CN1253580A - Soaker compositions - Google Patents
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- CN1253580A CN1253580A CN98804568.0A CN98804568A CN1253580A CN 1253580 A CN1253580 A CN 1253580A CN 98804568 A CN98804568 A CN 98804568A CN 1253580 A CN1253580 A CN 1253580A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/667—Neutral esters, e.g. sorbitan esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Lubricants (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Control Of Eletrric Generators (AREA)
- Percussion Or Vibration Massage (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Soaking compositions are disclosed which comprise oxygen bleach, a sorbitan ester in combination with a highly alkoxylated nonionic surfactant. Said compositions are diluted in water to form soaking liquors. The invention is particularly effective in removing particulate soils like silt and clay from fabrics as well as enzymatic stains and/or bleachable stains.
Description
Technical field
The present invention relates to cleaning fabric under soaking conditions, promptly under this condition, fabric soaks in comprising the immersion aqueous solution of water and detergent component, generally without any mechanical stirring, with its first step before as general washing operation, or as single step.
Background of invention
Soaking fabric operation is described in the prior art.In this dip operation, fabric contacts for a long time with soaking the aqueous solution, generally from several minutes to spending the night or even 24 hours.The advantage that this washing methods has is that it can make reach the longest duration of contact between active ingredient crucial in the fabric and the immersion aqueous solution.Its advantage that also has is to reduce or saved need relating generally to the needs of churned mechanically washing operation, or has improved the effect of follow-up general washing operation.
This dip operation generally is fit to remove outdoor incrustation from fabric, such as mud, flour sand and/or argillous particulate fouling.For example earth has the mineral structure (for example hydrated aluminium silicate such as illite, montmorillonite, kaolinite etc.) of micro-crystallization usually, wherein has organic moiety.This organic moiety can contain all cpds (for example humic acid, fulvinic acid, plant/animal organism amount etc.).Earth also can contain several metals (for example magnesium, calcium, potassium, iron etc.).Yet this particulate fouling is difficult especially to be removed from fabric.In fact, it is believed that very thin dirty particle such as earth or flour sand, granularity generally is lower than 0.002mm, can embed in the fabric fibre and easily to stick on the fiber surface.Be exposed to for the flour sand and argillous socks that carries for the easiest, this problem is sharp-pointed especially.But in addition about to enzyme stain or even the decontamination stain performance that provides of bleach spot, this dip operation is not exclusively satisfactory.Enzyme stain generally is made up of carbohydrate and albumen dirt such as bloodstain.Now observed enzyme stain and can play the effect of binding agent, therefore removed this kind of enzyme stain and can help from the fabric particle-removing dirt that gets on to the particulate fouling on the fabric.
Therefore, but the present invention seeks to improve removal to particulate fouling, mud and/or earth and enzyme stain and/or bleach spot.
Found that this purpose can be by realizing in the immersion aqueous solution that fabric is immersed in the washing by soaking agent composition that comprises significant quantity that described washing by soaking agent composition comprises the oxygen bleaching agent and the highly oxyalkylated nonionogenic tenside of hereinafter definition.In fact, found under soaking conditions (promptly, when contact is long-time, generally more than 1 hour to 24 hours), compare with the decontamination stain performance that the same combination that does not contain this height alkoxy-based non-ionic surface active agent provides, this height alkoxy-based non-ionic surface active agent in the immersion composition and oxygen bleaching agent are to providing the decontamination stain of improving performance such as outdoor incrustation, the enzyme stain of particulate fouling and/or the spot that can bleach.Therefore, aspect the most widely, the present invention includes the method for soaking fabric, wherein said fabric dipping in the immersion aqueous solution of the composition of height alkoxy-based non-ionic surface active agent that comprises this paper definition that comprises water and significant quantity and oxygen bleaching agent took out from the described immersion aqueous solution then more than 1 hour.
An advantage of the invention is when soaking fabric in the presence of the immersion composition of this height alkoxy-based non-ionic surface active agent that is comprising oxygen bleaching agent and this paper definition, finally cause in the presence of the hardness ions, also can improve decontamination stain performance at relative high-content.In fact, the naturally occurring hardness ions (calcium or magnesium ion) that causes especially can reduce surfactant properties in soaking the aqueous solution, finally tensio-active agent can be settled out as calcium or magnesium salts from soak the aqueous solution.This phenomenon is rare when using the alkoxy-based non-ionic surface active agent of this paper definition.Therefore, washing by soaking agent manufacturers can utilize the free not so good washing assistant of hardness ions that causes of chelating, therefore can use not too expensive washing assistant in this immersion composition.
In addition, found in washing by soaking agent composition, to pass through described height alkoxy-based non-ionic surface active agent and oxygen bleaching agent are combined with the sorbitan esters of hereinafter definition, performance has been steeped in the decontamination of particulate fouling, enzyme stain and/or bleach spot but also improved.Therefore, the present invention includes the sorbitan esters that comprises this paper definition, the height alkoxy-based non-ionic surface active agent of this paper definition and the washing by soaking agent composition of oxygen bleaching agent, and the method for in the immersion aqueous solution that makes with described washing by soaking agent composition, soaking fabric.
An advantage of the invention is not only provides the degranulation fouling performance that improves, but also has suppressed the again deposition of dirt on fabric under the long period of soaking condition.In addition, the immersion composition that the present invention comprises sorbitan esters, this height alkoxy-based non-ionic surface active agent and oxygen bleaching agent also to other type such as the butyrous spot, for example dirty motor oil, macaroni condiments provide effective decontamination stain performance.Background technology
EP-A-736594 discloses and has comprised sorbitan esters and a large amount and help the immersion composition of washing with the combination of dirt suspension system, wherein helps to wash to comprise with dirt suspension system to be selected from citric acid or Citrate trianion, silicate, zeolite, multi-carboxylate, phosphatic compound and their mixture.Oxygen bleaching agent is included in the optional component.Not open, do not illustrate alkoxy-based non-ionic surface active agent yet.
Summary of the invention
The present invention includes granular immersion composition, it comprises :-pressing general composition weight meter, 0.001%-15% is according to formula C
6H
9O
2(C
2H
4O)
xR
1R
2R
3Sorbitan esters, wherein x is the integer of 0-40, R
1, R
2Be OH or (C independently
nH
2n+1) COO, R
3Be (C
nH
2n+1) the COO group, wherein n is the integer of 11-17 ,-pressing general composition weight meter, 0.001%-20% is according to formula RO-(A)
nThe alkoxy-based non-ionic surface active agent of H, wherein R is replacement or unsubstituted, the saturated or unsaturated straight or branched hydrocarbon chain with 6-40 carbon atom, and A is the alkoxyl group with 2-10 carbon atom, and wherein n is the integer of 9-100 ,-and oxygen bleaching agent.
The present invention also comprises the method for soaking fabric, wherein described fabric is flooded the effective time in the immersion aqueous solution of this paper above-mentioned composition that comprises water and significant quantity, takes out from the described immersion aqueous solution then.
Aspect the most widely, the present invention includes the method for soaking fabric, wherein described fabric dipping in the immersion aqueous solution of the composition of oxygen bleaching agent that wherein comprises this paper definition that comprises water and significant quantity and alkoxy-based non-ionic surface active agent was taken out from the described immersion aqueous solution then more than 1 hour.
Detailed Description Of The Invention
The present invention includes the composition and the method for soaking fabric.Said composition is hereinafter referred to as soaked composition, is used in this immersion process.The A-composition:
Particulate composition of the present invention comprises the specific alkoxy-based non-ionic surface active agent and the oxygen bleaching agent of sorbitan esters, this paper definition at least.Sorbitan esters:
Therefore, the necessary component of first of the present composition is according to formula C
6H
9O
2(C
2H
4O)
xR
1R
2R
3Sorbitan esters, wherein x is the integer of 0-40, R
1, R
2Be OH or (C independently
nH
2n+1) COO, R
3Be (C
nH
2n+1) the COO group, wherein n is the integer of 11-17.
In preferred compositions of the present invention, x is 0 or 20, and the most preferred composition of the present invention comprises polyethoxylated (20) anhydrosorbitol tristearate, i.e. C
6H
9O
2(C
2H
4O)
20(C
17H
35COO)
3Or polyethoxylated (20) anhydrosorbitol monostearate, i.e. C
6H
9O
2(C
2H
4O)
20(OH)
2(C
17H
35Or anhydrosorbitol monostearate, i.e. C COO),
6H
9O
2(OH)
2(C
17H
35Or sorbitan-monopalmityl ester, i.e. C COO),
6H
9O
2(OH)
2(C
15H
31COO) or its mixture.
All these materials can be purchased by several trade(brand)names, for example the Glycosperse TS20 that buys from Lonza (polyethoxylated anhydrosorbitol tristearate), the Glycosperse S20 (polyethoxylated anhydrosorbitol monostearate) that buys from Lonza, the Radiasurf 7145 (anhydrosorbitol monostearate) that buys from Fina, the Radiasurf 7135 (sorbitan-monopalmityl ester) that buys from Fina, the Armotan MP (sorbitan-monopalmityl ester) that buys from Akzo.
Its independent a kind of better properties that provides of ethoxylation sorbitan esters and non-ethoxylated sorbitan esters binding ratio also is provided.
The present invention soaks composition, by composition total weight, comprises described sorbitan esters of 0.001%-15% or their mixture, preferred 0.01%-10%, more preferably 0.1%-5%, most preferably 0.5%-4%.Nonionogenic tenside
Second kind of necessary component of the present composition is according to formula RO-(A)
nThe alkoxy-based non-ionic surface active agent of H or their mixture, wherein R is replacement or unsubstituted, the saturated or unsaturated straight or branched hydrocarbon chain with 6-40 carbon atom, and A is the alkoxyl group with 2-10 carbon atom, and wherein n is the integer of 9-100.
Preferred R has 6-40 carbon atom, preferred 8-25, the more preferably replacement of 12-20 carbon atom or unsubstituted, saturated or unsaturated straight or branched alkyl or aryl.General aryl comprises the C12-C18 alkyl phenyl.Preferred n is the integer of 9-100, more preferably 10-80, most preferably 10-30.Preferred A has 2-8 carbon atom, and the alkoxyl group of preferred 2-5 carbon atom is more preferably propoxy-and/or oxyethyl group.
Therefore being used for the alkoxy-based non-ionic surface active agent that the present invention is fit to is that (R is C to Dobanol 91-10
9-C
11The mixture of alkyl chain, A are oxyethyl groups, and n is 10), (wherein R is the mixture of straight chain C 16-C18 alkyl chain or the C13-C15 of non-branching for Luthensol AT or AO tensio-active agent, A is an oxyethyl group, and n can be 11,18,25,50 or 80), or their mixture.These Dobanol tensio-active agents can be purchased from SHELL, and Luthensol tensio-active agent can be buied from BASF.
The chemical process that is fit to that preparation is used for alkoxy-based non-ionic surface active agent of the present invention comprises with oxyalkylene in required ratio condensation correspondent alcohol.This method is well known to a person skilled in the art, and describes in the prior art widely.
This height alkoxy-based non-ionic surface active agent is particularly suitable for the present invention, because they improve the performance of degranulation spot.In fact, people infer that they are to work as soil-suspending agent, and promptly they make particulate fouling suspend and suppress/avoid described redeposition.
The present invention soaks composition, by composition total weight, comprises the described alkoxy-based non-ionic surface active agent of 0.001%-20% this paper definition or their mixture, preferred 0.01%-15%, more preferably 0.1%-10%, most preferably 0.5%-5%.Oxygen bleaching agent
Composition according to the present invention comprises oxygen bleaching agent or its mixture as the third necessary component.In fact, oxygen bleaching agent provides multiple effect, for example bleach spot, deodorization and disinfection.The sorbitan esters and the alkoxy-based non-ionic surface active agent of this paper definition also have the special benefits of oxytolerant SYNTHETIC OPTICAL WHITNER oxidation.Oxygen bleaching agent in the present composition can have various sources, for example any addition compound of hydrogen peroxide or hydrogen peroxide or organic peroxide acid or their mixture.The addition compound meaning of hydrogen peroxide is that hydrogen peroxide is added to the compound that forms so that addition compound to be provided on second kind of compound, and described second kind of compound for example can be inorganic salt, urea or organic carboxylate.The example of hydrogen peroxide addition compound comprises compound that inorganic perhydrate salt, hydrogen peroxide and organic carboxylate, urea form and the compound that closed by cage of hydrogen peroxide wherein.
The example of inorganic perhydrate salt comprises perborate, percarbonate, superphosphate and persilicate.Inorganic perhydrate salt is an alkali metal salt normally.Alkali metal percarbonate, perborate or their mixture are to be used for the preferred inorganic perhydrate salt of the present invention.Preferred alkali metal percarbonate is a SPC-D.
Other oxygen bleaching agents that are fit to comprise persulphate, particularly Potassium Persulphate K
2S
2O
8With Sodium Persulfate Na
2S
2O
8The example of inorganic perhydrate salt comprises perborate, percarbonate, superphosphate and persilicate.Inorganic perhydrate salt is an alkali metal salt normally.
Generally, the present invention soaks composition, by composition total weight, comprises 0.01%-80% oxygen bleaching agent or its mixture, preferred 5%-45%, more preferably 10%-40%.
It is particulate composition that the present invention soaks composition.Said composition can be used prepared in various methods commonly known in the art, comprise do to mix, spraying drying, agglomeration and granulation and their combination.The present composition can be prepared into has different bulk densities, from the particulate product of routine to so-called " concentrating " product (being that bulk density is higher than 600g/l).Optional components
The present invention soaks composition also can comprise various other components.
The preferred present composition also comprises the bleach-activating agent that accounts for composition total weight maximum 30% or their mixture.The example of this suitable compounds is disclosed among English Patent GB1586769 and the GB2143231.The preferred example of this compound is: tetra acetyl ethylene diamine (TAED), 3; 5; 5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt, such as for example at the diperoxy dodecylic acid described in the US4818425 with such as for example at the peroxide hexanodioic acid nonyl acid amides described in the US4259201 and positive nonanoly acyloxy benzene sulfonate (NOBS) with for example in the acetyl triethyl citrate (ATC) described in the european patent application 91870207.7.Also particularly preferably be the N-acyl caprolactam, it is selected from: replacement or unsubstituted benzoyl caprolactam, capryloyl hexanolactam, nonanoyl hexanolactam, caproyl hexanolactam, decanoyl hexanolactam, undecylene acyl caprolactam, formyl radical hexanolactam, ethanoyl hexanolactam, propionyl hexanolactam, butyryl radicals hexanolactam, pentanoyl hexanolactam.The present invention soaks the mixture that composition can comprise described bleach-activating agent.
The preferred bleach-activating mixtures of the present invention comprise positive nonanoly acyloxy benzene sulfonate (NOBS) with second kind to produce diacyl peroxide trend low and the combining of bleach-activating agent of peracid mainly be provided.Described second kind of bleach-activating agent can comprise tetraacetyl ethylene diamine (TAED), acetyl triethyl citrate (ATC), ethanoyl hexanolactam, formyl radical hexanolactam etc. or their mixture.In fact; found to comprise that the bleach-activating agent of positive nonanoly acyloxy benzene sulfonate and the mixture of described second kind of bleach-activating agent help further to promote the degranulation fouling performance, and shown good performance to the dirt (for example β-Hu Luobusu) of diacyl peroxide sensitivity with to the dirt (for example human body dirt) of peracid sensitivity simultaneously.
Therefore, the present invention soaks composition, by composition total weight, can comprise the positive nonanoly acyloxy benzene sulfonate of 0%-15%, preferred 1%-10%, more preferably 3%-7%; With by composition total weight, the described second kind of bleach-activating agent of 0%-15%, preferred 1%-10%, more preferably 3%-7%.
Can comprise acid system in the preferred optional component of the present composition.The purpose of described acid system is in order to control the alkalescence that any basic cpd of existing in the source that can get oxygen and the washing soln produces.Described system comprises anhydrous acidizing reagent or their mixture, and they need mix in the product and under well-oxygenated environment with anhydrous form has good stability.Being used for the anhydrous acidizing reagent that the present invention is fit to is carboxylic acid, for example citric acid, hexanodioic acid, pentanedioic acid, 3chetoglutaric acid, citromalic acid (citramalic acid), tartrate and toxilic acid or their salt or their mixture.Other acidizing reagents that are fit to comprise sodium bicarbonate, concentrated crystal soda and silicic acid.Be used for the highly preferred acid system of the present invention and comprise citric acid and/or Trisodium Citrate.In fact, citric acid can its sour form or with its salt (single, two-, three-salt) form use and all can be anhydrous and form hydration or their mixture.It also can be used as washing assistant and sequestrant, and it is biodegradable.According to composition of the present invention, by composition total weight, comprise maximum 20% Citric Acid, usp, Anhydrous Powders, preferred 5%-15%, most preferably from about 10%.
The present composition can comprise alkalimetal silicate or their mixture in the preferred optional component.Being used for the preferred alkalimetal silicate of the present invention is water glass.In the preferred embodiment of the invention, wherein soak composition and comprise oxygen bleaching agent, found that when soaking composition dissolves owing to there are at least hundred 40/10000ths parts of water glass in the described immersion aqueous solution, the decomposition of therefore soaking the got oxygen that produces in the aqueous solution is lowered.
The present invention can use the alkalimetal silicate of any kind, comprises crystallization type and unbodied described alkalimetal silicate or its mixture.
The crystal type water glass that is fit to use is to have the crystalline layered silicate particle of following formula or their mixture:
NaMSi
xO
2X+1.yH
2O wherein M is sodium or hydrogen, and x is the numerical value of 1.9-4, and y is the numerical value of 0-20.Such crystalline layered sodium silicate is disclosed among the EP-A-164514, and their preparation method is disclosed among DE-A-3417649 and the DE-A-3742043.For the object of the invention, the numerical value of the x in the above general formula is 2,3 or 4, is preferably 2.More preferably M is a sodium, and y is 0, and this formula preferred examples comprises a, b, g and d type Na
2Si
2O
5These materials can be buied from Hoechst AG FRG, are respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6.Most preferred material is d-Na
2Si
2O
5, NaSKS-6.Crystalline layered silicate can be done mixed solid form or soak in the composition as being incorporated into the present invention with the agglomerant solid ingredient of other components.
Be used for the amorphous sodium silicate that the present invention is fit to and have following general formula:
NaMSi
xO
2X+1Wherein M is sodium or hydrogen, and x is the numerical value of 1.9-4, or their mixture.Be used for preferably amorphous Si of the present invention
2O
5Na
2O.
Being used for the zeolite that the present invention is fit to is silico-aluminate, comprises those with following empirical formula:
M
z(zAlO
2.ySiO
2) wherein M be the ammonium of sodium, potassium, ammonium or replacement, z is about 0.5-about 2; Y is 1; It is that the anhydrous silico-aluminate of every gram is at least about 50 milligramequivalent CaCO that this material has magnesium ion exchange capacity
3Hardness.Preferred zeolite has following formula:
Naz[(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 about 0.5 scope, and x is about 15 to about 264 integer.
Useful alumino-silicate materials is commercially available.These silico-aluminates can be crystallization or amorphous structure, and can naturally occurring silico-aluminate or synthetic obtaining.The method for preparing aluminosilicate ion exchange material is disclosed in the people's such as Krummel that authorized on October 12nd, 1976 the U.S. Pat 3985669.The preferred synthetic crystallization aluminosilicate ion exchange material that is used for this paper can buy by trade(brand)name zeolite A, zeolite P (B) and X zeolite.In particularly preferred embodiments, the crystal aluminosilicate ion-exchange material has following formula:
Na
12[(AlO
2)
12(SiO
2)
12] .xH
2O wherein x is 20-30, especially about 27.This material is called zeolite A.Silico-aluminate preferably has the granularity that diameter is about the 0.1-10 micron.
Generally, the present composition by composition total weight, can comprise 0.5%-15% alkalimetal silicate or their mixture, preferred 1%-10%, more preferably 2%-7%.
Also can comprise washing assistant in the preferred optional component of the present composition.Well known to a person skilled in the art that all washing assistants all can be used for the present invention.Be used for phosphate builders that the present invention is fit to and comprise tripoly phosphate sodium STPP and potassium, trisodium phosphate and potassium, the polymerization degree polymeric sodium-metaphosphate and potassium and sodium orthophosphate and potassium for about 6-21.Other phosphorous washing-aid compound is disclosed in United States Patent (USP) 3159581; 3213030; 3422021; 3422137; In 3400176 and 3400148, these patent documentations are quoted for referencial use at this paper.
Be used for the multi-carboxy acid salt washing agent that the present invention is fit to and comprise the ether multi-carboxylate, comprising as on January 18th, 3,128,287 and 1972 authorized the United States Patent (USP) 3 of Lamberti etc. at the United States Patent (USP) that on April 7th, 1964 was authorized Berg, disclosed oxygen di-succinate in 635,830.Also can be referring to " TMS/TDS " washing assistant in the United States Patent (USP) 4,663,071 of authorizing Bush etc. on May 5th, 1987.Suitable ether multi-carboxylate also comprises ring compound, alicyclic compound class particularly, and for example at United States Patent (USP) 3,923,679,3,835,163,4,120,874 and 4,102, those described in 903.
Other washing assistant that is suitable for comprises ether hydroxypolycarboxylic acid salt, 1,3,5-trihydroxybenzene-2,4, the 6-trisulfonic acid, carboxyl methoxyl group succsinic acid, the ammonium salt of various an alkali metal salts, ammonium salt and the replacement of polyacetic acid such as ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA), and multi-carboxylate, for example mellitic acid, succsinic acid, oxygen di-succsinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyl oxosuccinic acid and soluble salt thereof.
The present invention soak in the composition also be fit to be authorize in the United States Patent (USP) 4,566,984 of Bush on January 28th, 1986 disclosed 3,3-dicarboxyl-4-oxa--1,6-adipate and related compound.The succsinic acid washing assistant that is suitable for comprises C
5-C
20Alkyl and alkenyl succinic and salt thereof.The particularly preferred compound of this class is the dodecenyl succinic succsinic acid.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 this type of preferred washing assistant, in the european patent application of announcing on November 5th, 1,986 86200690.5/0,200,263 explanation is arranged.
Authorize the United States Patent (USP) 4,144,226 of Crutchfield etc. and authorized on March 7th, 1967 in the United States Patent (USP) 3,308,067 of Diehl on March 13rd, 1979 and disclose other multi-carboxy acid salt washing agent who is suitable for.Be also shown in the United States Patent (USP) 3,723,322 of Diehl.
Being used for other multi-carboxy acid salt washing agents that are fit to of the present invention comprises according to the washing assistant of formula I or their mixture:
Wherein Y is the mixture of comonomer or comonomer; R
1And R
2Be to SYNTHETIC OPTICAL WHITNER and alkali stable polymer end group; R
3Be H, OH or C
1-4Alkyl; M is the ammonium of H, basic metal, alkaline-earth metal, ammonium or replacement; P is 0-2; N is at least 10.
Be used for preferred polymers of the present invention and be divided into two classes.The first kind belongs to the copolymerized polymer class, its by unsaturated poly carboxylic acid for example toxilic acid, citraconic acid, methylene-succinic acid, methylfumaric acid and their salt as first monomer and unsaturated monocarboxylic for example vinylformic acid or a-C
1-4Alkyl acrylic makes as second monomer.With reference to this paper following formula I, the polymkeric substance that belongs to the described first kind is that wherein p is not 0, and Y is selected from those polymkeric substance of the above listed acid of this paper.Such preferred polymkeric substance is that wherein Y is a toxilic acid according to those of following formula I.In addition, in preferred embodiments, R
3With M be H, n makes that the molecular weight of polymkeric substance is the 1000-400000 atomic mass unit.
Be used for the second class preferred polymers of the present invention and belong to base polymer down, wherein with reference to following formula I, p is 0, R
3Be H or C
1-4Alkyl.In preferred embodiments, n makes that the molecular weight of polymkeric substance is the 1000-400000 atomic mass unit.In highly preferred embodiment, R
3With M be H.
Alkali stable polymer terminal group R among the following formula I
1And R
2Compatibly comprise alkyl, oxyalkyl and alkane carboxyl and their salt and ester.
In following formula, the polymerization degree n of polymkeric substance can be by determining divided by the monomer molecular-weight average with the polymkeric substance weight-average molecular weight.Therefore, be 15500 and comprise 30 moles of unitary maleic acid-acrylic acid copolymers of % toxilic acid deutero-that for weight-average molecular weight n is 182 (i.e. 15500/ (116 * 0.3+72 * 0.7)).
The controlled temperature post of relative sodium polystyrene sulfonate polymkeric substance standard can be by Polymer Laboratories Ltd. down at 40 ℃, Shropshire, and UK obtains.This polymkeric substance standard is 0.15M SODIUM PHOSPHATE, MONOBASIC and the 0.02M Tetramethylammonium hydroxide in 80/20 water/acetonitrile.
In all above polymkeric substance, being used for the highly preferred polymkeric substance of the present invention is first kind polymkeric substance, wherein n average out to 100-800, preferably 120-400.
Being used for the preferred washing assistant of the present invention is toxilic acid or polymerizing acrylic acid thing, or toxilic acid and acrylic acid multipolymer.
Generally, the present composition by composition total weight, comprises maximum 50% washing assistants or their mixture, preferred 0.1%-20%, more preferably 0.5%-11%.
Preferred the present invention soaks composition and also comprises sequestrant or its mixture.Sequestrant is the present invention's needs, because it helps to be controlled at the free heavy metal ion amount of soaking in the aqueous solution, has therefore avoided the quick decomposition of the oxygen of oxygen bleaching agent release.Can be used for suitable aminocarboxylate sequestrant of the present invention and comprise diethylentriamine pentacetate, edetate (EDTA), the N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, with ethanol Diglycocol, their an alkali metal salt, ammonium salt and substituted ammonium salt and their mixture.Also the sequestrant of Shi Heing comprises quadrol-N, the ammonium salt of N '-disuccinic acid (EDDS) or their basic metal, alkaline-earth metal, ammonium or replacement.Particularly suitable EDDS compound is free acid form and their sodium or magnesium salts or title complex.Other sequestrants that also are fit to can be organic phosphonates, comprise amino alkylidenyl (polyalkylene phosphonate), basic metal ethane 1-hydroxyl diphosphonate, nitrilo trimethylene phosphonic salt, ethylenediamine tetramethylene phosphonic acid salt and diethylenetriamine pentamethylenophosphonic acid(DTPP) salt.Phosphonate compounds can their sour forms or alkali metal salt existence.Preferably, the organic phospho acid salt compound exists with the form of their magnesium salts.
The present invention soaks composition so can comprise and accounts for the described sequestrant of composition total weight 0%-5%, preferred 0%-3%, more preferably 0.05%-2%.
Except aforesaid sorbitan esters of this paper and alkoxy-based non-ionic surface active agent, the present composition also can comprise other tensio-active agents.This tensio-active agent needs, because they can further help the effect of the present composition, promptly improves the decontamination stain performance to particulate fouling and other types dirt such as enzyme stain and/or oil stain.
Except aforesaid sorbitan esters of this paper and alkoxy-based non-ionic surface active agent, this tensio-active agent can be present in the present invention and soak in the composition, and by composition total weight, its content is 0.1%-50%, preferred 0.1%-20%, more preferably 1%-10%.Be used for tensio-active agent of the present invention and comprise nonionogenic tenside, anion surfactant, cats product, amphoterics, zwitterionics and their mixture.
The anion surfactant that the present invention is suitable for comprises formula ROSO
3The water-soluble salt of M or acid, wherein R C preferably
10-C
24Alkyl preferably has C
10-C
20The alkyl of moieties or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, M is H or positively charged ion, alkali metal cation (for example sodium, potassium, lithium) for example, or the ammonium of ammonium or replacement (for example methyl, dimethyl and trimethyl ammonium positively charged ion, with quaternary ammonium cation for example tetramethyl-ammonium and lupetidine positively charged ion, and by alkylamine for example ethamine, diethylamine, triethylamine and its mixture deutero-quaternary ammonium cation etc.).Generally, for low wash temperature (for example being lower than about 50 ℃), C
12-16Alkyl chain is preferred, and for higher wash temperature (for example being higher than about 50 ℃), C
16-18Alkyl chain is preferred.
Being used for the anion surfactant that other is fit to of the present invention is formula RO (A)
mSO
3The water-soluble salt of M or acid, wherein R is unsubstituted C
10-C
24Alkyl or have C
10-C
24The hydroxyalkyl of moieties, preferred C
12-C
20Alkyl or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is greater than 0, generally between about 0.5-6, more preferably between about 0.5-3, M is H or positively charged ion, it can be a metallic cation (for example sodium, potassium, lithium, calcium, magnesium etc.) for example, the ammonium cation of ammonium or replacement.Alkyl ethoxylated sulfate and alkyl propoxylated sulphates are that the present invention expects.The object lesson of the ammonium cation that replaces comprises methyl, dimethyl, trimethyl ammonium and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine and by alkanolamine for example ethamine, diethylamine, triethylamine and its mixture deutero-positively charged ion etc.Exemplary tensio-active agent is C
12-C
18Alkyl polyethoxylated (1.0) vitriol (C
12-C
18E (1.0) M), C
12-C
18Alkyl polyethoxylated (2.25) vitriol (C
12-C
18E (2.25) M), C
12-C
18Alkyl polyethoxylated (3.0) vitriol (C
12-C
18E (3.0)) and C
12-C
18Alkyl polyethoxylated (4.0) vitriol (C
12-C
18E (4.0) M), wherein M is selected from sodium and potassium usually.
The present invention also can use other to be used for the anion surfactant of decontamination purpose.They can comprise soap salt (comprise, for example the ammonium salt of sodium, potassium, ammonium and replacement for example one, two and tri ethanol ammonium salt), C
9-C
20Linear alkylbenzene sulfonate, C
8-C
24The sulfonation poly carboxylic acid that alkene sulfonate, the pyrolysis product by the sulfonation alkaline earth metal citrate make for example at british patent specification No1, is described C in 082,179
8-C
24Methyl polyethylene glycol ether sulfate (containing as many as 10 mole oxygen ethene); Alkyl ester sulfonate is C for example
14-C
16Alkyl ester sulfonate, acylglycerol sulfonate, fatty oil acylglycerol vitriol, alkyl phenol epoxy ethane ether salt, alkylphosphonic, isethionate be acyl isethinate, N-acyl amino esilate, amber alkyl amide salts and sulfosuccinate, sulfosuccinate monoesters (especially saturated and undersaturated C for example
12-C
18Monoesters), sulfosuccinate diester (especially saturated and undersaturated C
6-C
14Diester), for example alkyl polyglucoside vitriol (compound of nonionic non-sulfuric acidization described below), chain primary alkyl sulfate, alkyl polyethoxye carboxylate salt for example have formula RO (CH for acyl sarcosinate, alkyl polysaccharide vitriol
2CH
2O)
KCH
2COO
-M
+Those, wherein R is C
8-C
22Alkyl, k are the integers of 0-10, and M is the positively charged ion that forms soluble salt.Resinous acid and hydrogenated resin acid also are fit to, rosin for example, staybelite and be present in tallol or by its deutero-resinous acid and hydrogenated resin acid.Other example is described in " tensio-active agent and washing composition " (I and II volume, Schwartz, Perry and Berch).Many this tensio-active agents also usually are disclosed in the people's such as Laughlin that authorized on December 30th, 1975 U.S.3, and in 929,678,23 hurdles 58 walk to 29 hurdles, 23 row (being quoted as a reference by this paper).
Being used for other anion surfactants that the present invention is fit to also comprises according to formula RSO
3Those of M, wherein R is replacement or unsubstituted, saturated or unsaturated, the straight or branched hydrocarbon chain with 6-40 carbon atom, M is H or positively charged ion, preferred R has 6-40 carbon atom, preferred 8-30 carbon atom, more preferably 10-25 carbon atom, the most preferably replacement of 12-18 carbon atom or unsubstituted, saturated or unsaturated, straight or branched alkyl.Preferred M is a positively charged ion, it can be that for example metallic cation is (for example, sodium, potassium, lithium, calcium, magnesium etc.), the ammonium of ammonium or replacement (for example methyl-, dimethyl-, with trimethyl ammonium positively charged ion and quaternary ammonium cation for example tetramethyl-ammonium and lupetidine positively charged ion and by alkylamine for example ethamine, diethylamine, triethylamine and its mixture deutero-quaternary ammonium cation etc.).Being used for the anionic sulphonate that the present invention is fit to is the paraffinic hydrocarbons sodium sulfonate.They can be from Hoescht by trade(brand)name Hostapur
Or Hostatat
Be purchased.
The present composition also can comprise filler such as mineral filler salt, for example alkaline carbonate, supercarbonate and vitriol.This filler is sodium bicarbonate for example, also can be used as acidizing reagent described below.Therefore, sodium bicarbonate and sodium sulfate are to be used for the preferred filler of the present invention.
Generally, the present composition by composition total weight, comprises as many as 50% filler or its mixture, preferred 0.1%-20%, more preferably 0.5%-10%.
The present composition generally also comprises enzyme or its mixture.The preferred present composition comprises proteolytic enzyme or its mixture.Proteolytic enzyme in the preferred embodiment of the invention usually to be enough to provide the active amount of every gram composition 0.005-0.2Anson unit (AU) to exist.Proteolytic ferment can be from animal, plant or preferably from microbial source.The serine proteinase enzyme of bacterial origin more preferably.Can use the enzyme of purifying or non-purifying.The proteolytic ferment that produces by chemistry or genetically altered mutant is included in this definition, and they are the close enzyme variants of structure.Particularly preferred proteolytic ferment is the bacterial serine proteolytic ferment that is obtained by subtilis of bacillus and/or bacillus licheniformis.The commercially available proteolytic ferment that is fit to comprises Alcalase
, Esperase
, Durazym
, Savinase
, Maxatase
, Maxacal
With Maxapem 15
(Maxacal of protein engineering); Purafect
With subtilysin BPN and BPN ' also be commercially available.Preferred proteolytic enzymes also comprises the bacterial serine proteolytic enzyme of modification, and as the disclosed proteolytic enzyme of EP patent application serial number 87303761.8 (1987.4.28 application) (particularly the 17th, 24 and 98 page), it is called as " proteolytic enzyme B " in this article; The EP199 that also comprises Venegas, disclosed proteolytic enzyme in 404 (announcements on October 29th, 1986), it relates to the bacterial serine protease of modification, and it is called as " protease A " in this article.More preferably be referred to herein as the proteolytic enzyme of " proteolytic enzyme C ", this proteolytic enzyme is three varients from the alkaline serine protease of bacillus, wherein, 104 place's tyrosine replace Xie Ansuan in the position, 123 place's Serines replace l-asparagine in the position, and 274 place's L-Ala replace Threonine in the position.Proteolytic enzyme C states in the EP90915958:4 corresponding to WO91/06637 (1991.5.16 is open), and the document is quoted for referencial use at this paper.Genetically altered varient, particularly the varient of proteolytic enzyme C is also included within the scope of the invention.What be used for that the present invention also is fit to is the proteolytic enzyme that is called " proteolytic enzyme D " here, it is a kind of carbonylic hydrolase varient, it has at the undiscovered aminoacid sequence of nature, it is according to the bacillus amyloliquefaciens subtilisin, a plurality of amino-acid residues are replaced with different amino acid at position+76 places by the precursor carbonylic hydrolase corresponding to described carbonylic hydrolase, be incorporated into the replacement of the corresponding one or more amino-acid residues that are selected from following position simultaneously and obtain :+99, + 101, + 103, + 107 and+123, as at A.Baeck, C.K.Ghosh, P.P.Greycerg, the U.S. Patent Application Serial Number of R.R.Bott and L.J.Willson co-applications is 08/136797 (P﹠amp; G case 5040), exercise question in " cleaning composition that contains proteolytic enzyme " and U.S. Patent Application Serial Number be in 08/136626 " bleaching composition that contains proteolytic enzyme " description to be arranged, they quote for referencial use at this paper.
Some preferred proteolytic enzymes are selected from Savinase
, Esperase
,, Maxacal
, Purafect
, BPN ', protease A and proteolytic enzyme B and their mixture.The bacterial serine proteolytic enzyme that is obtained by subtilis and/or bacillus licheniformis is preferred.Particularly preferably be Savinase
, Alcalase
, protease A and proteolytic enzyme B.
Generally, the present composition also comprises amylase or their mixture.Improve stability, for example the enzyme engineering of oxidative stability is known.Referring to, for example " journal of biological chemistry ", the 260th volume, o. 11th, in June, 1985,6518-6521 page or leaf." reference enzyme " hereinafter is meant the amylase outside amylase compositional range of the present invention and it can measure any diastatic stability in the scope of the invention relatively.
Therefore, the present invention can utilize and have the amylase that improves stability, the amylase that especially has the oxidative stability of improvement in washing composition.The amylase that uses among the present invention shows that a kind of absolute stable easily reference point of a kind of detectable improvement institute reference is the stability at the TERMAMYL (R) that is buied by Novo Nordisk A/S of industrial use in 1993.This TERMAMYL (R) amylase is " with reference to amylase ".The amylase that belongs in the spirit and scope of the invention has the diastatic feature of " stability strengthens ", with top definite with reference to the amylase comparative determination, its feature is to have one or more detectable improvement at least: oxidative stability, for example, in the buffered soln of pH9-10 to the stability of hydrogen peroxide/tetra acetyl ethylene diamine; Thermostability, for example, under the common wash temperature according to appointment under 60 ℃ the temperature; Or alkaline stability, for example under the about 8-11 of pH.What the preferred amylase susceptible of proof of the present invention was relatively more challenging has further improvement with reference to amylase, the latter with reference to amylase by exemplifying explanation for diastatic any precursor amylase of mutant in the scope of the invention.They itself can be the product of natural or genetic engineering for this precursor amylase.Stability can be used disclosed any experimental technique mensuration in the prior art.Referring to disclosed reference in WO94/02597, this patent and the reference of wherein quoting are quoted for referencial use at this paper.
Generally, can obtain from Novo NordiskA/S or from Genencor International about stable enhanced amylase of the present invention.
The preferred amylase of the present invention has a common ability, promptly uses site-directed mutagenesis method from one or more bacillus amylases, and especially the bacillus α-Dian Fenmei is derived and obtained, no matter and whether have a kind ofly, two or more amylase strains are direct precursors.
As described, be used for the preferably amylase of " oxidative stability enhancing " of the present invention, this amylase carries out unrestricted explanation by following example:
(a) according to the amylase among the WO94/02597 of the Novo Nordisk A/S that announces the 3 days February in 1994 of above quoting, it can be further specified by a kind of mutant, and (it is known TERMAMYL wherein to use L-Ala or Threonine (preferred Threonine) replacement to be positioned at the bacillus licheniformis α-Dian Fenmei
) the methionine residue of 197 positions, or similar homology amylase, as bacillus amyloliquefaciens, subtilis, or the homology positional variant of fatty thermophilic bacteria;
(b) the stable enhanced amylase of being described by Genencor International, this amylase is announced in the article of " oxidation resistant α-Dian Fenmei " with exercise question in the national meeting of the 207th American Chemical Society that holds 13-17 day in March, 1994 by C.Mitchinson.It should be noted that wherein the SYNTHETIC OPTICAL WHITNER in the automatic dishwashing washing composition makes the α-Dian Fenmei inactivation, but the amylase that improves oxidative stability is obtained from bacillus licheniformis NCIB8061 by Genencor.Methionine(Met) (Met) is confirmed as the residue that most probable is modified.Met is substituted one at every turn, and the position of substitution is 8,15, and 197,256,304,366 and 438, obtain special mutant, particularly importantly M197L and M197T, wherein the M197T variant is the variant that the most stable quilt is expressed.CASCADE (R) and SUNLIGHT (R) stability have been measured; This kind of enzyme can be purchased by trade(brand)name Plurafact Oxam from Genencor.
(c) particularly preferably be the amylase variant of buying from Novo Nordisk A/S that direct parent, has other modifications among the present invention.These amylase also do not have trade(brand)name, but they are to be called QL37+M197T by supplier.This kind of enzyme can be purchased by trade(brand)name SP 703 from Novo.
Can use any other oxidative stability enhanced amylase, for example known chimeric from what can buy by site-directed mutagenesis, the amylase of blended or simple mutant parent form is derived and is obtained.
The present invention soaks composition also can comprise soil-suspending agent or its mixture, generally its content as many as 20% weight, preferably 0.1%-10%, more preferably 0.5%-2%.The soil-suspending agent that is fit to comprises the ethoxylation diamines as describing among the EP-A-112593, the ethoxylation polyamine, and ethoxylated amine polymer, the document is quoted for referencial use at this paper.Be used for the preferred soil-suspending agent of the present invention and be included in ethoxylation polyvinylamine, ethoxylation 15-18 tetren, ethoxylation 15-18 polyvinylamine, ethoxylation 15-18 quadrol, the ethoxylation polymine that before ethoxylation, has molecular weight 600-1800 and their mixture that ethoxylation has molecular weight 140-310 before.
The present invention soaks composition also can comprise other optional components, for example for example phthalocyanine sulfonic acid zinc, dyestuff, dye transfer inhibitor, pigment, spices etc. of the SYNTHETIC OPTICAL WHITNER of white dyes, other enzymes, other sequestrants, dispersion agent, dirt release agent, photoactivation.Described optional components can add with the difference amount on demand.The B-method
The present invention includes the method for soaking fabric.In fact, the present invention includes a kind of method of soaking fabric, wherein said fabric floods effective for some time in the immersion aqueous solution of this paper above-mentioned composition that comprises water and significant quantity, takes out from the described immersion aqueous solution then.
" soaking the method for fabric " used herein this term is meant fabric is immersed in the immersion aqueous solution that comprises water and this paper above-mentioned composition through the sufficiently long time, to clean the effect of described fabric.Opposite with the general washing operation that uses washing machine, this paper immersion process allows fabric to contact for a long time general maximum 24 hours between the aqueous solution with soaking.This immersion process can carry out being independent of under for example general washing operation of any other method, or as second step be the first step before the general washing step.In the preferred immersion process of the present invention, fabric was soaked 10 minutes-24 hours, preferred 30 minutes-24 hours, more preferably more than 1 hour to 24 hours, even more preferably 2 hours to 24 hours, most preferably 4 hours-24 hours.After the sufficiently long time, they can be taken out and the water rinse in the described immersion aqueous solution at textile impregnation.Fabric also can wash in normal washing operation after the immersion, can carry out or not carry out rinse between dip operation and subsequent washing operation.
In immersion process of the present invention, the immersion composition that this paper is above-mentioned is diluted in the suitable quantity of water, makes the immersion aqueous solution.The dosage range that is fit to can be the 40-55 gram and soaks composition and be diluted in and soak composition to the 90-100 gram in the 3.5-5 premium on currency and be diluted in the 20-45 premium on currency.A kind of typical doses of dense immersion (container/groove) is that 40-55 gram immersion composition is diluted in the 3.5-5 premium on currency.Soak for washing machine, dosage is that 90-100 gram immersion composition is diluted in liter (US) water of about 20 liters of (Europe)-45.The fabric that soaks is the suitably long time of dipping in soaking the aqueous solution then.There are many factors can influence the overall performance of this method to particle earth/dirt.This factor comprises long immersion.In fact, fabric soaks long-time more, and net result is good more.Ideally, soak time is to spend the night, and as many as was 24 hours in promptly 8 hours, preferred 12 hours to 24 hours.Another factor is initial gentle or warm temperature.In fact, soak the higher initial temperature of the aqueous solution and guaranteed big benefit is arranged at aspect of performance.
The inventive method is applicable to cleans various fabrics, but finds to be preferably applied to soak socks, particularly is exposed to the flour sand and the argillous socks that carry.
Aspect the most widely, the present invention includes the method for soaking fabric, wherein described fabric was flooded in the immersion aqueous solution of the composition that comprises water and significant quantity more than 1 hour, preferred 2-24 hour, more preferably 4-24 hour, take out from the described immersion aqueous solution then, wherein said composition comprises oxygen bleaching agent and according to formula RO-(A)
nThe alkoxy-based non-ionic surface active agent of H, wherein R is replacement or unsubstituted, the saturated or unsaturated straight or branched hydrocarbon chain with 6-40 carbon atom, and A is the alkoxyl group with 2-10 carbon atom, and wherein n is the integer of 9-100.In fact, found when adding this height alkoxy-based non-ionic surface active agent in the immersion composition at oxygen-bearing bleaching agent, to have improved the degranulation dirt and gone enzyme stain performance.Decontamination stain method for testing performance
Can evaluate given composition by following test method and under soaking conditions, performance be steeped in the decontamination of polluting fabric.For example 45g the present invention is soaked that composition is diluted in 3.78 premium on currency or 90g is soaked composition and be diluted to and make the immersion aqueous solution in 45 premium on currency.Then fabric is flooded more than 1 hour to 18 hours in the immersion aqueous solution that makes.At last, fabric is taken out from soak the aqueous solution, the water rinse washs with conventional washing composition also with conventional washing methods, hand washing or machine washing, reuses the immersion aqueous solution again or not, then described fabric is placed dry.
For example, the typical pollution fabric that uses in this decontamination stain performance test can be from EMC (Empirical Manufacturing Company) Cincinnati, Ohio, USA is purchased, for example at two different substrates: earth, grass stain, macaroni condiments, gravy, dirty motor oil, makeup, barbecue condiments, tea, bloodstain are arranged on cotton (CW120) and poly-cotton (PCW28).
To use according to the pollution fabric of immersion compositions-treated of the present invention with use object of reference, for example do not contain this those fabrics of handling according to the same combination of height alkoxy-based non-ionic surface active agent of the present invention and relatively evaluate decontamination side by side and steep performance.Can use visual grading standard, determine difference by scoring unit of the panel of 0-4 scope (psu).
Following examples further specify the present invention: embodiment
Prepare following composition by the listed component of listed mixed. 1 ( ％/ ) 2 ( ％/ ) 3 ( ％/ ) 0.5 0.5 0.5 ( SMS ) 11 11 11NOBS 6 6 6 ( Acusol 445ND ) 11 11 11 31 31 31C14-C16EO25 2--C12-C16EO11-2-C12-C16EO50--2 8 8 8 ( LAS/AS/AES ) DTPA 0.2 0.2 0.2TAED 5 5 5 100 100 100 4 ( ％/ ) 5 ( ％/ ) 6 ( ％/ ) 2.5-- ( SMS ) EO 20-3.0 ( SMS EO20 ) EO20 0.5-3.0 ( STS EO 20 ) 10 10 10 ( Acusol 445ND ) 11 11 11 ( ； 1.6r) 0.4 0.4 0.4 SODIUM PERCARBONATEs, 31 31 31NOBS, 66 6TAED, 555 anion surfactant 777 (LAS/AS/AES) C14-C16 (EO25) alcohol, 222 other, (% weight/weight) 9 (% weight/weight) anhydrosorbitol monostearate--0.5 (SMS) citric acid, 10 10 10 polyacrylates (Acusol 445ND), 11 11 11 silicate are (amorphous for inertia and accessory constituent to 100 to 100 to, 100 components 7 (% weight/weight) 8; 1.6r) the pure 2-2NaPS 2 2-SODIUM PERCARBONATEs of 0.4 0.4 0.4C12-C16 (EO11) alcohol-2 2C14-C16 (EO25) 31 31 31 sodium sulphate 24 24 24NOBS 66 6TAED 5 11 5 anion surfactants 888 (LAS/AS/AES) other, inertia and accessory constituent to 100 be that tetrem acyl ethylenediamine NOBS is that positive nonanoly acyloxy benzene sulfonate NaPS is that alkane sodium sulfonate DTPA is diethylene-triamine pentaacetic acid to 100 to 100TAED.
The 45g above-mentioned composition is diluted at every turn and makes the immersion aqueous solution in the 3.5-5.0 premium on currency.Then at every turn with the 0.5-2Kg textile impregnation in the described immersion aqueous solution.The soak time that comprises the immersion aqueous solution of arbitrary above-mentioned immersion composition 1-6 or 9 generally is 10 minutes-24 hours.
For the immersion aqueous solution that comprises the above-mentioned immersion composition 7 of this paper or 8, the soak time of immersion process is more than 1 hour according to the present invention, preferred 4-24 hour.
At last, fabric is taken out from soak the aqueous solution, the water rinse washs with conventional washing composition also with conventional washing methods, hand washing or machine washing, reuses the immersion aqueous solution again or not, then described fabric is placed dry.These compositions comprise mud/soil stain and enzyme stain to various spots and/or the spot that can bleach etc. has obtained good decontamination stain performance.
Claims (13)
1. granular immersion composition, it comprises :-pressing general composition weight meter, 0.001%-15% is according to formula C
6H
9O
2(C
2H
4O)
xR
1R
2R
3Sorbitan esters, wherein x is the integer of 0-40, R
1, R
2Be OH or (C independently
nH
2n+1) COO, R
3Be (C
nH
2n+1) the COO group, wherein n is the integer of 11-17 ,-pressing general composition weight meter, 0.001%-20% is according to formula RO-(A)
nThe alkoxy-based non-ionic surface active agent of H, wherein R is replacement or unsubstituted, the saturated or unsaturated straight or branched hydrocarbon chain with 6-40 carbon atom, A be have the alkoxyl group of 2-10 carbon atom and wherein n be the integer of 9-100 ,-and oxygen bleaching agent.
2. according to the composition of claim 1, by composition total weight, it comprises 0.01%-10%, preferred 0.1%-5%, more preferably described sorbitan esters of 0.5%-4% or their mixture.
3. according to the composition of arbitrary aforesaid right requirement, wherein said sorbitan esters is polyethoxylated (20) anhydrosorbitol tristearate, polyethoxylated (20) anhydrosorbitol monostearate, anhydrosorbitol monostearate, sorbitan-monopalmityl ester or their mixture.
4. according to the composition of arbitrary aforesaid right requirement, it comprises non-ethoxylated sorbitan esters and ethoxylation sorbitan esters.
5. according to the composition of arbitrary aforesaid right requirement, it comprises 0.01%-15%, preferred 0.1%-10%, more preferably described alkoxy-based non-ionic surface active agent of 0.5%-5% or their mixture.
6. according to the composition of arbitrary aforesaid right requirement, wherein said alkoxy-based non-ionic surface active agent has formula RO-(A)
nH, wherein R has 6-40 carbon atom, preferred 8-25, the more preferably replacement of 10-20 carbon atom or unsubstituted, saturated or unsaturated straight or branched alkyl, n is 9-100, more preferably 10-80, the integer of 10-30 most preferably, A is the alkoxyl group with 2-8 carbon atom, preferably propoxy-and/or oxyethyl group.
7. according to the composition of arbitrary aforesaid right requirement, by composition total weight, it comprises 0.01%-80%, preferred 5%-45%, more preferably 10%-40% oxygen bleaching agent or its mixture.
8. according to the composition of arbitrary aforesaid right requirement, wherein said oxygen bleaching agent is an alkali metal percarbonate.
9. according to the composition of arbitrary aforesaid right requirement, it also comprises the activator that is used for described SYNTHETIC OPTICAL WHITNER that accounts for composition total weight maximum 30%.
10. the composition that requires according to arbitrary aforesaid right, it also comprises and is selected from following at least a optional components: acidizing reagent, alkalimetal silicate, washing assistant, soil-suspending agent, filler, other tensio-active agents, white dyes, enzyme, sequestrant, dispersion agent, dirt release agent, dyestuff, dye transfer inhibitor, pigment, spices and their mixture.
11. a method of soaking fabric, wherein with described fabric comprise water and significant quantity according to the immersion aqueous solution of the composition of arbitrary aforementioned claim in effective for some time of dipping, from the described immersion aqueous solution, take out then.
12. according to the method for claim 11, the wherein said time is at 10 minutes-24 hours, and preferred 30 minutes-24 hours, more preferably more than 1 hour to maximum 24 hours, most preferably in 4 hours-24 hours scopes.
13. method of soaking fabric, wherein described fabric was flooded in the immersion aqueous solution of the composition that comprises water and significant quantity more than 1 hour, preferred 2-24 hour, more preferably 4-24 hour, take out from the described immersion aqueous solution then, wherein said composition comprises oxygen bleaching agent and according to formula RO-(A)
nThe alkoxy-based non-ionic surface active agent of H, wherein R is replacement or unsubstituted, the saturated or unsaturated straight or branched hydrocarbon chain with 6-40 carbon atom, A be have the alkoxyl group of 2-10 carbon atom and wherein n be the integer of 9-100.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP97870028.4 | 1997-02-27 | ||
| EP97870028A EP0861884B1 (en) | 1997-02-27 | 1997-02-27 | Soaker compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1253580A true CN1253580A (en) | 2000-05-17 |
Family
ID=8230982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98804568.0A Pending CN1253580A (en) | 1997-02-27 | 1998-02-13 | Soaker compositions |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0861884B1 (en) |
| JP (1) | JP2001513136A (en) |
| CN (1) | CN1253580A (en) |
| AT (1) | ATE271595T1 (en) |
| AU (1) | AU6277298A (en) |
| BR (1) | BR9812423A (en) |
| DE (1) | DE69729933T2 (en) |
| ES (1) | ES2221683T3 (en) |
| HU (1) | HUP0002009A2 (en) |
| NO (1) | NO994142L (en) |
| PL (1) | PL335507A1 (en) |
| WO (1) | WO1998038272A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002528654A (en) * | 1998-10-23 | 2002-09-03 | ザ、プロクター、エンド、ギャンブル、カンパニー | Cloth color protection method |
| US7041630B1 (en) | 1998-10-23 | 2006-05-09 | The Procter & Gamble Company | Fabric color care method for rejuvenating and/or restoring color to a faded fabric |
| DE102004036067A1 (en) * | 2004-07-24 | 2006-02-16 | Goldschmidt Gmbh | Aqueous cleaning agent concentrates for rough, in particular profiled tiles |
| GB0805908D0 (en) * | 2008-04-01 | 2008-05-07 | Reckitt Benckiser Inc | Laundry treatment compositions |
| MX2010013389A (en) * | 2008-06-06 | 2011-03-29 | The Procter & Gamble Company Star | Hand fabric laundering system. |
| WO2009148801A1 (en) * | 2008-06-06 | 2009-12-10 | The Procter & Gamble Company | Hand fabric laundering method |
| US20130111677A1 (en) * | 2010-08-30 | 2013-05-09 | Novozymes A/S | Concentrated Soak Wash |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| LU30381A1 (en) * | 1950-08-05 | |||
| LU52892A1 (en) * | 1967-01-27 | 1968-08-28 | ||
| US4441881A (en) * | 1982-09-07 | 1984-04-10 | Lever Brothers Company | Detergent compositions containing ethoxylated fatty alcohols with narrow ethylene oxide distributions |
| DE3424987A1 (en) * | 1984-07-06 | 1986-02-06 | Unilever N.V., Rotterdam | METHOD FOR PRODUCING A POWDERED DETERGENT WITH INCREASED SHOULDER WEIGHT |
| JPS621792A (en) * | 1985-06-28 | 1987-01-07 | 花王株式会社 | Bleaching composition |
| US5089162A (en) * | 1989-05-08 | 1992-02-18 | Lever Brothers Company, Division Of Conopco, Inc. | Cleaning compositions with bleach-stable colorant |
| JPH03287700A (en) * | 1990-04-04 | 1991-12-18 | Yuukou Yakuhin Kogyo Kk | Mildew remover |
| EP0736594A1 (en) * | 1995-04-03 | 1996-10-09 | The Procter & Gamble Company | Soaker compositions |
| EP0738777B1 (en) * | 1995-04-20 | 2004-04-14 | Kao Corporation | Bleaching detergent composition |
| JPH1017894A (en) * | 1996-07-04 | 1998-01-20 | Kao Corp | Liquid bleaching composition |
-
1997
- 1997-02-27 ES ES97870028T patent/ES2221683T3/en not_active Expired - Lifetime
- 1997-02-27 DE DE69729933T patent/DE69729933T2/en not_active Expired - Fee Related
- 1997-02-27 EP EP97870028A patent/EP0861884B1/en not_active Expired - Lifetime
- 1997-02-27 AT AT97870028T patent/ATE271595T1/en not_active IP Right Cessation
-
1998
- 1998-02-13 HU HU0002009A patent/HUP0002009A2/en unknown
- 1998-02-13 AU AU62772/98A patent/AU6277298A/en not_active Abandoned
- 1998-02-13 BR BR9812423-4A patent/BR9812423A/en not_active IP Right Cessation
- 1998-02-13 JP JP53768898A patent/JP2001513136A/en not_active Withdrawn
- 1998-02-13 WO PCT/US1998/002720 patent/WO1998038272A1/en not_active Application Discontinuation
- 1998-02-13 CN CN98804568.0A patent/CN1253580A/en active Pending
- 1998-02-13 PL PL98335507A patent/PL335507A1/en unknown
-
1999
- 1999-08-26 NO NO994142A patent/NO994142L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| PL335507A1 (en) | 2000-04-25 |
| DE69729933D1 (en) | 2004-08-26 |
| DE69729933T2 (en) | 2005-08-25 |
| AU6277298A (en) | 1998-09-18 |
| EP0861884A1 (en) | 1998-09-02 |
| NO994142D0 (en) | 1999-08-26 |
| JP2001513136A (en) | 2001-08-28 |
| WO1998038272A1 (en) | 1998-09-03 |
| ATE271595T1 (en) | 2004-08-15 |
| ES2221683T3 (en) | 2005-01-01 |
| NO994142L (en) | 1999-10-21 |
| HUP0002009A2 (en) | 2000-12-28 |
| EP0861884B1 (en) | 2004-07-21 |
| BR9812423A (en) | 2000-09-26 |
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
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