CN1207781A - Liquid bleaching compositions packaged in spray-type dispenser and process for pretreating fabrics therewith - Google Patents
Liquid bleaching compositions packaged in spray-type dispenser and process for pretreating fabrics therewith Download PDFInfo
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- CN1207781A CN1207781A CN96199727A CN96199727A CN1207781A CN 1207781 A CN1207781 A CN 1207781A CN 96199727 A CN96199727 A CN 96199727A CN 96199727 A CN96199727 A CN 96199727A CN 1207781 A CN1207781 A CN 1207781A
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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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0017—Multi-phase liquid compositions
- C11D17/0021—Aqueous microemulsions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/391—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Textile Engineering (AREA)
- Detergent Compositions (AREA)
Abstract
Liquid pretreater compositions packaged in a spray-type dispenser are described, said compositions comprising a peroxygen bleach, a surfactant and a bleach activator. A process of cleaning fabrics with a liquid composition comprising a peroxygen bleach and a surfactant, said process comprising the steps of dispensing said composition from a spray-type dispenser onto at least a portion of said fabrics, allowing said composition to remain in contact with said fabrics and then washing said fabrics, is said to reduce the loss of tensile strength and/or the color damage in said fabrics.
Description
Technical field
The present invention relates to the pretreating agent composition BLEACHED FABRIC that contains peroxygen bleach that is packaged in the spray-type dispenser.
Background technology
In the art, at laundering of textile fabrics pre-treatment fabric, usually being referred to as the fabric preliminary treatment, is well-known.In fact, but knownly in the laundry preliminary treatment is used, use the composition that contains peroxygen bleach so that improve the removal that is difficult to bleaching soilng/dirt of removing with other method especially.Directly apply such liquid peroxy bleach compositions by being poured on dirt/stain fabric, then randomly by leniently rubbing so that help to make this washing agent to penetrate in the fabric.
, the convenient use to peroxygen bleach has some restriction.Especially, we observe: when it is used for the preliminary treatment application, promptly be coated to fabric and before the described fabric of washing, stay on the described fabric for a long time so that when working when directly (pure), the composition that contains peroxygen bleach can damage fabric, thereby causes tensile strength loss and/or color to be damaged.
Therefore, the objective of the invention is safety to fabrics and/or the color safety that improves to be offered described fabric when when containing peroxygen bleach composition pretreating fabrics.
We have been found that now: contain the fluid composition of peroxygen bleach and surfactant by preparation, and by with described composition by with spray-type dispenser with its spray application in wanting can to realize this purpose effectively on pretreated this fabric.In fact, have now found that: before the described fabric of washing, with not being that it is sprayed to mode on dirt/stain fabric, for example by described composition is poured on the described fabric simply, applying identical fluid composition compares, with with the identical fluid composition of spraying but compare without any surfactant, be sprayed on dirt/stain fabric by the fluid composition that will contain peroxygen bleach and surfactant, wash described fabric then, the color that can be reduced in the tensile strength loss in the described fabric and/or reduce described fabric is damaged.The preferred composition that the present invention uses also contains bleach-activating.Therefore, the present invention includes the fluid composition that contains peroxygen bleach, surfactant and bleach-activating, described composition is packaged in the spray-type dispenser.
With by directly it being poured on the dirty fabric rather than according to the present invention described liquid pretreating agent composition being used in its spraying and compared, an advantage of the invention is: the pretreating agent that will contain the liquid peroxy bleaching agent easily is coated on the fabric of dirt/stain, uses minimum described composition simultaneously.In fact, when using spray-type dispenser to carry out described coating, reduced the dangerous and in disorder tendency that described liquid pretreating agent composition overflows when being coated on the dirty fabric.
Another advantage of the present invention is: to the stain and the dirt of wide region, comprise the stain that can bleach such as wine, tea, coffee, grass, and enzyme stain such as blood, grease stain such as macaroni flavouring, dirt that contains mud/clay etc. provides fabulous scourability.
Another advantage that contains peroxygen bleach, surfactant and bleach-activating and be packaged in the fluid composition in the spray-type dispenser according to the present invention is: when it is used for other purposes except the laundry pretreating agent is used, the laundry purposes such as laundry detergent or the laundry additive that for example are used for other, or in the carpet cleaning method using time, also provide fabulous performance.
According to the fluid composition that is packaged in spray-type dispenser and contains peroxygen bleach, surfactant and bleach-activating of the present invention, another advantage that especially is mixed with those compositions of microemulsion is to demonstrate fabulous chemical stability.Also have, make in them some to whiteness with remove stain if desired, particularly the performance of particle and enzyme stain, especially clay and blood is better talked about, so described composition allows to mix a large amount of anion surfactants.
EP-A-209228 discloses can be as the domestic fabric bleaching composition of " pre-stain remover ".Described composition contains bleaching agent such as hydrogen peroxide, non-ionic surface active agent, amino polyphosphonate chelating agent and free radical scavenger.Spray application is not disclosed.
WO 95/16023 discloses the fluid composition that uses two kinds to separate, its the 1st composition contains acid or the neutral composite that comprises peroxide, its the 2nd composition contains alkaline compositions, and the described the 1st and the 2nd composition branch comes and stores and be sprayed to from single unit the general point/surface that will be cleaned.Surfactant may reside in the described the 1st or the 2nd fluid composition.Bleach-activating is not disclosed.The preliminary treatment of openly not doing washing.
GB 2194547 discloses the laundry that comprises surfactant and benzylalcohol mixture and has removed the spot composition in advance, and described composition is heavy dirt district microemulsion form and that be applicable to the processing fabric.As optional components, mentioned bleaching agent, for example hydrogen peroxide can exist with the 0-3% of total composition weight.Do not mention bleach-activating.Do not mention spray application.
US 4648987 discloses the pre-cleaning composition of laundry that is used for keeping the thickening of Local treatment on selected fabric stain.Described pre-cleaning composition comprises water, surfactant, cosurfactant, hydrotropic agent and thickener such as xanthum glue.The pre-cleaning composition of this thickening can be suitable for having the purposes that different distributors for example comprise those distributors of pump pressure or trigger sprayer element.Yet, bleaching agent is not disclosed, said nothing of hydrogen peroxide.
EP-A-629693 discloses the method for the BLEACHED FABRIC that comprises following step: apply the liquid that contains acetyl triethyl citrate or the paste composition of effective dose at least a portion of described fabric, then described fabric is immersed in the aqueous cleaning solution and the hydrogen peroxide of effective dose is provided in described fluid composition or described cleaning solution.Spray application is not disclosed.
Autre action pendante European Patent Application No. 95870026.2 discloses the microemulsion of hydrophobic liquid bleach-activating in the matrix that comprises water, hydrogen peroxide or its water-soluble sources and hydrophilic surfactant system, and this surfactant system comprises anion and non-ionic surface active agent.Disclose the laundry preliminary treatment, still, do not disclose spray application.
J 2099662 discloses the volatility bleaching composition by the aqueous hydrogen peroxide solution composition that contains 10-90% (weight) methyl alcohol and/or ethanol.Wherein disclosed another volatility bleaching composition contains the glycol ether of hydrogen peroxide and 1-10% (weight) and/or the silicone oil (dimethyl polysiloxane) of 0.1-1% (weight).Also claimed in the claim by containing that the volatility bleaching composition that is up to 10% hydrogen peroxide is sprayed but the method that do not have the BLEACHED FABRIC product of follow-up rinsing with above-mentioned.But the composition spray that J 0299662 is open to contain liquid peroxygen bleach/surfactant described fabric of preliminary treatment to the fabric reduces in the described fabric tensile strength loss and/or color and damages.
Summary of the invention
The present invention includes with the fluid composition method of cleaning fabrics that contains peroxygen bleach and surfactant, described method comprises following step: from spray-type dispenser with described composition sprayed at least a portion of described fabric, allow described composition keep contacting, wash described fabric then with described fabric.
The present invention comprises that also the fluid composition that is packaged in the spray-type dispenser is used for the dirty fabric of preliminary treatment before the described fabric of washing so that reduce the purposes of described fabric tensile strength loss, described composition contains hydrogen peroxide and surfactant, and be packaged in described fluid composition in the spray-type dispenser be used for washing described before the yarn-dyed fabric preliminary treatment dirty yarn-dyed fabric so that reduce the purposes that color is damaged.
The present invention also comprises the fluid composition that is used for pretreating fabrics that is packaged in the spray-type dispenser, and described composition comprises peroxygen bleach, surfactant and bleach-activating.In preferred compositions of the present invention, wherein said bleach-activating is the hydrophobic liquid bleach-activating, composition of the present invention is formulated into the microemulsion of described hydrophobic liquid bleach-activating in the matrix that comprises water, described peroxygen bleach and surfactant system, and this surfactant system contains anion and non-ionic surface active agent.
Detailed Description Of The Invention
In its wideest embodiment, the present invention includes with the fluid composition method of cleaning fabrics that contains peroxygen bleach and surfactant, described method comprises following step: with described composition sprayed at least a portion of described fabric, allow described composition keep contacting, wash described fabric then with described fabric.Preferably, before described laundry operations, described composition (with pure form) is stayed described part the preceding paragraph time of fabric so that work at this fabric.Preferably, the described time is 1 minute-24 hours, more preferably 1 minute-1 hour, and most preferably 1 minute-30 minutes.Randomly, when this fabric is made dirty by the stain/dirt of the crust that is difficult to relatively with other method remove, preprocess method according to the present invention may further include to be rubbed and/or scrubs, for example with sponge or brush, perhaps simply by 2 fabrics are rubbed each other.
" washing " is construed as water rinse fabric simply in this article, and perhaps fabric can be with the conventional composition washing that contains at least a surfactant, by washing machine or wash with hand simply.
In by the method for using the dirty fabric of spray-type dispenser preliminary treatment, this sprayed composition should preferably not stayed on the fabric to doing.In fact, have been found that: the water evaporation helps to increase the free number of free radical on the fabric face, and the result has increased the speed of chain reaction.Also infer: stay on the fabric when doing when sprayed composition, automatic oxidation reaction has taken place when water evaporates.Described automatic oxidation reaction has produced the peroxy radical that can impel cellulose degradation.Therefore, as described herein, in passing through the method for the dirty fabric of spray-type dispenser preliminary treatment, sprayed composition is not stayed on the fabric to dried be one of the reason of benefit of the present invention, benefit of the present invention promptly reduces the tensile strength loss and/or the color damage of fabric when with the fluid composition preliminary treatment that contains peroxygen bleach.
In fact, the present invention is based on discovery: when the fluid composition that contains peroxygen bleach and surfactant is sprayed to when wanting on pretreated dirty the yarn-dyed fabric, with when by direct identical fluid composition is applied on it but do not use spray-type dispenser for example by simply it is toppled over preliminary treatment thereon dirty yarn-dyed fabric compare, with with the identical composition of spraying but compare without any surfactant, reduced the color of certain dyestuff that on yarn-dyed fabric, exists and damaged, be i.e. color change and/or fade.In other words, the fluid composition that will contain peroxygen bleach and surfactant is sprayed on dirty the yarn-dyed fabric, make it possible to prevent from/reduce to be present in usually the decomposition (oxidation) of (, comprising copper-first overstep the authority dyestuff and/or metallized azo dye) of dyestuff on the painted fabric face for example to the dyestuff and/or the metallized dyestuff of bleaching agent sensitivity.
By measuring misalignment (DE), as visible among the embodiment hereinafter for example by using the color method of damageing to estimate the color damage of fabric.The main points of this method are to measure misalignment (DE) with " TheHunterlab tristimulus MINISCAN "." misalignment " be interpreted as when will as the fabric of reference as the color of the color that do not have processed fabric and pretreated identical fabric according to the present invention poor relatively the time.To the misalignment of the dyestuff of bleaching agent sensitivity is 0 to mean that not observing color damages.
Therefore, in one aspect, the present invention includes the fluid composition that is packaged in the spray-type dispenser be used for before dirty the yarn-dyed fabric of washing preliminary treatment should be dirty yarn-dyed fabric so that reduce the method for described painted fabric color damage, described composition contains peroxygen bleach and surfactant.
" the dirty fabric of preliminary treatment " is interpreted as fluid composition to be coated on the dirty fabric and to stay on the described fabric before the described fabric of washing with pure form and works.According to the present invention, fluid composition is sprayed on the dirty fabric and before the described fabric of washing, stays on the described fabric with pure form and work.
The present invention is also based on such discovery: when the fluid composition that contains peroxygen bleach and surfactant is sprayed to when wanting on the pretreated dirty fabric, with when identical fluid composition is applied on it but not using spray-type dispenser for example to compare by simply it being toppled over the dirty fabric of preliminary treatment thereon by direct, with with the identical composition of spraying but compare without any surfactant, reduced and cause the fabric of tensile strength loss to damage.
Therefore, in yet another aspect, the present invention comprises that also the fluid composition that is packaged in the spray-type dispenser is used for this dirty fabric of preliminary treatment before the dirty fabric of washing so that reduce the method for described fabric tensile strength loss, and described composition contains peroxygen bleach and surfactant.
Can measure the tensile strength loss of fabric by using the tensile strength method.The main points of this method are to break up to it by the described fabric that stretches to damage the tensile strength of measuring given fabric.Breaking the required power of fabric and represent with kg, is " ultimate tensile stress " and can measure with " The Stress-Strain INSTRON Machine "." tensile strength loss " be interpreted as when will as the fabric of reference as the tensile strength of the tensile strength that do not have processed fabric and pretreated identical fabric according to the present invention the difference relatively the time.Tensile strength loss is 0 to mean that not observing fabric damages.
In addition, when the composition spray that contains peroxygen bleach of the present invention also being obtained the reduction of fabric tensile strength loss and/or the reduction that color is damaged on wanting pretreated dirty fabric the time, not only do not damaged bleachability but also infringement remove the stain performance.
Be applicable to that composition of the present invention is to be packaged in the spray-type dispenser and to contain peroxygen bleach and the liquid aqueous composition of surfactant.
Therefore, they contain solvent peroxygen bleach or its mixture.The preferred peroxygen bleach that is used for herein is hydrogen peroxide or its water-soluble sources, perhaps their mixture.Peroxide source herein refers to any compound that can produce hydrogen peroxide when described compound contacts with water.Except hydrogen peroxide, its suitable water-soluble sources comprises: perborate, percarbonate, benzylhydroperoxide and mistake alkylbenzoic acid, persilicate and persulfate etc.What be used for most convenient herein is hydrogen peroxide.Composition of the present invention should contain the 0.5-20% of total composition weight, preferred 2-15%, the most preferably hydrogen peroxide of 3-10% or its water-soluble sources, perhaps their mixture.
Composition of the present invention contains surfactant as solvent.Being present in the present invention, to contain described surfactant in the peroxygen bleach fluid composition be to obtain benefit of the present invention promptly to reduce tensile strength loss in the pretreating fabrics and/or reduce one of reason that color damages.When according to the present invention during pretreating fabrics, be present in the described surfactant that the present invention contains in the peroxygen bleach fluid composition and can also comprise the stain that to bleach such as tea, grass dissimilar stains, enzyme stain such as blood, grease stain such as barbecue sauce, macaroni sauce, bacon fat etc. provide good cleaning performance.All types of surfactants be can use in the present invention, nonionic, anion, CATION, both sexes or zwitterionic surfactant comprised.Also can use above-mentioned surfactant mixtures and not break away from spirit of the present invention.
The suitable non-ionic surface active agent that is used for herein is the oxyalkylated fatty alcohol nonionic surfactant that can prepare easily by method of condensing known in the art.In fact, a variety of so oxyalkylated fatty alcohol with different HLB values can be buied.The HLB value of above-mentioned oxyalkylated non-ionic surface active agent depends on the chain length of fatty alcohol, oxyalkylated character and oxyalkylated degree basically.Hydrophilic non-ionic surface active agent tends to have high degree of alkoxylation and short chain fatty alcohol, and hydrophobic surfactant tends to have low degree of alkoxylation and long-chain fatty alcohol.Show a lot of surfactants comprise non-ionic surface active agent with and separately the surfactant catalogue of HLB value be available.
Therefore, be used for herein preferred alkoxylated alcohol and be the non-ionic surface active agent according to formula RO (E) e (P) pH, wherein R is the hydrocarbyl chain of 2-24 carbon atom, and E is an oxirane, P is an expoxy propane, represents that respectively the e of average ethoxylation and propoxylation degree and p are 0-24.The hydrophobic part of this non-ionic compound can be uncle or the secondary straight or branched alcohol with 8-24 carbon atom.The preferred nonionic that is used for the present composition is an oxirane and have 6-22 carbon atom, have the condensation product of linear alkyl chain alcohol, and wherein ethoxylation degree is 1-15, preferably 5-12.For example, so suitable non-ionic surface active agent is can be from Shell with trade name Dobanol
Or from Shell with trade name Lutensol
Buy.These non-ionic surface active agents are preferred, need not to add stabilizing agent or hydrotropic agent because find them can form stable product.When using other non-ionic surface active agent, may need to add for example cumene sulfonate or solvent butyldiglycol ether for example of hydrotropic agent.
Suitable anion surfactant herein comprises formula ROSO
3The salt of M or acid, wherein R C preferably
10-C
24Alkyl preferably has C
10-C
20The alkyl of moieties or hydroxy alkyl, more preferably C
12-C
18Alkyl or hydroxy alkyl, M is H or CATION, alkali metal cation (for example sodium, potassium, lithium) for example, or ammonium or (for example replace ammonium, methyl-, dimethyl-and trimethyl ammonium CATION and quaternary ammonium cation for example tetramethyl-ammonium and lupetidine CATION and from alkylamine for example ethamine, diethylamine, the triethylamine quaternary ammonium cation of deriving and its mixture etc.).Usually, for low wash temperature (for example being lower than about 50 ℃) C
12-C
16Alkyl chain is preferred, for higher wash temperature (for example being higher than about 50 ℃) C
16-C
18Alkyl chain is preferred.
Other the suitable anion surfactant that is used for herein 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 hydroxy alkyl of moieties, preferred C
10-C
20Alkyl or hydroxy alkyl, more preferably C
12-C
18Alkyl or hydroxy alkyl, A are ethyoxyl or propoxyl group unit, and m is greater than 0, generally between about 0.5-about 6, more preferably between about 0.5-about 3, M is H or CATION, it can be a metal cation (for example sodium, potassium, lithium, calcium, magnesium etc.) for example, ammonium or replace ammonium cation.The propenoxylated sulfate of the sulfate of alkyl ethoxylated and alkyl is considered herein.The object lesson that replaces ammonium cation comprises: methyl-, dimethyl-and trimethyl ammonium CATION and quaternary ammonium cation for example tetramethyl-ammonium and lupetidine CATION and from alkanolamine ethamine, diethylamine, the triethylamine quaternary ammonium cation of deriving for example, its mixture etc.Illustrative surfactant is C
12-C
18Alkyl polyethoxylate (1.0) sulfate (C
12-C
18E (1.0) M), C
12-C
18Alkyl polyethoxylate (2.25) sulfate (C
12-C
18E (2.25) M), C
12-C
18Alkyl polyethoxylate (3.0) sulfate (C
12-C
18E (3.0) M) and C
12-C
18Alkyl polyethoxylate (4.0) sulfate (C
12-C
18E (4.0) M), wherein M is selected from sodium and potassium easily.
Other also can use in this article to the useful anion surfactant of washing purpose.These surfactants comprise: the salt of soap (comprise, for example sodium, potassium, ammonium and substituted ammonium salt such as list, two and triethanolamine salt), C
9-C
20Linear alkylbenzene sulfonate (LAS), C
8-C
22Uncle or secondary paraffin sulfonate, C
8-C
24The sulfonation polycarboxylic acid of alkene sulfonate, the preparation of the sulfonation by the alkaline earth metal citrate thermal decomposition product, for example, as at sulfonation polycarboxylic acid, the C described in the british patent specification numbers 1082179
8-C
24Alkyl polyglycol ether sulfate (containing the most nearly 10 moles oxirane); Alkyl ester sulfonate is C for example
14-16Monoesters (the particularly saturated and unsaturated C of methyl ester sulfonate, acylglycerol sulfonate, fat oil base glycerol sulfate, alkyl phenol epoxy ethane ether salt, paraffin sulfonate, alkylphosphonic, isethionate such as acyl isethinate, N-acyl taurine salt, amber alkyl amide salts and sulfosuccinate, sulfosuccinic acid
12-C
18Monoesters), the diester of sulfosuccinic acid (particularly saturated and unsaturated C
6-C
14Diester), the sulfate of acyl sarcosinates, alkyl polysaccharide sulfate, chain primary alkyl sulfate, alkyl polyethoxy carboxylate those formulas RO (CH for example of alkyl polyglucoside (compound of nonionic non-sulfuric acidization described below) for example
2CH
2O)
k-CH
2COO
-M
+Salt, wherein R is C
8-C
22Alkyl, k are that integer and the M of 0-10 is the CATION that forms water soluble salt.The resin acid of resin acid and hydrogenation also is suitable, for example rosin, Foral, and the resin acid and the hydrogenated resin acid that are present in or are derived from tall oil.In " surfactant and washing agent (Surface Active Agents and Detergents) " (volume I and II, Schwartz, Perry and Berch work), provided other example.Above-mentioned various surfactant also is disclosed in 58 row-29 hurdles, 23 hurdles, 23 row of the United States Patent (USP) 3929678 that people such as Laughlin issued on December 30th, 1975 (document is incorporated herein by reference) prevailingly.
The preferred anionic surfactants surfactant that is used for this paper composition is alkylbenzenesulfonate, alkyl sulfate, alkyl alkoxylated sulfate and its mixture.Anion surfactant provides improved cleaning performance.In this article in the preferred compositions, these surfactants be microemulsion form and comprise hydrophobic non ionic surfactants and anion surfactant, for the described anion surfactant of hydrophilic compounds plays balanced hydrophobic surfactant negative effect with described hydrophobic surfactant.Described anion surfactant plays wetting agent, i.e. their wet fabrics spot on the hydrophilic fabric especially in laundry applications, and help hydrogen peroxide to carry out its discoloration, but help to improve scourability thus to bleaching soilng.
Suitable cationic surfactants used herein comprises the derivative of quaternary ammonium, Phosphonium, imidazoles and sulfonium compound.The preferred cationic surfactants that is used for herein is according to formula R
1R
2R
3R
4N
+X
-Compound, wherein X is a counter anion, R
1Be C
8-C
20Hydrocarbon chain, R
2, R
3And R
4Be selected from H or C independently of one another
1-C
4Hydrocarbon chain.In the preferred embodiment of the invention, R
1Be C
12-C
18Hydrocarbon chain, most preferably C
14, C
16Or C
18, R
2, R
3And R
4All be that methyl and X are halogens, preferred bromide or chloride, most preferably bromide.The example of cationic surfactant is stearyl trimethylammonium bromide (STAB), softex kw (CTAB) and myristyl trimethylammonium bromide (MTAB).
Suitable zwitterionic surfactant contains CATION and anionic hydrophilic group in wide relatively pH scope on same molecular.General cation group is a quaternary ammonium group, although also can use other positive charge group Xiang Phosphonium, imidazoles and sulfonium group.General anionic hydrophilic group is carboxylate radical and sulfonate radical, although also can use other group to resemble sulfate radical, phosphonate radical etc.The general formula of some preferred zwitterionic surfactant is: R
1-N
+(R
2) (R
3) R
4X
-, R wherein
1It is hydrophobic group; R
2And R
3Each is C naturally
1-C
4The alkyl of alkyl, hydroxy alkyl or other replacement, it also can combine with N and form ring structure; R
4Be that the cationic nitrogen atom is connected to the part of hydrophobic grouping and generally be alkylidene, hydroxy alkylidene or the poly-alkoxyl that contains 1-4 carbon atom; X is a hydrophilic radical, and it is carboxylate radical or sulfonate radical preferably.Preferred hydrophobic group R
1Be to contain 8-22, preferably be less than 18, more preferably less than the alkyl of 16 carbon atoms.This hydrophobic group can contain unsaturated and/or substituting group and/or linking group for example aryl, acylamino-, ester group etc.Usually, because cost and stability, simple alkyl is preferred.
Other concrete zwitterionic surfactant has following general formula:
R
1-C(O)-N(R
2)-(C(R
3)
2)
n-N(R
2)
2 (+)-(C(R
3)
2)
n-SO
3 (-)
Or R
1-C (O)-N (R
2)-(C (R
3)
2)
n-N (R
2)
2 (+)-(C (R
3)
2)
n-COO
(-)
Each R wherein
1Be hydrocarbon, for example contain 8-20, preferably be up to 18, more preferably be up to the alkyl of 16 carbon atoms, each R
2Be hydrogen (on being connected to the acyl ammonia nitrogen time), contain the short-chain alkyl of 1-4 carbon atom or the alkyl of replacement, preferred group is selected from ethyl or propyl group and its mixture that methyl, ethyl, propyl group, hydroxyl replace, preferable methyl, each R
3Be selected from hydrogen and hydroxyl, each n is the number of 1-4, preferred 2-3, and more preferably 3, at any (C (R
3)
2) part has no more than 1 hydroxyl.This R
1Group can be a side chain and/or undersaturated.Also can connect this R
2Group forms ring structure.This class surfactant is can be from SheerCompany with trade name " Varian CAS sulfobetaines "
The C that buys
10-C
14Fatty acyl group acylamino-propylidene (hydroxy propylidene) sulfobetaines.
Suitable amphoteric surfactant be similar to zwitterionic surfactant but should season the surfactant of group.Yet they contain under the low pH of composition protonated so that form cationic amine groups and they also can have anionic group under these pH.
Other suitable amphoteric surfactant comprises having following formula R
1R
2R
3The amine oxide of NO, wherein each R
1, R
2And R
3Be 1-30 carbon atom independently of one another, preferred 6-30 carbon atom, more preferably 10-20 carbon atom and the most preferably replacement or the alkyl unsubstituted, straight or branched of 12-18 carbon atom.Observe: in fabric preliminary treatment according to the present invention, exist described amine oxide further to improve cleaning performance particle and/or grease stain.The suitable amine oxide that is used for herein is preferably compatible with peroxygen bleach.
The present composition preferably contain account for total composition weight be up to 40%, more preferably 0.05-30%, more preferably 1-20%, the most preferably surfactant of 2-15% or its mixture.
Composition of the present invention also contains bleach-activating as component optional but very preferably.Bleach-activating refers to the compound that forms peracid with hydroperoxidation in this article.The peracid that forms constitutes the bleaching agent of activation thus.For the object of the invention, preferably this bleach-activating is hydrophobic so that guaranteeing itself and hydrophilic bleaching agent separates, and avoids the premature reaction between these two compounds thus.Therefore, hydrophobic bleach activator in this article refers to basically and water unmixing and miscible with water astatically activator.Usually, such hydrophobic bleach activator has and is lower than 11 HLB.Suitable liquid hydrophobic bleach activator so generally belongs to ester, acid amides, acid imide or anhydrides.The example of this suitable compounds is disclosed among BP GB1586769 and the GB2143231, and its method that is mixed with particle form is disclosed among the European publication application EP-A-62523.The suitable example of such compound used herein is a tetra acetyl ethylene diamine (TAED), 3; 5,5-trimethyl acetyl base Oxybenzene sodium sulfonate, the diperoxy dodecylic acid described in US4818425 and the nonyl acid amides of crossing oxy hexanoic acid described in US4259201 and positive pelargonyl group Oxybenzene sulfonate (NOBS).Also suitable is the N-acyl caprolactam, and it is selected from: replace or unsubstituted benzoyl caprolactam, caprylyl caprolactam, pelargonyl group caprolactam, caproyl caprolactam, capryl caprolactam, endecatylene acyl caprolactam, formoxyl caprolactam, acetyl group caprolactam, propiono caprolactam, bytyry caprolactam and valeryl caprolactam.An interested especially class bleach-activating is disclosed among the EP624154, particularly preferably is acetyl triethyl citrate (ATC) in such.The advantage of acetyl triethyl citrate is that it is favourable to environment, promptly is degraded into citric acid and alcohol at last.In addition, having good hydrolytic stability in the acetyl triethyl citrate composition in this article, is that effective bleach-activating also offers composition with the good ability of washing that helps.Because its hydrophobicity, so such bleach-activating such as acetyl triethyl citrate are tended in pretreatment operation rather than during being dissolved in the aqueous cleaning solution of this fabric of washing affinity on the surface of fabric that their apply and/or stain, therefore the bleaching of superficial bleaching rather than solution is provided, acetyl triethyl citrate promptly taking place on fabric and/or stain surface rather than in cleaning solution cross hydrolysis formation peracid, has increased total effectiveness of bleaching process.Therefore, make the especially affinity maximum of its dirt part of bleach-activating and fabric.When the preliminary treatment synthetic textiles, because synthetic textiles has hydrophobic property, so this effect is favourable.Therefore in addition, acetyl triethyl citrate also plays the solvent of water-insoluble basically of dissolving stain, prepares and makes this step carry out easily for the fabric subsequently in the follow-up step that described fabric is immersed in cleaning solution cleans.
Therefore, composition herein contains and is up to total composition weight 20%, preferred 1-10%, the most preferably described bleach-activating of 2-7% or its mixture.
The preferred present composition of preparation so also contains particularly liquid hydrophobic bleach activator of bleach-activating except that described peroxygen bleach, so that make described bleach-activating and described peroxygen bleach keep separating.This can demonstrate fabulous chemical stability thus by described composition being mixed with emulsion or microemulsion is realized.Therefore, preferably composition of the present invention is formulated as the microemulsion of described liquid bleach activator in the matrix that contains water, described peroxygen bleach and hydrophilic surfactant system, this hydrophilic surfactant system contains anion and non-ionic surface active agent.
Therefore, preferred composition herein contains the surfactant system that comprises anion surfactant and non-ionic surface active agent.In order stably this hydrophobic activation agent to be incorporated in the described microemulsion, The key factor is that at least a described surfactant has and the visibly different HLB of this hydrophobic activation agent.In fact,, can form continuous single phase so, therefore reduce the chemical stability of bleach/bleach activator system if all described surfactants have the HLB value identical with this hydrophobic activation agent.Preferably, the HLB value of at least a described surfactant and the HLB value of described bleach-activating differ 1.0HLB unit at least, preferred 2.0HLB unit.
The method that preferred preparation is mixed with the present composition of microemulsion comprises: with surfactant and water premixed, then add other component, comprise hydrogen peroxide.Add hydrophobic bleach activator at last.Preferably to add order irrelevant with this, importantly: between the component mixing period, under high relatively agitation energy, composition is kept stirring constantly, preferably under 750rpm 30 minutes, most preferably under 1000rpm 30 minutes.
The present invention is mixed with the preferred composition of microemulsion can be by being transparent further the characterizing of macroscopic view there not being under opacifier and the dyestuff condition them, and described composition can also further characterize by micro-examination and centrifugation.In centrifugation, observe described composition herein and under 6000RPM, be not separated after 15 minutes.At microscopically, described composition performance is the dispersion liquid of drop in matrix.This matrix is previously described hydrophilic substrate, and this drop is made of the liquid hydrophobic bleach activator.We observe: this particle has general about 3 microns or be lower than 3 microns diameter.
As choosing wantonly but preferable feature, should be in the acid pH scope, preferred 2-6, more preferably preparation composition herein between the 3-5.
Composition of the present invention is moisture.Therefore, they preferably contain the 10-95% that accounts for total composition weight, more preferably 20-80%, the most preferably water of 40-75%.
As other optional components, composition herein can contain and be up to 5% of total composition weight, the formula HO-CR ' R of preferred 0.5-4% "-OH alcohol, wherein R ' and R " be H or C independently of one another
2-C
10Hydrocarbon chain and/or ring.Preferably the alcohol according to this formula is propylene glycol.In fact, we observe: the pure and mild specific propylene glycol of general these has also improved the chemical stability of the composition that contains peroxygen bleach and bleach-activating, promptly reduces the decomposition of bleaching agent and bleach-activating.In addition, described alcohol has reduced the surface tension of composition herein, therefore prevents the formation of skin covering of the surface or gel.Therefore, described alcohol has improved the aesthetic effect of composition herein.The chemically stable effect that it is believed that described alcohol is two aspects.The first, they play free radical scavenger, and the second, they and hydrogen peroxide interact and prevent or limiting hydrolysis, have therefore reduced the decomposition rate of peroxide.
As another optional components, composition herein can contain the viscosity adjustment compound, comprises the alcohol according to following formula:
Wherein n is the integer of 0-10, R, R ', R " and R
IvCan be H or C
1-C
10Straight or branched alkyl chain, or C
1-C
10Straight or branched alkenyl or alkynyl chain.Preferred alcohol according to this formula is benzylalcohol.In fact, we observe: when needs are prepared the present composition with low viscosity, promptly when measuring under 20 ℃ of 50rpm with No. 3 main shafts of Brookfield, when viscosity was the fluid composition of the preferred 10-1000cps of 5-2000cps, such compound was particularly advantageous.
Therefore, composition of the present invention contains and is up to 20% of total composition weight, preferred 0.1-10%, more preferably alcohol or its mixture with following formula of 0.5-5%.
As another optional components, fluid composition of the present invention can contain chelating agent or its mixture.Being applicable to that herein chelating agent comprises is selected from following chelating agent: the aromatic chelating agent of phosphine acid salt chelator, aminocarboxylate chelating agent, multi-functional replacement, polyamine chelating agent and other chelating agent resemble glycine, salicylic acid, aspartic acid, glutamic acid, malonic acid or its mixture.
Suitable phosphine acid salt chelator used herein can comprise ethydronic acid and aminophosphonic acid salt compound, comprises that amino alkylidenyl gathers (alkylene phosphonic acids salt), alkali metal ethane 1-hydroxyl diphosphonate, nitrilo-trimethylene phosphonic salt, ethylenediamine tetramethylene phosphonic acid salt and diethylenetriamine pentamethylenophosphonic acid salt.This phosphonate can exist with sour form or as the different cationic salt form on its some or all acid functional group.Preferred phosphine acid salt chelator used herein is a diethylenetriamine pentamethylenophosphonic acid salt.Such phosphonate is can be from Monsanto with trade name DEQUEST
Buy.
In the composition of this paper, the aromatic chelating agent of multi-functional replacement also is useful.See the people's such as Connor of promulgation on May 21st, 1974 US3812044.This compounds of preferred sour form is a dihydroxy disulfobenzene for example 1,2-dihydroxy-3,5-disulfobenzene.
The biodegradable cheating agent that preferably is used for herein is ethylenediamine N, N '-disuccinic acid or its alkali metal, alkaline-earth metal, ammonium or substituted ammonium salt, or its mixture.Ethylenediamine N, N '-disuccinic acid, especially (S, S) isomers has been described in the Hartman of on November 3rd, 1987 promulgation and the US4704233 of Perkins has suffered widely.For example, ethylenediamine N, N '-disuccinic acid can be from Palmer Research Laboratories with trade name ssEDDS
Buy.
The suitable aminocarboxylate that is used for herein comprises: the edetate of sour form or its alkali metal, ammonium and substituted ammonium salt form, diethylentriamine pentacetate, diethylentriamine pentacetate (DTPA), N-Oxyethylethylenediaminetriacetic acid salt, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid salt, triethylenetetraaminehexaacetic acid salt, ethanol diamino-acetic acid, trimethylene diamine tetraacetate (PDTA) and methyl aminoacetic acid oxalic acid (MGDA).Specially suitable aminocarboxylate used herein is diethylentriamine pentacetate, trimethylene diamine tetraacetate (PDTA), and it for example can be from BASF with trade name Trilon FS
Buy and methyl aminoacetic acid oxalic acid (MGDA).
Suitable polyamine chelating agent comprises common alkyl polyamine, for example 1,2 alkyl diamine as 1,2 propyl diamine, 1,3 alkyl diamine as 1,3 propyl diamine, 1,4 alkyl diamine as 1,4 butyl diamines, propane diamine, isopropylidene diamines, ethylenediamine.Polyamines very preferably used herein is ethylenediamine (EDA).Be applicable to that this polyamines herein can obtain from Union Carbide.For example ethylenediamine can be from Union Carbide with trade name EDA
Buy.
Particularly preferred chelating agent used herein is diethylenetriamines methylene phosphonic acid salt, ethylidene N, N '-disuccinic acid, diethylentriamine pentacetate, ethylenediamine, amion acetic acid, salicylic acid, aspartic acid, glutamic acid, malonic acid or its mixture it is most preferred that salicylic acid.Salicylic acid can be from Rhone-Poulenc with trade name Salicylic Acid
Buy.
Therefore, composition of the present invention contains and is up to 5% of total composition weight, preferred 0.01-3%, the more preferably chelating agent of 0.01-1.5% or its mixture.
As another optional components, composition of the present invention can contain free radical scavenger or its mixture.Suitable free radical scavenger used herein comprises: the list of known replacement and dihydroxy benzenes and its analog, alkyl and aryl carboxylic acid salt and its mixture.The such free radical scavenger that preferably is used for herein comprises: di-tert-butyl hydroxy toluene (BHT), quinhydrones, di-tert-butyl hydroquinone, a tertiary butylated hydroquinone, tert-butyl group hydroxyl anysole, benzoic acid, toluic acid, tert-butyl catechol, benzyl amine, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, n-pro-pyl gallate or its mixture it is most preferred that di-tert-butyl hydroxy toluene.
Therefore, composition of the present invention contains and is up to total composition weight 5%, preferred 0.01-2%, the more preferably free radical scavenger of 0.05-1% or its mixture.
Composition herein can also contain various other optional components, for example builder, other chelating agent, other free radical scavenger, enzyme, brightening agent, dyestuff, spices etc.
The type of spray-type dispenser used according to the invention, composition of the present invention can be newton's or shear thinning.Can add optional components so that obtain required composition rheology character with suitable form.
" newton's " refers in this article when being subjected to different shear stresses, and in the time of for example when spraying by spray-type dispenser and on attached to fabric, composition has identical viscosity." shear thinning " refers in this article when different shear stresses puts on described composition, and composition has different viscosity.For example, when spraying by spray-type dispenser such as trigger sprayer, thereby the composition of shear thinning causes shear-thinning property to distribute easily, and promptly described composition is rarer under higher shear rate.Therefore the described composition pumping installations by the high spray-type dispenser of shear rate easily, and to be processedly recover the character of its thickness immediately when surperficial and adhere to from the teeth outwards when arriving afterwards.
As another essential characteristic, composition of the present invention is packaged in the spray-type dispenser.
Suitable spray-type dispenser used according to the invention comprises: aerosol and manually operated foam trigger type distributor, and for example by Specialty Packing Products, Inc. or Continental Sprayers, the distributor that Inc. sells.The distributor of these types is disclosed in, for example people's such as Dunning US4701311 and all be among the US4646973 and US4538745 of Focarracci.The spray-type dispenser that particularly preferably is used herein, for example T 8500 that can buy from Continental Spray International
Maybe can be from Canyon, the T 8100 that Northen Ireland buys
In such distributor, fluid composition is divided into tiny liquid drop, and the result forms and is directly injected to the mist of wanting on the treatment surface.In fact, in such spray-type dispenser, the user drives pumping installations and transfers the energy to the fog-spray nozzle of described pumping installations by spray-type dispenser and spray the composition that is contained in the described distributor body.More particularly, in described spray-type dispenser head, composition is applied defeats barrier for example on grid or the taperer etc., provides thus to impact so that help the fluid composition atomisation promptly to be helped to form liquid drop.
Advantage of the present invention is: be packaged in the spray-type dispenser according to the present invention and contain peroxygen bleach and the fluid composition of surfactant can be coated on the relative large-area dirty fabric to be processed equably, therefore guaranteed that the good cleaning performance to dissimilar stains is ultra-safe to the dirty fabric of described processing simultaneously.
Another advantage of the present invention is: the fluid composition that the present invention contains peroxygen bleach can easily be distributed on dirt/stain fabric.
Another advantage of the present invention is: carry out the preliminary treatment of fabric in the mode of economy, promptly do not use the product of more actual needs.
Further specify the present invention by following embodiment.
Embodiment
Prepare following composition by the component of listing being mixed with listed ratio.Listed ratio is that the % with general composition weight meter represents. composition (wt%) 123456 7Neodol 23.3 6.4 2--12--3.5 6.4Neodol 45.7 8.6--6--3 6 8.6Dobanol 91-10--5----------Dobanol 23-6.5----6--------C25 AE3S 2------------NaAS-----12 12 26 2H,202 4366744 acetyl lemon triethylenetetraminehexaacetic acid ester 3.5--3.5 3.5--2 3.5 caprylyl caprolactams--3.5----------propane diols---5--------amine oxide---3--------benzyl alcohol---------3.0--water and a small amount of component------------------arriving--100%----------H2SO
4To pH4
NaAS represents alkyl sulfate
C25AE3S represents the C25 alkyl ethoxy sulfate
By using spray-type dispenser (for example with trade name Calmar TS800-1A
The trigger sprayer of buying) above-mentioned composition is sprayed on the dirty fabric to be processed, has obtained fabulous cleaning performance and improved safety to fabrics and/or color safety simultaneously.
Claims (13)
1. one kind with the fluid composition method of cleaning fabrics that contains peroxygen bleach and surfactant, described method comprises following step: described composition is assigned at least a portion of described fabric from spray-type dispenser, allow described composition and described fabric keep in touch, wash described fabric then.
2. according to the cleaning fabric method of claim 1, wherein said composition also contains bleach-activating.
3. fluid composition that is used for pretreating fabrics that is packaged in the spray-type dispenser, described composition contains peroxygen bleach, surfactant and bleach-activating.
4. according to the method or the composition of aforementioned arbitrary claim, wherein said peroxygen bleach is a hydrogen peroxide, or its water-soluble sources, or their mixture, and the amount of its existence is the 0.5-20% of total composition weight, preferred 2-15%.
5. according to the method or the composition of aforementioned arbitrary claim, the amount that wherein said surfactant or its mixture exist is up to 40% of total composition weight, preferred 0.05-30%, more preferably 1-20%.
6. according to the method for claim 2 or according to any composition of claim 3-5, the amount that wherein said bleach-activating or its mixture exist is up to 20% of total composition weight, preferred 1-10%, more preferably 2-7%.
7. according to the method or the composition of claim 6, wherein said bleach-activating is liquid hydrophobic bleach activator and acetyl triethyl citrate preferably.
8. according to the method or the composition of claim 7, wherein described composition is mixed with described hydrophobic liquid bleach-activating and is containing water, described peroxygen bleach and as the microemulsion in the matrix of the hydrophilic surfactant system of described surfactant, this hydrophilic surfactant system contains anion and non-ionic surface active agent.
9. composition according to Claim 8, wherein in described surfactant system, the HLB value of at least a described surfactant and the HLB value of described bleach-activating differ 1HLB unit at least, preferred 2HLB unit.
10. according to the method or the composition of aforementioned arbitrary claim, wherein said composition also contains the 1-10% of total composition weight, the formula HO-CR ' R of preferred 2-4% "-OH alcohol, wherein R ' and R " be H or C independently of one another
2-C
10Hydrocarbon chain and/or ring, or its mixture, and/or be up to total composition weight 20%, preferred 0.1-10%, more preferably alcohol or its mixture of 0.5-5% with following formula:
Wherein n is the integer of 0-10, R, R ', R " and R
IvCan be H or C
1-C
10Straight or branched alkyl chain, or C
1-C
10Straight or branched alkenyl or alkynyl chain.
11. according to the method or the composition of aforementioned arbitrary claim, wherein said spray-type dispenser is a trigger sprayer.
12. be packaged in the purposes of the fluid composition in the spray-type dispenser, described composition comprises peroxygen bleach and surfactant, it is used for the painted dirt fabric of preliminary treatment, washs described painted dirt fabric then, damages with the color that reduces described fabric.
13. be packaged in the purposes of the fluid composition in the spray-type dispenser, described composition comprises peroxygen bleach and surfactant, it is used for preliminary treatment dirt fabric, washs described dirt fabric then, to reduce the loss of tensile strength in the described fabric.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95203331A EP0776966B1 (en) | 1995-12-02 | 1995-12-02 | Liquid bleaching compositions packaged in spray-type dispenser and a process for pretreating fabrics therewith |
| EP95203331.4 | 1995-12-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1207781A true CN1207781A (en) | 1999-02-10 |
Family
ID=8220905
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96199727A Pending CN1207781A (en) | 1995-12-02 | 1996-11-27 | Liquid bleaching compositions packaged in spray-type dispenser and process for pretreating fabrics therewith |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0776966B1 (en) |
| JP (1) | JP3121841B2 (en) |
| KR (1) | KR19990071834A (en) |
| CN (1) | CN1207781A (en) |
| AR (1) | AR004831A1 (en) |
| AT (1) | ATE223965T1 (en) |
| AU (1) | AU720040B2 (en) |
| BR (1) | BR9611860A (en) |
| CA (1) | CA2239229A1 (en) |
| DE (1) | DE69528179T2 (en) |
| ES (1) | ES2182864T3 (en) |
| MX (1) | MX9804391A (en) |
| TR (1) | TR199800994T2 (en) |
| WO (1) | WO1997020980A1 (en) |
| ZA (1) | ZA9610007B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100406546C (en) * | 2002-07-29 | 2008-07-30 | 花王株式会社 | Foam composition for bleaching clothes |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19801086C1 (en) * | 1998-01-14 | 1998-12-17 | Henkel Kgaa | Aqueous bleaching agent in microemulsion form |
| EP1001011B2 (en) † | 1998-11-11 | 2010-06-23 | The Procter & Gamble Company | Bleaching composition comprising an alkoxylated benzoic acid |
| GB9930697D0 (en) * | 1999-12-24 | 2000-02-16 | Unilever Plc | Method of treating a textile |
| WO2003027220A1 (en) * | 2001-09-21 | 2003-04-03 | The Procter & Gamble Company | Article of manufacture |
| US6910579B2 (en) | 2002-05-28 | 2005-06-28 | Georgia-Pacific Corporation | Refillable flexible sheet dispenser |
| JP4030831B2 (en) * | 2002-08-14 | 2008-01-09 | 花王株式会社 | Laundry pretreatment composition |
| JP4101585B2 (en) * | 2002-08-14 | 2008-06-18 | 花王株式会社 | Laundry pretreatment composition |
| JP5379963B2 (en) * | 2007-08-24 | 2013-12-25 | ライオン株式会社 | Cleaning composition for wiping and cleaning method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3812044A (en) | 1970-12-28 | 1974-05-21 | Procter & Gamble | Detergent composition containing a polyfunctionally-substituted aromatic acid sequestering agent |
| US3929678A (en) | 1974-08-01 | 1975-12-30 | Procter & Gamble | Detergent composition having enhanced particulate soil removal performance |
| GB1586769A (en) | 1976-10-06 | 1981-03-25 | Procter & Gamble Ltd | Laundry additive product |
| US4259201A (en) | 1979-11-09 | 1981-03-31 | The Procter & Gamble Company | Detergent composition containing organic peracids buffered for optimum performance |
| US4399049A (en) | 1981-04-08 | 1983-08-16 | The Procter & Gamble Company | Detergent additive compositions |
| GB8304990D0 (en) | 1983-02-23 | 1983-03-30 | Procter & Gamble | Detergent ingredients |
| US4538745A (en) | 1983-05-19 | 1985-09-03 | The Clorox Company | Trigger sprayer |
| US4563186A (en) * | 1984-04-05 | 1986-01-07 | Purex Corporation | Multi-functional laundry product and employment of same during fabric laundering |
| IT1181462B (en) | 1984-10-25 | 1987-09-30 | Consiglio Nazionale Ricerche | PROCEDURE FOR THE SEPARATION OF ARSENIC FROM ACID SOLUTIONS THAT CONTAIN IT |
| US4648987A (en) | 1985-02-13 | 1987-03-10 | The Clorox Company | Thickened aqueous prewash composition |
| DE3665482D1 (en) | 1985-06-17 | 1989-10-12 | Clorox Co | Stabilized liquid hydrogen peroxide bleach compositions |
| US4646973A (en) | 1985-08-07 | 1987-03-03 | The Clorox Company | Impingement foamer |
| US4818425A (en) | 1986-05-28 | 1989-04-04 | Akzo N.V. | Process for the preparation of diperoxydodecanedioic acid-containing agglomerates and compositions in which these agglomerates are used as bleaching component |
| ZA876158B (en) | 1986-09-02 | 1989-04-26 | Colgate Palmolive Co | Laundry pre-spotter composition providing improved oily soil removal |
| US4704233A (en) | 1986-11-10 | 1987-11-03 | The Procter & Gamble Company | Detergent compositions containing ethylenediamine-N,N'-disuccinic acid |
| JPH0299662A (en) | 1988-09-30 | 1990-04-11 | Mizuho Chem:Kk | Bleaching agent for fiber and method for bleaching |
| FR2660859B1 (en) * | 1990-04-12 | 1992-07-10 | Hanna Khalil | KERATOTOME FOR THE MAKING OF ARCIFORM INCISIONS. |
| JP3450326B2 (en) | 1991-12-13 | 2003-09-22 | ザ、プロクター、エンド、ギャンブル、カンパニー | Acylated citrate as a peracid precursor |
| EP0598692A1 (en) * | 1992-11-16 | 1994-05-25 | The Procter & Gamble Company | Pseudoplastic and thixotropic cleaning compositions |
| ES2121982T3 (en) | 1993-06-09 | 1998-12-16 | Procter & Gamble | PROCEDURE FOR LAUNDRY OF TISSUES. |
| ES2137246T3 (en) * | 1993-07-12 | 1999-12-16 | Procter & Gamble | STABLE AQUEOUS EMULSIONS OF NON-ION SURFACES WITH A VISCOSITY CONTROL AGENT. |
| BR9408256A (en) | 1993-12-07 | 1996-12-10 | Unilever Nv | Parts and process kit for cleaning hard surfaces |
| EP0752469B1 (en) * | 1995-07-05 | 2004-09-22 | The Procter & Gamble Company | Laundry pre-treatment with improved fabric/colour safety |
-
1995
- 1995-12-02 DE DE69528179T patent/DE69528179T2/en not_active Revoked
- 1995-12-02 ES ES95203331T patent/ES2182864T3/en not_active Expired - Lifetime
- 1995-12-02 AT AT95203331T patent/ATE223965T1/en not_active IP Right Cessation
- 1995-12-02 EP EP95203331A patent/EP0776966B1/en not_active Revoked
-
1996
- 1996-11-27 KR KR1019980704116A patent/KR19990071834A/en active IP Right Grant
- 1996-11-27 TR TR1998/00994T patent/TR199800994T2/en unknown
- 1996-11-27 CN CN96199727A patent/CN1207781A/en active Pending
- 1996-11-27 JP JP09521328A patent/JP3121841B2/en not_active Expired - Fee Related
- 1996-11-27 CA CA002239229A patent/CA2239229A1/en not_active Abandoned
- 1996-11-27 AU AU10250/97A patent/AU720040B2/en not_active Ceased
- 1996-11-27 BR BR9611860A patent/BR9611860A/en not_active IP Right Cessation
- 1996-11-27 WO PCT/US1996/018943 patent/WO1997020980A1/en active IP Right Grant
- 1996-11-28 ZA ZA9610007A patent/ZA9610007B/en unknown
- 1996-12-02 AR ARP960105455A patent/AR004831A1/en unknown
-
1998
- 1998-06-02 MX MX9804391A patent/MX9804391A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100406546C (en) * | 2002-07-29 | 2008-07-30 | 花王株式会社 | Foam composition for bleaching clothes |
Also Published As
| Publication number | Publication date |
|---|---|
| AU1025097A (en) | 1997-06-27 |
| TR199800994T2 (en) | 1998-08-21 |
| KR19990071834A (en) | 1999-09-27 |
| CA2239229A1 (en) | 1997-06-12 |
| JPH11500778A (en) | 1999-01-19 |
| AU720040B2 (en) | 2000-05-25 |
| ES2182864T3 (en) | 2003-03-16 |
| DE69528179T2 (en) | 2003-04-30 |
| BR9611860A (en) | 1999-05-04 |
| EP0776966A1 (en) | 1997-06-04 |
| MX9804391A (en) | 1998-09-30 |
| AR004831A1 (en) | 1999-03-10 |
| EP0776966B1 (en) | 2002-09-11 |
| JP3121841B2 (en) | 2001-01-09 |
| WO1997020980A1 (en) | 1997-06-12 |
| DE69528179D1 (en) | 2002-10-17 |
| ATE223965T1 (en) | 2002-09-15 |
| ZA9610007B (en) | 1997-06-13 |
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