source that for example percarbonate, perborate, persulphate, hydrogen peroxide etc. are used in combination.They are used for " solution bleaching ", promptly are suppressed on the dyestuff that comes off from basic thing in the washing process or pigment migration other basic thing to the washing soln.Peroxidase is being known in the art, comprises for example horseradish peroxidase, lignoenzyme and halo peroxidase, as chloro and bromoperoxidase.The detergent composition that contains peroxidase is disclosed in, and for example in the PCT International Application No. WO 89/099813, on October 19th, 1989 is open, transfers Novo Industries A/S by O.Kirk.Wish to be considered to the material of peroxidase promotor, for example phenolsulfonate and/or thiodiphenylamine are used in combination with these peroxidase.
Various enzyme materials and the method that they are mixed in the synthetic detergent composition also are disclosed in the United States Patent (USP) 3553139 that licensed to people such as McCarty on January 5th, 1971.Some enzymes also be disclosed in the people's such as Place that authorized on July 18th, 1978 United States Patent (USP) 4101457 and the people's such as Hughes that authorized on March 26th, 1985 United States Patent (USP) 4507219 in.The method that is used for the enzyme material of liquid detergent preparation and they are incorporated in these preparations is disclosed in the people's such as Hora that authorized on April 14th, 1981 the United States Patent (USP) 4261868.The enzyme that is used for washing composition can make its stabilization with various technology.The enzyme stabilization technology open and illustrate the United States Patent (USP) 3600319 that licenses to people such as Gedge on August 17th, 1971 and October in 1986 disclosed Venegas on the 29th European patent application publication No. 0199405, application number 86200586.5.The enzyme stabilization system for example also is described in the United States Patent (USP) 3519570.
Enzyme stabilizers-enzyme used herein can be by water-soluble calcium in the composition finished product and/or magnesium ion thing source, and it provides this ion to enzyme, is stabilized under existing.(calcium ion is generally more effective than magnesium ion, and if only use one type of positively charged ion, calcium ion is that the present invention is preferred).Stability in addition can referring to the U.S.4537706 of Severson, exist down to obtain by at various other prior art disclosed stablizer, especially borate families.General washing composition, especially liquid washing agent comprise by every liter of composition finished product about 1 to about 30, preferred about 2 to about 20, and more preferably from about 5 to about 15, most preferably from about 8 calcium ions to about 12 mmoles.Reaction to calcium or magnesium ion can slightly change this content according to the amount of the enzyme that exists and enzyme.Should select the amount of calcium or magnesium ion like this, make its with composition in complexing such as washing assistant, lipid acid after, for enzyme, always have available minimum.Any water-soluble calcium or magnesium salts all can be used as calcium or magnesium ion thing source, and it comprises, but non-limiting in, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formiate and lime acetate and corresponding magnesium salts.Because enzyme slurries and prescription contain calcium ion in the water, make this small amount of calcium ion, general about 0.05 to about 0.4 mmole/every liter, also often is present in the composition.For solid detergent composition, preparation can comprise that the water-soluble calcium ion thing source of q.s is to be provided at required amount in the laundry aqueous solution.On the other hand, natural water hardness may be enough.
The amount that it should be understood that above-mentioned calcium and/or magnesium ion is enough to guarantee enzyme stability.More calcium and/or magnesium ion can be added in the composition to provide realization to remove greasy supplementary means.Therefore, general recommendations composition of the present invention generally comprises about 0.05% to about 2% (weight) water-soluble calcium or magnesium ion thing source, or the two.Certainly, this amount can change with the amount and the type of employed enzyme in the composition.
The present composition also can be randomly, but preferably contain various other stablizers, especially borate family stablizer.Usually, the consumption of this stablizer in composition is calculated as about 0.25% to about 10% by the boric acid in the composition or other borate compound (calculating based on boric acid) that can form boric acid, preferred about 0.5% to about 5%, and more preferably from about 0.75% to about 3% (weight).Though other compound is to suit as boron oxide, borax and other alkali metal borate (for example ortho-boric acid sodium, sodium metaborate and sodium pyroborate and pentaborate), preferred boric acid.The boric acid that replaces (for example phenyl-boron dihydroxide, butane boric acid and to bromophenyl boric acid) also can replace boric acid to use.It should be understood that this class material also can be used for preparation as stablizer separately, and can be used in combination with the calcium and/or the magnesium ion that add.
At last, wish chlorine scavenger is added the influence that is not subjected to generally to be present in the chlorine in the Urban water supply in the composition that especially contains proteolytic enzyme with protective enzyme.This class material is described in people's such as Pancheri for example the United States Patent (USP) 4,810,413.Bleaching compounds---SYNTHETIC OPTICAL WHITNER and bleach-activating agent
Detergent composition of the present invention can randomly contain SYNTHETIC OPTICAL WHITNER or contain SYNTHETIC OPTICAL WHITNER and the bleaching composition of one or more bleach-activating agents.When containing SYNTHETIC OPTICAL WHITNER, in particular for the detergent composition of laundering of textile fabrics, its content be generally detergent composition about 1% to about 30%, more preferably from about 5% to about 20%.If contain bleach-activating agent, its content is generally about 0.1% to about 60%, more preferably about 0.5% to about 40% of the bleaching composition that contains SYNTHETIC OPTICAL WHITNER and bleach-activating agent.
SYNTHETIC OPTICAL WHITNER used herein can be that detergent composition is cleaned at fabric, or useful any SYNTHETIC OPTICAL WHITNER in other the present known cleaning use that maybe will know.These comprise oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.Can use perborate bleach herein, for example Sodium peroxoborate (for example monohydrate or tetrahydrate).
Operable without restriction another kind of SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The example that is fit to of this class SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium, 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid magnesium and diperoxy dodecanedioic acid magnesium.These SYNTHETIC OPTICAL WHITNER are disclosed in the United States Patent (USP) 4483781 of the Hartman that authorized on November 20th, 1984, in the people's such as Chung that U.S. Patent application 20, people's such as disclosed Banks in 740446,1985 on February of the people such as Burns of application on June 3rd, 1985 european patent application 0133354 and November 1 nineteen eighty-three authorize the United States Patent (USP) 4412934.SYNTHETIC OPTICAL WHITNER very preferably also comprises 6-amino in the ninth of the ten Heavenly Stems-6-oxo-mistake oxy hexanoic acid of describing as in the United States Patent (USP) 4634551 that licenses to people such as Burns on January 6th, 1987.
Also can use peroxygen bleach.The peroxy bleaching compound that is fit to comprises " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate and the sodium peroxide of yellow soda ash peroxyhydrate and equivalent.Also can use persulphate SYNTHETIC OPTICAL WHITNER (for example, OXONE is by the DuPont industrial production).
Preferred percarbonate bleach comprise mean particle size be about 500 microns to about 1000 microns dried particles, less than no more than about 10% (weight) of about 200 microns described particle, greater than no more than about 10% (weight) of about 1,250 micron described particle.Percarbonate can randomly be coated by silicate, borate or water soluble surfactant active.Percarbonate can be obtained by various commercial things source, for example FMC, Solvay and Tokai Denka.
Also can use the mixture of SYNTHETIC OPTICAL WHITNER.
Peroxygen bleach, perborate, percarbonate etc. preferably are used in combination with bleach-activating agent, and this causes producing on the spot the peroxy acid corresponding to bleach-activating agent in the aqueous solution (promptly at washing process).The various non-limiting examples of activator are disclosed in the United States Patent (USP) 4915854 and United States Patent (USP) 4412934 that licenses to people such as Mao April 10 nineteen ninety.Nonanoly acyloxy benzene sulfonate (NOBS) and tetra acetyl ethylene diamine (TAED) activator are used always, also can use its mixture.Typical SYNTHETIC OPTICAL WHITNER of useful herein other and activator are in addition referring to United States Patent (USP) 4634551.
Acid amides deutero-bleach-activating agent very preferably is to have those of following formula:
R
1N (R
5) C (O) R
2C (O) L or R
1C (O) N (R
5) R
2R in C (O) the L formula
1Be to contain 6 the alkyl of having an appointment, R to about 12 carbon atoms
2Be to contain 1 alkylidene group, R to about 6 carbon atoms
5Be H or contain have an appointment 1 alkyl, aryl or alkaryl that L is the leavings group of any suitable to about 10 carbon atoms.Leavings group is by crossing hydrolysis negatively charged ion nucleophilic attack bleach-activating agent, result's substituted any group from the bleach-activating agent, and preferred leavings group is a phenylbenzimidazole sulfonic acid salt.
The example of preferred bleach-activating agent comprises (6-decoyl amino-caproyl) oxygen benzene sulfonate, (the amino caproyl of 6-nonanoyl) oxygen benzene sulfonate, (6-caprinoyl amino-caproyl) oxygen benzene sulfonate and its mixture in the following formula; they are described in U.S.4; 634; in 551, the document is quoted as a reference at this paper.
Another kind of bleach-activating agent comprises the U.S.4 that is authorized in October 30 nineteen ninety by people such as Hodge, disclosed benzoxazine type activator in 966,723, and the document is quoted as a reference at this paper.Benzoxazine type activator very preferably is:
Also have another kind of preferred bleach-activating agent to comprise the acyl lactam activator, especially have the acyl caprolactam and the acyl group Valerolactim of following molecular formula:
R in the formula
6For H or contain 1 alkyl, aryl, alkoxy aromatic yl or alkaryl to about 12 carbon atoms.Lactan activator very preferably comprises benzoyl caprolactam, capryloyl hexanolactam, 3; 5; 5-trimethyl acetyl base hexanolactam, nonanoyl hexanolactam, decanoyl hexanolactam, undecylene acyl caprolactam, benzoyl Valerolactim, capryloyl Valerolactim, decanoyl Valerolactim, undecylene acyl group Valerolactim, nonanoyl Valerolactim, 3; 5,5-trimethyl acetyl base Valerolactim and its mixture.Also license to the United States Patent (USP) 4,545,784 of Sanderson referring on October 8th, 1985, it discloses acyl caprolactam, comprises benzoyl caprolactam, and it is adsorbed in the Sodium peroxoborate.
Those SYNTHETIC OPTICAL WHITNER except oxygen bleaching agent also are well known in the art, and can be with in the present invention.The non-oxygen bleaching agent that one class is good especially comprises photoactivation SYNTHETIC OPTICAL WHITNER such as sulfonated Phthalocyanine Zinc and/or aluminium.License to people's such as Holcombe United States Patent (USP) 4033718 referring on July 5th, 1977.If you are using, detergent composition generally contains this SYNTHETIC OPTICAL WHITNER of about 1.25% (weight) of the 0.025%-that has an appointment, especially sulfonated Phthalocyanine Zinc.
If necessary, bleaching compounds can be used manganic compound catalysis.These compounds are as known in the art, comprise for example being disclosed in U.S.5,246,621; U.S.5,244,594; U.S.5,194,416; U.S.5,114,606; With European patent application publication No. 549,271A1,549,272A1,544,440A2 and 544, the manganese-based catalyst among the 490A1.Preferred example comprises Mn in these catalyzer
IV 2(u-O)
3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2(PF
6)
2, Mn
III 2(u-O)
1(u-OAc)
2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2(ClO
4)
2, Mn
IV 4(u-O)
6(1,4, the 7-7-triazacyclononane)
4(ClO
4)
4, Mn
IIIMn
IV 4(u-O)
1(u-OAc)
2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2(ClO
4)
3, Mn
IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH
3)
3(PF
6) and its mixture.The bleaching catalyst of other metal matrix comprises and is disclosed in U.S.4, those in 430,243 and U.S.5,114,611, and manganese also is reported in the following United States Patent (USP) with the application that cooperates ligand of various enhancing bleaching effects: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; With 5,227,084.
In fact, unrestricted, can adjust the compositions and methods of the invention so that approximately 1/10,000,000 active bleaching agent catalyst substance to be provided in aqueous cleaning solution, preferably provide about 0.1ppm to about 700ppm in washing liquid, more preferably from about 1ppm is to the catalyst substance of about 500ppm.The polymerization dirt release agent
Well known to a person skilled in the art that any polymerization dirt release agent can randomly be used for the compositions and methods of the invention.The polymerization dirt release agent is characterised in that it contains hydrophilic segment and hydrophobic part simultaneously, and wherein hydrophilic segment makes hydrophobic fiber, as the surface hydrophilic of polyester and nylon; Hydrophobic part be deposited on the surface of hydrophobic fiber and in whole washing, rinse cycle all the time attached to fiber surface on, therefore hydrophilic segment is played fixed action.This feasible spot easier cleaning in washing process thereafter that after dirt release agent is handled, produces.
The polymerization dirt release agent that the present invention uses especially comprises the polymerization dirt release agent with following composition: (a) basically by (i) or (ii) or one or more nonionic hydrophilic components of (iii) forming, wherein (i) is that the polymerization degree is at least 2 polyoxyethylene part, it (ii) is the polyoxypropylene part that the propylene oxide or the polymerization degree are at least 2-10, wherein said hydrophilic segment does not comprise any propylene oxide unit, unless this unit is attached at the two ends of adjacent part by ehter bond, the mixture that (iii) contains the oxyalkylene units of about 30 propylene oxide units of ethylene oxide and 1-, wherein said mixture contains the ethylene oxide unit of q.s, thereby the wetting ability that makes hydrophilic component is even as big as increasing the wetting ability on normal polyester synthon surface, dirt release agent is promptly attached on this surface, described hydrophilic segment preferably contains the ethylene oxide unit at least about 25%, contains 20-30 the propylene oxide unit and be particularly preferred at least about the component of 50% ethylene oxide unit of having an appointment; Or (b) by (i), (ii), (iii) or (iv) one or more hydrophobic components of forming, wherein (i) is C
3Oxyalkylene terephthalic acid ester moiety, if wherein described hydrophobic components also comprises the ethylene oxide terephthalate, then ethylene oxide terephthalate and C
3The ratio of oxyalkylene terephthalate units is about 2: 1 or is lower, (ii) is C
4-C
6Or oxidation C
4-C
6Alkylene moiety, or their mixture (iii) are poly-(vinyl ester) parts, and preferred degree of polymerization is at least 2 poly-(vinyl-acetic ester), (iv) is C
1-4Alkyl oxide or C
4Hydroxyalkyl ether substituting group, or their mixture, substituting group wherein is with C
1-4Alkyl oxide or C
4Hydroxyalkyl ether derivatived cellulose or its form of mixtures exist, and this derivatived cellulose is an amphipathic, therefore make them have the C of q.s
1-4Alkyl oxide and/or C
4The hydroxyalkyl ether unit to be being deposited on the conventional polyethylene terephthalate surface and keeping the hydroxyl of q.s, in case be adsorbed on these conventional synthon when surperficial when it, wetting ability that can the increased fiber surface; Or combination (a) and (b).
Generally speaking, be about 200 in the polymerization degree of (a) polyoxyethylene part in (i), although also can use the higher polymerization degree, preferred 3-is about 150, more preferably 6-about 100.The oxidation C that is fit to
4-6The alkylidene group hydrophobic part includes, but are not limited to, as MO
3S (CH
2) nOCH
2CH
2The polymerization dirt release agent end-blocking part of O-, M is a sodium in the formula, n is the integer of 4-6, license to as on January 26th, 1988 in the United States Patent (USP) 4721580 of Gosselink disclosed those.
The polymerization dirt release agent that uses among the present invention also comprises derivatived cellulose, for example copolymerization block thing of hydroxy ethers cellulose polymer compound, glycol terephthalate or propylene glycol terephthalate and polyoxyethylene terephthalate or polyoxypropylene terephthalate etc.These reagent all have commercially available, comprising the Mierocrystalline cellulose hydroxy ethers as METHOCEL (Dow).The Mierocrystalline cellulose dirt release agent that the present invention uses also comprises and is selected from C
1-4Alkyl and C
4Those of hydroxy alkyl cellulose; License to people's such as Nicol United States Patent (USP) 4000093 referring on December 28th, 1976.
The dirt release agent that is characterised in that poly-(vinyl ester) hydrophobic part comprises that poly-(vinyl ester) is as C
1-6The graft copolymer of vinyl ester preferably grafts on poly-(vinyl-acetic ester) on polyalkylene oxide skeleton such as the polyoxyethylene skeleton.European patent application 0219048 referring to people such as disclosed Kud on the 22nd April in 1987.This commercially available class dirt release agent comprises SOKALAN type material, and for example SOKALAN HP-22 is produced by BASF (West Germany).
The preferred dirt release agent of one class is the multipolymer with glycol terephthalate and the random block of polyoxyethylene (PEO) terephthalate.The molecular weight of this polymerization dirt release agent is about 25000-about 55000.Referring to the United States Patent (USP) 3959230 that licensed to Hays on May 25th, 1976 with licensed to the United States Patent (USP) 3893929 of Basadur on July 8th, 1975.
Another kind of preferred polymerization dirt release agent is the polyester that has the glycol terephthalate repeating unit, wherein contain the glycol terephthalate unit of 10%-15% (weight) and the polyoxyethylene terephthalate unit of 90%-80% (weight), it is that the polyoxyethylene glycol of 300-5000 obtains from molecular-weight average.The example of this polymkeric substance comprises commercially available ZELCON 5126 (Dupont production) and MILEASET (ICI production).Also license to the United States Patent (USP) 4702857 of Gosselink referring on October 27th, 1987.
Also having a kind of preferred polymerization dirt release agent is the sulfonated products that is essentially the linear ester oligopolymer, and this oligopolymer is by terephthaloyl and the multiple unit of oxyalkylene oxygen basic weight oligomer ester skeleton, and the terminal portions that links to each other with this skeleton covalency is formed.License to November 6 nineteen ninety in the United States Patent (USP) 4968451 of J.J.Scheibel and E.P.Gosselink these dirt release agents are had complete description.Other polymerization dirt release agent that is suitable for comprises the terephthalate polyester in the United States Patent (USP) 4711730 that licensed to people such as Gosselink on December 8th, 1987, licenses to the end capped oligomer ester of negatively charged ion in the United States Patent (USP) 4721580 of Gosselink on January 26th, 1988 and licenses to block polyester oligopolymer in the United States Patent (USP) 4702857 of Gosselink on October 27th, 1987.
Preferred polymerization dirt release agent also comprises the dirt release agent in the United States Patent (USP) 4877896 that licensed to people such as Maldonado on October 31st, 1989, this patent disclosure negatively charged ion, the particularly end capped terephthalate of sulfo group aroyl.Preferred in addition dirt release agent is the oligopolymer with following repeating unit: terephthaloyl unit, sulfo group isophthaloyl unit, ethylene oxide oxygen and oxidation-1,2-propylene units.These repeating units have constituted the skeleton and the preferred isethionate end-blocking with modification of oligopolymer.Particularly preferred this type of dirt release agent comprises an about sulfo group isophthaloyl unit, 5 terephthaloyl unit, ratio is about 1.7 to about 1.8 ethylene oxide oxygen and oxidation-1, the end-blocking unit of 2-propylene oxygen unit and two 2-(2-hydroxy ethoxy) ethane sulfonic acid sodium.Described dirt release agent also comprises the minimizing crystalline stablizer by the about 0.5%-of oligopolymer weight about 20%, and this stablizer is preferably selected from xylenesulfonate, cumene sulfonate, tosylate and its mixture.
If the use dirt release agent, then to be generally about 0.01%-of detergent composition weight of the present invention about 10.0% for its consumption, and it is about 5% to be generally about 0.1%-, preferably about 0.2%-about 3.0%.Sequestrant
Detergent composition of the present invention can also randomly contain one or more iron and/or manganese sequestrant.This class sequestrant can be selected from fragrant chelating agent of aminocarboxylate, amino phosphonates do, multifunctional replacement and composition thereof, and all sequestrants are as definition hereinafter.Do not accept the restriction of opinion, it is believed that the advantage of these materials is that partly they have by forming the soluble chelating agent removes de-iron and manganese from washing soln superperformance.
The aminocarboxylate that can be used as optional sequestrant comprises edetate, N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, their an alkali metal salt, ammonium salt and substituted ammonium salt and their mixture.
When allowing at least to have low total phosphorous in detergent composition of the present invention, amino phosphonates do also is suitable as the sequestrant in the present composition, comprising: ethylenediamine tetraacetic (methylene phosphonic acid salt) is DEQUEST.These amino phosphonates do preferably do not contain alkyl or the alkenyl that surpasses about six carbon atom.
In the present composition, can also use the aromatic chelating agent of multifunctional replacement.Referring to licensing to people's United States Patent (USP)s 3812044 such as Connor on May 21st, 1974.The compound of preferred this class acid form is the dihydroxyl disulfobenzene, for example: 1,2-dihydroxyl-3,5-disulfobenzene.
The preferred in the present invention biodegradable cheating agent of using is ethylenediamine disuccinate (" EDDS "), [S, S] isomer especially, and it is described in the United States Patent (USP) 4704233 that on November 3rd, 1987 licensed to Hartman and Perkins.
If the use sequestrant, then its consumption is about 0.1%-about 10% of detergent composition weight of the present invention.Preferred amount of chelant is about 0.1%-about 3.0% of said composition weight.Remove clay soil/anti redeposition agent
Composition of the present invention can also randomly contain the water-soluble ethoxylated amine with removal clay soil and antiredeposition performance.The granular detergent composition that contains these compounds generally contains the water-soluble ethoxylated amine of about 10.0% (weight) of the 0.01%-that has an appointment.Liquid detergent composition generally contains the 0.01%-that has an appointment about 5%.
Most preferred removal dirt and anti redeposition agent are the ethoxylation tetrens.The example of ethoxylated amine has description in the United States Patent (USP) 4597898 of the VanderMeer of mandate on July 1st, 1986.Another kind of preferred removal clay soil/anti redeposition agent be on June 27th, 1984 disclosed Oh and the european patent application 111965 of Gosselink in disclosed cation compound.Other that can use are in the present invention removed disclosed ethoxylated amine polymer in the european patent application 111984 that clay soil/anti redeposition agents comprise disclosed Gosselink on the 27th June in 1984; July in 1984 disclosed Gosselink on the 4th european patent application 112592 in disclosed amphiphilic polymers; With the amine oxide in the United States Patent (USP) 4548744 of the Connor that authorized on October 22nd, 1985.As known in the art other remove clay soil and/or anti redeposition agent also can be used in the composition of the present invention.Another kind of preferred anti redeposition agent comprises carboxymethyl cellulose (CMC).These materials are as known in the art.Polymeric dispersant
Content can be advantageously used in the present composition for the polymeric dispersant of about 0.1%-about 7% (weight).The polymeric dispersant that is fit to comprises polymeric polycarboxylate and polyoxyethylene glycol, although other known polymeric dispersants also can use in this area.
By making suitable unsaturated monomer, preferably polymerization or the copolymerization with the unsaturated monomer of its sour form can prepare the polymer poly-carboxylate.Can comprise vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid through the suitable polymer poly-carboxylate's of polymerization preparation unsaturated monomer acid.In polymer poly-carboxylate of the present invention or monomer segment, contain the monomer segment that does not have carboxylate groups such as vinyl methyl ether, vinylbenzene, ethene etc. and be fit to, as long as it is no more than about 40% (weight).
Especially the polymer poly-carboxylate of Shi Heing can obtain from vinylformic acid.The polymkeric substance of such acrylic that uses among the present invention is the water-soluble salt of polymeric acrylic acid.The molecular-weight average of this base polymer that exists with sour form is preferably about 2000-10000, and more preferably about 4000-7000 most preferably is about 4000-5000.The example of the water-soluble salt of such acrylate copolymer comprises as an alkali metal salt, ammonium salt and substituted ammonium salt.Such polymer soluble is known.Such application of polypropylene hydrochlorate in detergent composition is disclosed in the United States Patent (USP) 3308067 of the Diehl that on March 7th, 1967 authorized.
The multipolymer of vinylformic acid/maleic also can be as the preferred ingredient of dispersion/anti redeposition agent.This class material comprises the water-soluble salt of vinylformic acid and maleic acid.The molecular-weight average of this analog copolymer of acid form is preferably about 2000-100,000.The molecular-weight average of preferred multipolymer is about 2000-15000, and more preferably from about 6000-is about 13000, and most preferably from about 7000-about 12000.The molecular-weight average of other preferred multipolymer is about 5000-75000,7000-65 most preferably from about, 000.The ratio of acrylate moiety and toxilic acid part was generally about 30: 1 to about 1: 2 in this analog copolymer, and more preferably from about 10: 1 to 1: 1, most preferably from about 2.5: 1 to 1: 1.The water-soluble salt of this class vinylformic acid/maleic acid can comprise, for example an alkali metal salt, ammonium salt and substituted ammonium salt.The soluble salt of this class vinylformic acid/maleic acid is a disclosed european patent application 66915 on December 15 nineteen eighty-two, and on September 3rd, 1986 known substance described among the disclosed EP193360, it has also described this base polymer that comprises the hydroxypropyl acrylate.Other useful dispersion agent also comprises toxilic acid/vinylformic acid/vinyl alcohol terpolymer.This class material also is disclosed in EP193, in 360, comprises for example 45/45/10 terpolymer of vinylformic acid/toxilic acid/vinyl alcohol.
Particularly preferred polymer dispersant is the polypropylene salt copolymer of lower molecular weight modification.This analog copolymer contains following monomeric unit: a) about 90%-is about 10%, about 20% (weight) vinylformic acid of preferably about 80%-or its salt, and b) about 10%-is about 90%, Acrylic Acid Monomer or its salt that about 80% (weight) of preferably about 20%-replaces, it has general formula-[C (R
2) C (R
1) (C (O) OR
3)]-, wherein undersaturated valency is a hydrogen in the square brackets, R
1, R
2Or R
3In at least one substituting group, preferred R
1Or R
2In at least one substituting group be the alkyl or the hydroxyalkyl of 1 to 4 carbon atom, R
1Or R
2Can be hydrogen, R
3Can be hydrogen or an alkali metal salt.The most preferably Acrylic Acid Monomer of Qu Daiing, wherein R
1Be methyl, R
2Be hydrogen, R
3Be sodium.
It is about 15,000 that the preferred molecular weight of low-molecular-weight polyacrylic acid salt polymer dispersant is lower than, and more preferably from about 500 to about 10,000, and most preferably from about 1000 to about 5000.The molecular weight of the most preferred polyacrylic acid salt copolymer that the present invention uses is 3500, and is the polymkeric substance that comprises in about 70% (weight) vinylformic acid and about 30% (weight) methylacrylic acid complete with form,
The polyacrylic acid salt copolymer of the modification that other is fit to comprises the multipolymer of low-molecular-weight unsaturation aliphatic carboxylic acid, and it is disclosed in United States Patent (USP) 4,530, and in 766 and 5,084,535, these two pieces of documents are hereby incorporated by.
Agglomerated form of the present invention can use the aqueous solution of polymeric dispersant to be used to prepare agglomerate (particularly when composition is made up of the mixture of Trisodium Citrate and yellow soda ash) as liquid adhesive.Particularly preferably being molecular-weight average is about 1,000 to about 10,000 polyacrylate, with molecular-weight average be about 2000 to about 80,000 acrylate/maleate or acrylate/fumarate multipolymer, wherein the ratio of acrylate and maleate or fumarate part is about 30: 1 to about 1: 2.Example based on this analog copolymer of unsaturated list and dicarboxylate monomer mixture is disclosed in the disclosed european patent application 66915 on December 15 nineteen eighty-two, and it is hereby incorporated by.
Other useful polymer dispersant of the present invention comprises that molecular weight is about 950 to about 30,000 polyoxyethylene glycol and polypropylene glycol, and they can obtain from the Dow ChemicalCompany of Midland Michigan.Can obtain molecular weight and be this compounds of 1450,3400,4500,6000,7400,9500 and 20,000, their fusing point is about 30 ° to about 100 ℃.This compounds can be with the preparation of following method: with the oxyethane of ethylene glycol or propylene glycol and required molal quantity or propylene oxide polymerization so that the corresponding polyoxyethylene glycol and the polypropylene glycol of desired molecule amount and fusing point to be provided.Polyoxyethylene glycol, polypropylene glycol and blended glycol can be represented with this formula: HO (CH
2CH
2O)
m(CH
2CH (CH
3) O)
n(CH (CH
3) CH
2O)
oH, wherein m, n and o are the integers that satisfies above-mentioned molecular weight and temperature requirement.
Be used for other polymer dispersant of the present invention and comprise cellulose sulfuric acid ester, for example sulfovinic acid Mierocrystalline cellulose, sulfate cellulose, sulfuric acid Natvosol, sulfuric acid methylcellulose gum and sulfuric acid hydroxypropylcellulose.Sodium cellulose sulfate is most preferred in this group polymkeric substance.
Other suitable polymer dispersant is the polysaccharide of carboxylation, particularly starch, Mierocrystalline cellulose and alginate, and they are described in the U.S.3 of the Diehl that authorized on March 27th, 1973, in 723,322; Be disclosed in the U.S.3 of the Thompson that authorized on November 11st, 1975, the dextrin ester of the poly carboxylic acid in 929,107; Be described in the U.S.3 of the Jensen that authorized on April 9th, 1974, hydroxyalkyl starch ether, starch ester, Sumstar 190, dextrin and starch hydrolysate in 803,285; Be described in the U.S.3 of the Eldib that authorized on December 21st, 1971, the starch of the carboxylation in 629,121; With the U.S.4 that is described in the McDanald that authorized on February 27th, 1979, the dextrin starch in 141,841; All documents are hereby incorporated by.The polymer dispersant of preferred cellulose-derived is a carboxymethyl cellulose.
Another organizes acceptable dispersion agent is organic dispersing agent polymkeric substance, for example polyaspartic acid salts.
The another kind of polymkeric substance that can be comprised is polyoxyethylene glycol (a PEG multipolymer).The PEG multipolymer also has the performance of dispersion agent except can be used as removal clay soil/anti redeposition agent.It is about 100,000 that the molecular-weight average that is used for the polyoxyethylene glycol of this purposes is generally about 500-, and it is about 50,000 to be preferably about 1000-, more preferably about 1, and 500-about 10,000.
Also can use polyaspartic acid salts and polyglutamic acid dipersant, especially be used in combination with zeolite builders.It is believed that, but do not mean that and be limited by theory, in containing the composition of detergent builders, when polymeric dispersant and other washing assistant (comprising low-molecular-weight polycarboxylate) when being used in combination, free the over-all properties that gelation and anti-redeposition have strengthened washing assistant by crystalline growth restraining effect, particulate fouling.Such as the preferred molecular weight of the dispersion agent of poly aspartic acid (on average) is about 10,000.Whitening agent
Any white dyes as known in the art or other whitening agent generally can mix in the detergent composition of the present invention by the content of about 0.05%-about 1.2% (weight).Commercially available white dyes of the present invention can be used for and following group can be divided into, it comprises, but unrestricted, stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanines, dibenzothiophene-5,5-dioxide, pyrroles, 5-and 6-unit heterocyclic derivative, and other trace reagents.The example of these whitening agent is disclosed in " production of white dyes and application (The Production andApplication of Fluorescent Brightening Agents) ", M.Zahradnik, John Wiley ﹠amp; Sons publishes, among the New York (1982).
Disclosed identical in the specific examples of the white dyes that in the present composition, uses and the United States Patent (USP) 4790856 that licensed to Wixon on December 13rd, 1988.These whitening agent comprise the PHORWHITE whitening agent series of Verona.Disclosed other whitening agent comprises in this reference: the Tinopal UNPA of Ciba-Geigy, Tinopal CBS and Tinopal 5BM: the Artic White CC and the Artic WhiteCWD that are located at gondola Hilton-Davis; 2-(4-styryl phenyl)-2H-naphthols [1,2-d] triazole; 4,4 '-two (1,2,3-triazoles-2-yl) stilbene; 4,4 '-bis-styrylbiphenyl and aminocoumarin.The specific examples of these whitening agent comprises 4-methyl-7-diethyl amino coumarin; 1, the two (ethene of benzimidazolyl-2 radicals-yl) of 2-; 1, the 3-diphenylpyrazoline; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-styryl-naphthalene-[1,2-d] oxazole and 2-(stilbene-4-yl)-2H-naphtho-[1,2-d] triazole.In addition referring to licensing to United States Patent (USP) 3646015 on February 29th, 1972.The negatively charged ion whitening agent is that the present invention is preferred.Suds suppressor
Be used for reducing or suppress the compound that foam forms and to mix the present composition.Foamy is suppressed at U.S.4, and 489,455 and 4,489, in so-called " high density purging method " described in 574 and in muzzle-loading European plan washing machine, be particularly important.
Can use various materials as suds suppressor, suds suppressor is that those skilled in the art are known.Referring to, Kirk Othmer Encyclopedia of ChemicalTechnology for example, the third edition, the 7th volume, 430-447 page or leaf (John Wiley ﹠amp; Sons, Inc., 1997).The suds suppressor of one class particularly important comprises monocarboxylic acid based lipid acid and its soluble salt.License to the United States Patent (USP) 2954347 of Wayne St.John referring to September 27 nineteen sixty.Monocarboxylic acid based lipid acid and salt thereof as suds suppressor generally have about 24 carbon atoms of the 10-of containing, the hydrocarbyl chain of preferred 12-18 carbon atom.The salt that is fit to comprises an alkali metal salt, for example sodium salt, sylvite and lithium salts; Ammonium salt and alkanol ammonium salts.
Detergent composition of the present invention can also contain the suds suppressor of nonsurfactant.The example of this class suds suppressor comprises: high-molecular-weight hydrocarbons, for example paraffin, fatty acid ester (as fatty acid triglyceride), the fatty acid ester of monohydroxy-alcohol, aliphatic C
18-40Ketone (as stearone) etc.Other suds suppressors comprise the alkylating aminotriazine of N-, for example three-six alkyl melamines or two-tetraalkyl diammonium chloride are for triazine, they are that cyanuric chloride and 2 or 3 moles contain the uncle of 1-24 carbon atom or the product of secondary amine, propylene oxide and single stearic alkyl phosphate are as single stearic alkanol phosphoric acid ester and single stearic alkylphosphonic acid carboxylic acid two basic metal (as K, Na and Li) salt and phosphoric acid ester.Hydrocarbon such as paraffin and halo paraffin can use with liquid form.This liquid hydrocarbon should be liquid state under room temperature and normal atmosphere, and should have-40 ℃-Yue 50 ℃ pour point approximately, and minimum boiling point is not less than about 110 ℃ (normal atmosphere).It is known using waxy hydrocarbon, and preferably it has and is lower than about 100 ℃ fusing point.Such hydrocarbon is the preferred suds suppressor of a class of detergent composition.For example license in people's such as Gandolfo the United States Patent (USP) 4265779 and described the hydrocarbon suds suppressor on May 5th, 1981.Therefore, this hydrocarbon comprises the aliphatic series that contains about 70 carbon atoms of the 12-that has an appointment, alicyclic, aromatics and heterocycle is saturated or unsaturated hydrocarbons.The term that uses in the discussion about such suds suppressor " paraffin " comprises the real paraffin and the mixture of cyclic hydrocarbon.
The suds suppressor of another kind of preferred nonsurfactant comprises the polysiloxane suds suppressor.This classification comprises the use polysiloxane oil, polydimethylsiloxane for example, and the dispersion agent of polysiloxane oil or resin or emulsifying agent, and the mixture of polysiloxane and silica dioxide granule, polysiloxane wherein is through chemisorption or be fused on the silicon-dioxide.The polysiloxane suds suppressor is well known in the art, for example license on May 5th, 1981 people such as Gandolfo United States Patent (USP) 4265779 and February 7 nineteen ninety disclosed Starch, disclosed in the european patent application 89307851.9 of M.S..
Other polysiloxane suds suppressor is disclosed in the United States Patent (USP) 3455839, and this patent relates to by mixing a small amount of polydimethylsiloxane fluid to eliminate aqueous solution foamy composition and method in composition.
The mixture of polysiloxane and silanized silica is described in as German patent application DOS2124526 to some extent.Polysiloxane defoamers in granular detergent composition and Foam Control be disclosed in people's such as Bartolotta United States Patent (USP) 3933672 and the people's such as Baginski that authorized on March 24th, 1987 United States Patent (USP) 4652392 in.
The example that is used for the suds suppressor of polysiloxane group of the present invention be foam inhibition amount basically by the following foam suds suppressor of forming:
(i) at 25 ℃ of polydimethylsiloxane fluids with the about 1500cs of the about 20cs-of viscosity;
(ii) per 100 parts (weight) (i) corresponding to the polyorganosiloxane resin of about 5-about 50 parts (weight), this resin is by (CH
3)
3SiO
1/2Unit and SiO
2The unit is by about 0.6: the ratio that 1-is about 1.2: 1 is formed; With
(iii) 100 parts of (i) (weight) are corresponding to the about 20 parts of solid silicones of about 1-(weight);
In the preferred polysiloxane suds suppressor that uses among the present invention, the solvent that is used for external phase is made up of some polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers or its mixture (preferably) or polypropylene glycol.Main polysiloxane suds suppressor is a side chain/crosslinked, preferred non-straight chain type.
In order to further specify this point, general liquid laundry detergent compositions with control foaming effect contains the 0.001%-that has an appointment about 1% usually, preferred about 0.01%-about 0.7%, the described polysiloxane suds suppressor of about 0.5% (weight) of 0.05%-most preferably from about, this suds suppressor contains the nonaqueous emulsion of (1) main suds suppressor, this suds suppressor is (a) polysiloxane, (b) the arborescens polysiloxane maybe can produce the polysiloxane compound of polyorganosiloxane resin, (c) filler in small, broken bits and (d) impel component of mixture (a), (b) and (c) react to generate the catalyzer of silane alkoxide; (2) at least a nonionic silicones tensio-active agent; (3) solubleness in water surpasses the polyoxyethylene glycol of about 2% (weight) or the multipolymer of polyethylene glycol-propylene glycol under the room temperature; Wherein there is not polypropylene glycol.Similarly amount can be used for particulate composition, silica gel etc.In addition referring to the United States Patent (USP) 4978471 of the Starch that authorizes December 18 nineteen ninety, United States Patent (USP) 4983316 with the Starch that authorized on January 8th, 1991, the people's such as Huber that on February 22nd, 1994 authorized United States Patent (USP) 5,288,431 and people's such as Aizawa United States Patent (USP) 4639489 and 4749740, the first hurdles the 46th walk to the 4th hurdle the 35th row.
Preferred polysiloxane suds suppressor comprises among the present invention: the multipolymer of polyoxyethylene glycol and polyethylene/polypropylene glycol, their molecular-weight average are lower than about 1000, are preferably about 100-800.Solubleness under the multipolymer room temperature of polyoxyethylene glycol of the present invention and polyethylene/polypropylene glycol in water surpasses about 2% (weight), preferably surpasses about 5% (weight).
It is about 1000 that the preferred solvent of the present invention is that molecular-weight average is lower than, and more preferably about 100-800 most preferably is the polyoxyethylene glycol of 200-400 and the multipolymer of polyethylene/polypropylene glycol, preferred PPG 200/PEG 300.Polyoxyethylene glycol: the weight ratio of polyethylene/polypropylene glycol preferably about 1: 1-1: 10, most preferably be 1: 3-1: 6.
The polysiloxane suds suppressor that the present invention preferably uses does not contain polypropylene glycol, does not especially contain molecular weight and be 4000 polypropylene glycol.The segmented copolymer of its also preferred oxygen-free ethene and propylene oxide is as PLURONIC L101.
Other suds suppressors that the present invention uses comprise the mixture of secondary alcohol (as the 2-alkyl chain triacontanol) and these alcohol and polysiloxane oil, as are disclosed in the polysiloxane in United States Patent (USP) 4798679,4075118 and the European patent 150872.Secondary alcohol comprises having C
1-16The C of chain
6-16Alkanol.Preferred alcohol is 2-butyl octanol, and this alcohol can obtain from Condea by the trade mark of ISOFOL 12.The secondary alcohol mixture can obtain from Enichem with the trade mark of ISALCHEM 123.It is 1 that the mixing suds suppressor generally contains weight ratio: 5-5: the mixture of 1 pure and mild polysiloxane.
For any detergent composition that is used for automatic washing machine, the foam of formation should not overflow washing machine.When using suds suppressor, preferably it exists with " foam inhibition amount "." foam inhibition amount " is meant that fully control foam that the prescription teacher of composition selects is to obtain being used for the low foam cloth-washing detergent of automatic washing machine.
Composition of the present invention contains the suds suppressor of 0%-about 5% usually.When using monocarboxylic acid based lipid acid and its salt as suds suppressor, its consumption is usually up to being about 5% of detergent composition weight.The preferred fatty monocarboxylate suds suppressor that uses about 0.5%-about 3%.Although also can adopt higher consumption, the consumption of polysiloxane suds suppressor the highest general about 2.0% of the detergent composition weight that is about.Because at first will consider to make cost to keep efficient minimum and the low effective control foam of consumption, this upper limit is practical.The preferred polysiloxane suds suppressor that uses about 0.01%-about 1%, more preferably about 0.25%-about 0.5%.Among the present invention, comprise whole silicon-dioxide that can use with polysiloxane and any additives material that may use in these weight percent numerical value.The consumption of single stearic alkylphosphonic suds suppressor is generally about 0.1%-about 2% of composition weight.Although can use the hydrocarbon suds suppressor of higher consumption, its consumption is generally about 0.01%-about 5.0%.The consumption of alcohol suds suppressor is generally the 0.2%-3% of composition finished weight.Fabric softener
Can randomly use the fabric softener of various experience washing whole processes in the present composition, particularly disclosed particulate smectic clays and other softening agent clay as known in the art in the United States Patent (USP) 4062647 of Storm that authorized on December 13rd, 1977 and Nirschl, thus the effect that in cleaning fabric, obtains soft fabric made.The consumption of softening agent is generally about 10% (weight) of about 0.5%-.The clay softening agent can be used with amine and cationic softener, as the people's such as Crisp in March 1 nineteen eighty-three United States Patent (USP) 4375416 and the people's such as Harris that authorized on September 22nd, 1981 United States Patent (USP) 4291071 is disclosed.Dye transfer inhibitor
Granular composition of the present invention also can comprise and is suppressed at dyestuff in the cleaning process is transferred to another kind of fabric from a kind of fabric one or more materials effectively.This dye transfer inhibitor generally comprises polyvinyl pyrrolidone polymers, the multipolymer of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole, manganese phthalocyanine, peroxidase and its mixture.If you are using, it is about 10% that these reagent are generally about 0.01%-of present composition weight, and preferably about 0.01%-is about 5%, and more preferably from about 0.05%-about 2%.
More particularly, be preferred for the unit that polyamine N-oxide pllymers of the present invention contains following structural formula: R-A
x-P, wherein P is that the polymerisable unit of connection N-O group or a part or the N-O group of N-O group formation polymerizable unit can be connected on these two kinds of unit; A is one of following structure :-NC (O) ,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; R is that the nitrogen or the N-O group that can connect in the N-O group are aliphatic series, ethoxylation aliphatic series, aromatics, heterocycle or alicyclic group or its arbitrary combination of its part.Preferred polyamine N-oxide compound is that wherein R is those of heterocyclic group such as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines and its derivative.
The N-O group can be represented by following general structure:
R wherein
1, R
2, R
3Be aliphatic series, aromatics, heterocycle or alicyclic group or its combination; X, y and z are 0 or 1; Nitrogen-atoms in the N-O group can be linked on any aforementioned group or the N-O group constitutes the part of aforementioned group.The unitary PKa of the amine oxide of polyamine N-oxide＜10, preferred PKa＜7, more preferably PKa＜6.
As long as the amine oxide polymers that forms is water miscible and has the character that suppresses dye transfer that polymer backbone can use arbitrarily.The example of suitable polymer blend skeleton is polyvinyl, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylate and its mixture.These polymkeric substance comprise random or segmented copolymer, and wherein a kind of monomer type is an amine n-oxide, and another kind of monomer type is the N-oxide compound.The amine of amine n-oxide polymkeric substance and the ratio of amine n-oxide were generally 10: 1 to 1: 1000, and 000.Yet the number of the amine oxide group that exists in the polyoxygenated amine polymer can change according to suitable co-polymerization or suitable N-degree of oxidation.Almost can obtain the polyoxygenated amine of any polymerization degree.Usually, its molecular-weight average is 500 to 1,000, in 000 scope, and more preferably 1,000, to 500,000, most preferably 5,000 to 100,000.The preferred material of this class can be described as " PVNO ".
Useful most preferred polyamine N-oxide is poly-(4-vinylpridine-N-oxide compound) in detergent composition of the present invention, and its molecular-weight average is about 50,000, and the ratio of amine and amine n-oxide is about 1: 4.
The multipolymer of N-vinyl pyridine alkane ketone and N-vinyl imidazole polymkeric substance (class that is called " PVPVI ") also is that the present invention preferably uses.The molecular-weight average of preferred PVPVI is 5,000 to 1,000,000, more preferably 5,000 to 200,000, most preferably 10,000 to 20,000.(this average molecular weight range is to measure by the light scattering technique described in the following document, and the document is people's such as Barth chemical analysis (Chemical Analysis) the 113rd volume." modernism of polymer characterization (Modern Metho ds of Polymer Characterization) ", its disclosure is hereby incorporated by) the PVPVI multipolymer mol ratio that generally has N-vinyl imidazole and a N-vinyl pyrrolidone is 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1, most preferably 0.6: 1 to 0.4: 1.These multipolymers can be straight chain or side chain.
The present composition also can use molecular-weight average for about 5,000 to 400,000, and preferred about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000 polyvinylpyrrolidone (" PVP ").PVP is that the technician in the detergent applications is known, referring to, EP-A-262 for example, and 897 and EP-A-256,696, it is hereby incorporated by.It is about 500 to about 100,000 that the composition that contains PVP also can contain mean molecule, preferred about 1000 to about 10,000 polyoxyethylene glycol (" PEG ").Preferably PEG that calculates in ppm in washing soln and the ratio of PVP are about 2: 1 to about 50: 1, more preferably from about 3: 1 to about 10: 1.
Detergent composition of the present invention also can randomly contain the 0.005% hydrophilic white dyes that some type that suppresses the dye transfer effect also is provided to about 5% (weight) of having an appointment.If you are using, the present composition will preferably include this white dyes of about 0.01%-1% (weight).
Useful in the present invention hydrophilic white dyes is to have those of following structural formula:
R wherein
1Be selected from anilino, N-2-double hydroxyethyl and NH-2-hydroxyethyl; R
2Be selected from N-2-double hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chlorine and amino; M is salt-forming cation such as sodium or potassium.
When in following formula, R
1Be anilino, R
2Be the N-2-double hydroxyethyl, when M was positively charged ion such as sodium, this whitening agent was 4,4 '-two [(4-anilino-6-(N-2-double hydroxyethyl)-S-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid and its disodium salt.This concrete whitening agent is sold by Ciba-Geigy Corporation commercial, and trade(brand)name is Tinopal-UNPA-GX.Tinopal-UNPA-GX is a preferred wetting ability white dyes useful in the detergent composition of the present invention.
When in following formula, R
1Be anilino, R
2Be N-2-hydroxyethyl-N-2-methylamino-, M is a positively charged ion, and during as sodium, this whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-S-triazine-2-yl) amino] 2,2 '-stilbene disulfonic acid disodium salt.This concrete whitening agent is sold by Ciba-Geigy Corporation commercial, and trade(brand)name is Tinopal 5BM-GX.
When in following formula, R
1Be anilino, R
2Be morpholino, when M was positively charged ion such as sodium, this whitening agent was 4,4 '-two [(4-anilino-6-morpholino-S-triazine-2-yl) amino] 2,2 '-stilbene disulfonic acid sodium salt.This concrete whitening agent is sold by Ciba-GeigyCorporation commercial, and trade(brand)name is Tinopal AMS-GX.
Be selected for these specific white dyess of the present invention when the performance benefit that particularly effectively suppresses dye transfer is provided when selecteed polymeric dye transfer inhibitor mentioned above is used in combination.Any of the combination of these selecteed polymeric materials (for example PVNO and/or PVPVI) and these selecteed white dyess (for example Tinopal UNPA-GX, Tinopal 5BM-GX, Tinopal-PLC and/or Tinopal AMS-GX) and these two kinds of detergent composition components of independent use compared, and the former provides the significantly good inhibition to dye transfer in wash water solution.Do not accept opinion and keep within bounds, believe that the mode of action of this whitening agent is:, therefore be deposited on relatively apace on these fabrics because they have high affinity to the fabric in the washing soln.Whitening agent is deposited on the degree on the fabric in the washing soln and defines with the parameter that is called " consumption coefficient ".This exhausts coefficient and refers generally to a) be deposited on whitening agent material and b on the fabric) ratio of initial whitening agent concentration in wash water solution.Have the high relatively whitening agent that exhausts coefficient and be suitable for suppressing dye transfer in the present invention most.
Certainly, can be appreciated that other types of conventional optical brightener compounds can randomly be used for the present composition and " brighten " benefit so that conventional fabric to be provided, is not real dye transfer restraining effect yet.This application is conventional and is known for the preparation of washing composition.Other compositions
In the present composition, can also include other useful in various detergent composition compositions, comprising other activeconstituentss, carrier, hydrotropic agent, processing aid, dyestuff or pigment, be used for liquid preparation solvent, be used for the solid packing of soap blank composition etc.High if desired foam then can mix as C in said composition
10-C
16The suds booster of alkanolamide, its consumption is generally 1%-10%.C
10-C
14Monoethanolamine and diglycollic amide are the representative instances of such suds booster.With this class suds booster and high bubble additive tensio-active agent, it also is favourable using together as above-mentioned amine oxide, trimethyl-glycine, sultaine.If necessary, also can add as MgCl
2, MgSO
4Deng the solubility magnesium salts obtaining more foam and to strengthen the degrease performance, the consumption of this magnesium salts is generally 0.1%-2%.
The various decontamination compositions that use in the present composition can also be by being adsorbed on these compositions on the porous hydrophobic matrix, and then with hydrophobicity apply agent with this matrix coated with further making its stabilization.Preferably before adsorbing, this decontamination composition is mixed with tensio-active agent with porous matrix.In use, this decontamination composition is discharged into the wash water solution from matrix, and finishes the washing functions of its expection in this washing soln.
In order to illustrate in greater detail this technology, with porous hydrophobic silicon-dioxide (trade mark SIPERNATD10, DeGussa) with contain 3%-5% C
13-15The proteolysis enzyme solution of the nonionogenic tenside of ethoxylated alcohol (EO 7) mixes.The amount of this enzyme/surfactant soln generally is 2.5 times of silica weight.The gained powder (can be used the various polysiloxane oils of viscosity as 500-12500) through dispersed with stirring in polysiloxane oil.Add in the final washing composition matrix with the polysiloxane oil dispersion thing emulsification of gained or with it.By this method; enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, light activating agent, dyestuff, white dyes, fabric conditioner and hydrolyzable tensio-active agent can be used for washing composition with " protected form " as the aforementioned, and this washing composition comprises liquid laundry detergent compositions.
Liquid detergent composition can contain the solvent of water and other as carrier.Low-molecular-weight uncle or secondary alcohol, for example methyl alcohol, ethanol, propyl alcohol and Virahol suit.Monohydroxy-alcohol is preferred for solubilizing surfactant, also can use to about 6 carbon atoms and 2 those polyvalent alcohols to about 6 hydroxyls (for example 1, ammediol, ethylene glycol, glycerine and 1,2-propylene glycol) but contain 2.Said composition can contain 5%-90%, is generally this carrier of 10%-50%.
The available for example spraying drying (finished product density is about 520g/l) or the method for agglomeration basic granules (finished product density is more than about 600g/l) prepare granulated detergent.Then with the dry ingredient of remainder with particle or form of powder and basic granules, for example in the rotation mixing drum, mix, and above liquid component (for example nonionogenic tenside and spices) can being sprayed on.
Detergent composition of the present invention is preferably prepared like this, and in moisture cleaning operation use, the pH of washing water is about 6.5 to about 11, preferred about 7.5 to 10.5.The preferred pH of liquid wash up product formulation is about 6.8-9.0.The pH of laundry product is generally 9-11.Control pH comprises use buffer reagent, alkali, acid etc. for the technology of suggestion use value, and these are that those of skill in the art are known.
In order to make the present invention be easier to understand, provide following examples for reference, it is intended to explanation, rather than limits the present invention in this scope.
Example I
This embodiment has illustrated the dirty granulated detergent of weight that contains surfactant system and oleoyl sarcosinate of the present invention.Composition in the exemplary typical granulated detergent of the present invention is listed among the following table I.
Table I
(% weight) component A B CC
12-18Alkyl ethoxy (0.6) vitriol 10.1 8.9 4.9C
11-13Alkylbenzene sulfonate--9.3Neodol 23-9
10.5 0.4 2.2Neodol 23-3
20.5 0.4-C
12-14N-methyl glucose amide 0.9 0.8-oleoyl sarcosinate 5.7 5.0 5.6 polyacrylates (MW=4500) 3.0 2.6 2.9 polyethylene glycol (MW=4000) 1.2 1.7 1.5 sodium metasilicate--0.7 sodium sulphate, 16.6 14.5 14.6 alumino-silicates, 24.3 21.3 25.7 sodium carbonate, 27.2 23.8 14.5 proteinase-10 .4,0.3 0.3 amylase 0.1--lipase 0.2--cellulase 0.1-2.1NOBS3-4.7 4.9 other components of Sodium peroxoborate-4.3 3.3 (water, spices etc.) 9.2 11.3 7.5
100.0 100.0 100.0
1C
12-13Alkylethoxylate (EO=9), commercial can buying by Shell Oil Company
2C
12-13Alkylethoxylate (EO=3), commercial can buying by Shell Oil Company
3The ninth of the ten Heavenly Stems acyloxy phenylsulfate
At first use a kind of in the multiple currently known methods, comprise conventional spray drying technology or for example in the commercial powder mixer that can buy by Lodige and Aeromatic and fluidized-bed, carry out agglomerant method respectively that preparation contains the basic recipe of starting liq and powder at equipment.Agglomeration technique is particularly useful for making current compact grain washing composition, and it at first requires to use the standard mixing machine to form surfactant paste, and this lotion is agglomerated into agglomerate and dry afterwards.This processing technology is as known in the art.For example enzyme is dried mixed in basic recipe with detergent ingredients, and/or subsequently composition such as spices is sprayed onto the basic recipe product upward to form the final granular detergent composition of example herein.
Example II
This embodiment has illustrated liquid laundry detergent compositions of the present invention.Table II has illustrated the various compositions of this liquid laundry detergent.
Table II
(% weight) component D E oleoyl sarcosinate 9.0 7.0C
12-18Alkyl ethoxy (0.6) vitriol 12.0 14.0C
12-14N-methyl glucose amide 6.0 6.0C
9-11Alkylethoxylate (EO=8) 3.0 3.0C
12-20Lipid acid 4.0 4.0 citric acids 0.5 0.5 proteinase-10 .5 0.5 lipase 0.2 0.2 amylase 0.1 0.1 cellulases 0.1 0.1 minor component (water, solvent, spices etc.) 58.1 58.1
100.0 100.0
EXAMPLE III
This embodiment has illustrated laundry bars of the present invention.The laundry bars of example of the present invention prepares with the standard extrusion process, and it is applicable to the fabric that hand washing is polluted.Table III has been listed the various compositions in this laundry bars.
Table III
(% weight) component F GC
12-18Alkyl ethoxy (0.6) vitriol 10.1 8.9Neodol 23-9
10.5 0.4Neodol 23-9
20.5 0.4C
12-14N-methyl glucose amide 0.9 0.8 oleoyl sarcosinates 5.7 5.0 sodium pyrophosphates 7.0 7.0 sodium phosphate trimers 7.0 7.0 sodium carbonate 25.0 25.0 alumino-silicate 5.0 5.0 carboxymethyl celluloses, 0.2 0.2 polyacrylates (MW=1400) 0.2 0.2 proteinase-10 .4,0.4 other components (water, filler, spices etc.) 37.5 39.7
100.0 100.0
1C
12-13Alkylethoxylate (EO=9), commercial can buying by Shell Oil Company.
2C
12-13Alkylethoxylate (EO=3), commercial can buying by Shell Oil Company.
Thus the present invention has been made detailed description, it will be apparent to one skilled in the art that not departing under the scope of the invention and can do multiple variation, and the present invention and do not mean that the content that is subject to described in specification sheets.
Claims (10)
1. detergent composition is characterized in that:
A) at least 1% surfactant system, it contains at least a anion surfactant that is selected from alkylbenzene sulfonate, alkyl ester sulfonate, alkyl-sulphate, alkyl ethoxy sulfate, secondary alkyl sulfate and its mixture; With
B) at least 0.1% oleoyl sarcosinate; Wherein the ratio of oleoyl sarcosinate and said surfactant system is 1: 20 to 10: 1.
2. detergent composition according to claim 1, its feature also is at least 1% (weight) detergency washing assistant.
3. detergent composition according to claim 1-2, wherein said detergency washing assistant is selected from yellow soda ash, zeolite and its mixture.
4. detergent composition according to claim 1-3, its feature also is to be selected from the additive component of SYNTHETIC OPTICAL WHITNER, bleach-activating agent, suds suppressor, enzyme, enzyme stabilizers, polymeric dispersant, dye transfer inhibitor and dirt release agent.
5. detergent composition according to claim 1-4, wherein said composition is the form of agglomerate, and the density of said detergent composition is 600g/l at least.
6. detergent composition according to claim 1-5, wherein the content of said oleoyl sarcosinate is 0.1%-90% (weight).
7. detergent composition according to claim 1-6, its feature also is the mixture of 0.1%-45% (weight) alkyl-sulphate and alkyl sulfonate surfactants.
8. detergent composition according to claim 1-7, wherein said composition is the form of agglomerate, and the density of said detergent composition is 600g/l at least.
9. detergent composition according to claim 1-8, wherein said composition is the form of laundry bars.
10. the method for the fabric of a contamination with wash is characterized in that the step that said fabric is contacted with the water-bearing media according to the detergent composition of claim 1-9 that contains significant quantity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95194348 CN1154136A (en) | 1994-06-01 | 1995-05-23 | Detergent composition containing oleoyl sarcosinate and anionic surfactants in optimum ratios |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/252,291 | 1994-06-01 | ||
| CN 95194348 CN1154136A (en) | 1994-06-01 | 1995-05-23 | Detergent composition containing oleoyl sarcosinate and anionic surfactants in optimum ratios |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1154136A true CN1154136A (en) | 1997-07-09 |
Family
ID=5082675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95194348 Pending CN1154136A (en) | 1994-06-01 | 1995-05-23 | Detergent composition containing oleoyl sarcosinate and anionic surfactants in optimum ratios |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1154136A (en) |
-
1995
- 1995-05-23 CN CN 95194348 patent/CN1154136A/en active Pending
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