CN1176656A - Laundry pretreatment with peroxide bleaches containing chelators for iron, copper or manganese for reduced fabric damage - Google Patents
Laundry pretreatment with peroxide bleaches containing chelators for iron, copper or manganese for reduced fabric damage Download PDFInfo
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- CN1176656A CN1176656A CN96192233A CN96192233A CN1176656A CN 1176656 A CN1176656 A CN 1176656A CN 96192233 A CN96192233 A CN 96192233A CN 96192233 A CN96192233 A CN 96192233A CN 1176656 A CN1176656 A CN 1176656A
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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
- C11D1/83—Mixtures of non-ionic with anionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/361—Phosphonates, phosphinates or phosphonites
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/364—Organic compounds containing phosphorus containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
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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
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
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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
- C11D1/72—Ethers of polyoxyalkylene glycols
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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
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
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- Oil, Petroleum & Natural Gas (AREA)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The present invention relates to the use of a liquid composition comprising a peroxygen bleach and a compound chelating copper and/or iron and/or manganese, for pretreating fabrics before said fabrics are washed, whereby the loss of tensile strength in said fabrics is reduced. The present invention further encompasses a process for pretreating soiled fabrics as well as compositions suitable to be used in said process.
Description
Technical field
The present invention relates to the pre-treatment of dirt fabric, the composition that is suitable as pretreating agent and pretreatment process.
Background of invention
The composition that contains peroxygen bleach be described in widely detergent for washing clothes for example, laundry additive or even the laundry articles for use of laundry pretreating agent in.
Really, people know and use the composition that contains peroxygen bleach to promote difficult especially stain/dirt of removing for example oil stain, coffee, tea stain, grass stain and contain the removal of the dirt etc. of mud/soil in the laundry pre-treatment is used.Yet we find with this shortcoming that contains the composition of peroxygen bleach is to be used for can damaging fabric when pre-treatment is used when said composition, that is, when directly being used on the fabric, before the said fabric of washing, it is left and acts on this fabric for a long time.
Therefore, the objective of the invention is, when usefulness contains the composition pretreating fabrics of peroxygen bleach, particularly before the said fabric of washing, said composition is left in those application that contact with said fabric for a long time, and the fabric integrity of improving is provided.
When comprising the composition pretreating fabrics of peroxygen bleach such as hydrogen peroxide, it is found that metal ion for example copper and/or iron and/or manganese be present in fabric face fabric damaged, cause the loss of tensile strength of fabric fibre.By inference metal ion for example copper and/or iron and/or manganese be present in fabric face, particularly on fibrinous fiber surface, catalysis the free radical of peroxygen bleach such as hydrogen peroxide decompose.So, along with the generation of free radical, on the surface of fabric free radical reaction takes place, cause loss of tensile strength.
Therefore we find, the control surface free radical reaction is necessary in the pre-treatment environment, provide the integrity of improving to fabric thus.
Have now found that the composition that contains peroxygen bleach that contains the compound of chelated copper and/or iron and/or manganese by preparation can realize above-mentioned purpose.In particular, found in containing the composition of peroxygen bleach, to use the compound of chelated copper and/or iron and/or manganese, preferred diethylenetriamine pentamethylenophosphonic acid(DTPP) (DTPMP), hydroxyl ethane di 2 ethylhexyl phosphonic acid (HEDP), quadrol N, N '-disuccinic acid (EDDS), methylglycine oxalic acid (MGDA), diethylene triaminepentaacetic acid(DTPA) (DTPA), trimethylene diamine tetraacethyl (PDTA), 2 hydroxy pyrimidine-N-oxide compound (HPNO) or ethylene nitrilo four (methylene phosphonic acid) N, the N-dioxide has significantly reduced the damage that causes with the pretreated fabric of this composition.
In the laundry pre-treatment was used, using the advantage of the composition that contains peroxygen bleach of this compound that comprises chelated copper and/or iron and/or manganese was the destruction of also having reduced color.
Another advantage of the present invention is to provide fabulous scourability to the spot that can bleach and to removing oil spot.
Additional advantages of the present invention are, be applicable to that composition of the present invention is when being used for except the laundry pre-treatment is used other and using, for example other laundry applications as detergent for washing clothes or laundry additive, or even also provides fabulous performance in hard surface cleaning is used.
In one embodiment of the present invention, sequestrant such as ethylene nitrilo four (methylene phosphonic acid) N have been found to use, two electron-donating groups of the adjacent coordination position that N-dioxide, hydroxyl ethane di 2 ethylhexyl phosphonic acid (HEDP) and/or have can occupy in the metallic ion coordination district are so that form title complex (wherein each metal ion and 3 chelator molecules with metal ion, cooperate as 2 hydroxy pyrimidine-N-oxide compound) sequestrant, can prepare the acidic liquid composition that is applicable to pretreating fabrics, it shows the chemical stability of improvement under storing for a long time.
The composition that contains peroxygen bleach is described in the prior art widely.EP-A-629691 discloses the emulsion of nonionogenic tenside, and it contains polysiloxane compound and is the hydrogen peroxide of optional components or its water-soluble sources body, and sequestrant.Disclosed unique sequestrant is S, the amino disuccinic acid (referring to embodiment) of S-ethylene.Though EP-A 629691 discloses composition and has been used for pre-treatment and uses, openly be not used for the application of the composition that contains peroxygen bleach of the compound that comprises chelated copper and/or iron and/or manganese that loss of tensile strength that pretreating fabrics makes said fabric thus reduces.
EP-A-629690 discloses the emulsion of nonionogenic tenside, and it contains based on the polymkeric substance of terephthalate with as hydrogen peroxide or its water-soluble sources body of optional ingredient, and sequestrant.Disclosed unique sequestrant is S, the amino disuccinic acid (referring to embodiment) of S-ethylene.Though EP-A 629690 discloses composition and has been used for pre-treatment and uses, openly be not used for the application of the composition that contains peroxygen bleach of the compound that comprises chelated copper and/or iron and/or manganese that loss of tensile strength that pretreating fabrics makes said fabric thus reduces.
EP-B-209228 discloses the composition that comprises peroxide source such as hydrogen peroxide, amino polyphosphonate sequestrant and free-radical scavengers.Diethylenetriamine pentamethylenophosphonic acid(DTPP) is clearly disclosed.Also have EP-B-209228 to disclose the available composition of hydrogen peroxide that contains as pre-stain remover.Yet the composition that contains peroxygen bleach of not mentioning the compound that comprises chelated copper and/or iron and/or manganese is used for pretreating fabrics reduces the loss of the tensile strength of said fabric.
Summary of the invention
Present invention resides in before the washing dirt fabric, use this fabric of liquid composition pre-treatment of the compound that comprises peroxygen bleach and chelated copper and/or iron and/or manganese, the loss of the tensile strength of said fabric is reduced.
The present invention also comprises the method with the liquid composition pre-treatment dirt fabric of the compound that comprises peroxygen bleach and chelated copper and/or iron and/or manganese, this method may further comprise the steps: before laundering of textile fabrics, said composition is applied on the fabric with its clean form, said composition and said fabric are kept in touch, but do not make said composition on said fabric, remain to drying.
The present invention also comprises liquid detergent composition, it comprises peroxygen bleach, compound with chelated copper and/or iron and/or manganese, it is methylglycine oxalic acid, trimethylene diamine tetraacethyl, 2 hydroxy pyrimidine-N-oxide compound, ethylene nitrilo four (methylene phosphonic acid) N, N-dioxide, hydroxyl ethane di 2 ethylhexyl phosphonic acid, or its mixture.
Detailed Description Of The Invention
In the ordinary course of things, present invention resides in before the washing dirt fabric, use this fabric of liquid composition pre-treatment of the compound that comprises peroxygen bleach and chelated copper and/or iron and/or manganese, the loss of the tensile strength of said fabric is reduced.
The present invention is based on a kind of like this discovery, promptly when using according to the compound compositions pre-treatment dirt fabric that comprises peroxygen bleach and chelated copper and/or iron and/or manganese of the present invention, do not have this fabric of same combination pre-treatment of any compound of chelated copper and/or iron and/or manganese to compare with use, the fabric that causes loss of tensile strength is damaged reduce.
Term " pre-treatment dirt fabric " should be understood to be in the method according to pre-treatment dirt fabric of the present invention, as hereinafter described, before the said fabric of washing, this liquid composition is applied on the dirt fabric and stays with its clean attitude form and acts on said fabric.
In other words, even before the said fabric of washing, said composition was stayed on the pretreated fabric 24 hours according to appointment for a long time, even with contaminated high-load copper and/or iron and/or the manganese of this fabric, use the composition that contains peroxygen bleach that comprises the compound of chelated copper and/or iron and/or manganese according to the present invention can reduce loss significantly owing to the tensile strength that on fabric face, exists copper and/or iron and/or manganese to cause.
The available tensile strength method of the loss of fabric tensile strength is measured, and this is found in embodiment hereinafter.This method is to measure the tensile strength of given fabric until fracture by the described fabric that stretches.The required power of representing with Kg of fracture fabric is " limit tensile stress ", and available " stress-strain instron machine " measured.Term " loss of tensile strength " is interpreted as the tensile strength by the pretreated fabric of the present invention, when with identical fabric as reference substance, the tensile strength that does not promptly have a pretreated fabric is relatively the time, the difference between them.Loss of tensile strength is that zero meaning is not observe fabric to damage.
Advantage of the present invention is also to have reduced color is destroyed.Really, when the band yarn dyed fabric that uses according to the composition pre-treatment dirt that contains peroxygen bleach of the compound that comprises chelated copper and/or iron and/or manganese of the present invention, with when using same combination to compare without any this compound of chelated copper and/or iron and/or manganese, observe colour-change or/and decolouring reduces, even before the said fabric of washing, said composition is stayed on the fabric through also being like this for a long time.Therefore, the present invention also is included in before the said fabric of washing, uses the band yarn dyed fabric of the liquid composition pre-treatment dirt of the compound that comprises peroxygen bleach and chelated copper and/or iron and/or manganese, has reduced thus the color of fabric is destroyed.
In addition, the liquid composition that use comprises the compound of peroxygen bleach and chelated copper and/or iron and/or manganese reduces the fabric loss of tensile strength and/or the reduction of fabric color destruction, and does not damage bleachability and the removal spot performance that said composition is given.
The present invention also comprises the method for handling the dirt fabric with the liquid composition of the compound that comprises peroxygen bleach and chelated copper and/or iron and/or manganese, this method may further comprise the steps: before laundering of textile fabrics, said composition is applied on the fabric with its clean attitude form, said composition and said fabric are kept in touch, do not make said composition on said fabric, remain to drying.Said composition can keep contacting general 1 minute to 24 hours with said fabric, and preferred 1 minute to 1 hour, more preferably 5 minutes to 30 minutes.Randomly, during the difficult relatively stain of removing on fabric pollutes/dirt, composition of the present invention can be by for example with sponge or brush or simply two fabrics are rubbed toward each other, makes it to be rubbed and/or brushed strong or weakly.Term " washing " is interpreted as the simple rinse fabric of water at this paper, or with washing machine or simply with the conventional composition washing fabric that comprises at least a tensio-active agent of hand use.
Term " with the form of clean attitude " is interpreted as composition described herein and is not applied on the pretreated fabric through any dilution.
The method of pre-treatment dirt fabric according to the present invention, the liquid composition of Shi Yonging is not taken in and remains to drying on the fabric in the method.Really, found that evaporation of water has promoted free radical to increase and must increase chain reaction speed in the concentration of fabric face.Infer also that when liquid composition remains to drying on fabric react when autoxidation can take place in the water evaporation, this autoxidation reaction has produced the peroxy radical that can impel cellulose degradation.Therefore, in the method for pre-treatment dirt fabric according to the present invention, liquid composition described herein is not remained to drying on fabric, this provides benefit of the present invention, that is, when using the liquid composition pretreating fabrics that contains peroxygen bleach, reduced the loss of tensile strength.
Be applicable to that composition of the present invention comprises the peroxygen bleach as main ingredient, preferred peroxygen bleach is hydrogen peroxide or its water-soluble sources body, or their mixture.Hydrogen peroxide most preferably uses in the present composition.Here used hydrogen peroxide cource body is meant any compound that can produce hydrogen peroxide when contacting with water.
Be used for the water-soluble source of suitable hydrogen peroxide of the present invention body and comprise percarbonate, persilicate, persulphate be a persulphate for example, and perborate and peroxy acid be diperoxy undecane diacid (DPDA), mistake magnesium phthalate and its mixture for example.
Be applicable to that composition of the present invention generally comprises the above-mentioned peroxygen bleach of the 0.5%-20% that accounts for total composition weight, preferred 2%-15%, most preferably 3%-10%.Really, peroxygen bleach, the existence of preferred hydrogen peroxide provides strong cleaning benefit, and this is tangible especially in laundry applications.
Be applicable to that composition of the present invention comprises as the chelated copper of second kind of main ingredient and/or the compound of iron and/or manganese.Generally, be applicable to that composition of the present invention comprises 0.005%-2% chelated copper and/or compound or its mixture of iron and/or manganese, preferably 0.01%-1%, the most preferably 0.01%-0.5% that accounts for total composition weight.
The compound of this chelated copper and/or iron and/or manganese can be can be in conjunction with any compound of copper and/or iron and/or manganese.The compound of this chelated copper and/or iron and/or manganese can be selected from the aromatic chelating agent of phosphine acid salt chelator, aminocarboxylate sequestrant, multifunctional replacement or the poly carboxylic acid of pyridine etc., or its mixture.
This phosphine acid salt chelator comprises ethydronic acid, hydroxyl ethane di 2 ethylhexyl phosphonic acid (HEDP) and ethylene nitrilo four (methylene phosphonic acid) N, N-dioxide, and aminophosphonic acid salt compound for example poly-(alkylene phosphonic acids salt), ethane 1-hydroxyl di 2 ethylhexyl phosphonic acid an alkali metal salt of amino alkylidenyl, nitrilo trimethylene phosphonic salt, ethylene diamine tetramethylene phosphonic acid salt and diethylenetriamine pentamethylenophosphonic acid(DTPP) salt.Phosphonate compounds can exist with its sour form, or exists with its some or all of acid functionality's different cationic salts.Phosphine acid salt chelator can be buied by Monsanto commercial, and trade mark is called DEQUEST.The preferred phosphine acid salt chelator that the present invention uses is diethylenetriamine pentamethylenophosphonic acid(DTPP) salt, hydroxyl ethane di 2 ethylhexyl phosphonic acid (HEDP) and ethylene nitrilo four (methylene phosphonic acid) N, the N-dioxide.
Found hydroxyl ethane di 2 ethylhexyl phosphonic acid and ethylene nitrilo four (methylene phosphonic acid) N, the N-dioxide can be resisted protonation and oxygenizement especially.So hydroxyl ethane di 2 ethylhexyl phosphonic acid and ethylene nitrilo four (methylene phosphonic acid) N, the compound that the N-dioxide is particularly suitable as chelated copper and/or iron and/or manganese is used in the acidic liquid composition of the present invention, and the integrity of fabric is improved thus.Really, hydroxyl ethane di 2 ethylhexyl phosphonic acid and/or ethylene nitrilo four (methylene phosphonic acid) N, the N-dioxide can be prepared the acidic liquid composition that contains peroxygen bleach, said composition compare with the same combination of this sequestrant not or with other sequestrant for example diethylenetriamine pentamethylenophosphonic acid(DTPP) replace the same combination of said sequestrant to compare, have the chemical stability of improvement.Therefore, another aspect of the present invention is to use hydroxyl ethane di 2 ethylhexyl phosphonic acid and/or ethylene nitrilo four (methylene phosphonic acid) N in containing the acidic liquid composition of peroxygen bleach, the N-dioxide, the chemical stability of said composition improves thus, that is, the rate of decomposition of said composition said SYNTHETIC OPTICAL WHITNER in storing for a long time reduces.
The aromatic chelating agent of multifunctional replacement also can be used in the composition of the present invention.Referring to the people's such as Connor that authorized on May 21st, 1974 U.S.3,812,044.The preferred compound of this sour form is the dihydroxyl disulfobenzene, for example 1, and 2-dihydroxyl-3,5-disulfobenzene.
Being used for the preferred biodegradable sequestrant of the present invention is quadrol N, N '-disuccinic acid or its basic metal, alkaline-earth metal, ammonium or its substituent ammonium salt or their mixture.Quadrol N, N '-disuccinic acid, particularly its (S, S) isomer has been described in detail in the Hartman that authorized on November 3rd, 1987 and the US4 of Perkins, in 704,233.Quadrol N, N '-disuccinic acid commercial can be from Palmer Research Laboratories for example with trade mark ssEDDS
Buy.
This aminocarboxylate as the compound of chelated copper and/or iron and/or manganese comprises edetate, diethylentriamine pentacetate, diethylentriamine pentacetate (DTPA), N-hydroxyethyl ethylene diamine triacetate, nitrilotriacetic acid(NTA) salt, ethylene diamine four propionic salts, triethylenetetraaminehexaacetic acid salt, ethanol Diglycocol, trimethylene diamine tetraacethyl (PDTA) and methylglycine oxalic acid (MGDA), and they not only existed with its sour form but also with the form of its basic metal, ammonium and substituted ammonium salt.Be specially adapted to of the present invention be diethylene triaminepentaacetic acid(DTPA) (DTPA), trimethylene diamine tetraacethyl (PDTA) its be for example commercial can be from BASF with trade name Trilon FS
Buy and methylglycine oxalic acid (MGDA).
Be applicable to that pyridine poly carboxylic acid of the present invention comprises pyridine dicarboxylic acid.The preferred pyridine dicarboxylic acid of the present invention is to use with the form of mixtures of the other compound of chelated copper according to the present invention and/or iron and/or manganese.Really, pyridine dicarboxylic acid be preferable over herein other sequestrant add according in the liquid composition of the present invention to improve the chemical stability of said composition.
Be applicable to that the present invention comprises two electron-donating groups with the adjacent coordination position that can occupy in the metallic ion coordination district as other sequestrant of the compound of chelated copper and/or iron and/or manganese so that form the sequestrant (3:1 sequestrant: metal ion, stoichiometric ratio) of title complex (wherein each metal ion cooperates with 3 molecule sequestrants) with metal ion.In other words, this sequestrant has occupied the metallic ion coordination district, makes it the catalysis inactivation thus.Special ability protonation of this sequestrant and/or oxygenizement have been found.Therefore this sequestrant compound of being particularly suitable as chelated copper and/or iron and/or manganese is used in the acidic liquid composition of the present invention, and the integrity of fabric improves thus.Really, this sequestrant with two electron-donating groups of the adjacent coordination position that can occupy in the metallic ion coordination district can be prepared the acidic composition that contains peroxygen bleach, said composition with compare without any the same combination of this sequestrant or with other sequestrant for example diethylenetriamine pentamethylenophosphonic acid(DTPP) replace the same combination of said sequestrant to compare, have improved chemical stability.Therefore another aspect of the present invention is to use two electron-donating groups with the adjacent coordination position that can occupy in the metallic ion coordination district so that form the sequestrant of title complex (wherein each metal ion cooperates with this sequestrant of 3 molecules) with metal ion in containing the acidic liquid composition of peroxygen bleach, the chemical stability of said composition improves thus, promptly, said composition is in storing for a long time, and the rate of decomposition of said SYNTHETIC OPTICAL WHITNER reduces.
This sequestrant with two electron-donating groups of the adjacent coordination position that can occupy in the metallic ion coordination district comprises the sequestrant of the ionization carboxyl (carboxylate) with direct neighbor at least one and the following group: unionization carboxyl (carboxylate), hydroxyl, amino or N-oxide groups.Being specially adapted to of the present invention is propanedioic acid, 2 hydroxy pyrimidine-N-oxide compound or its mixture.
2 hydroxy pyrimidine-N-oxide compound for example can be buied with trade(brand)name 2 hydroxy pyrimidine-N-oxide compound by Pyrion Chemie (Germany) commercial.
According to the present invention, with comprising peroxygen bleach and as the trimethylene diamine tetraacethyl (PDTA) of the compound of chelated copper and/or iron and/or manganese, methylglycine oxalic acid (MGDA), diethylenetriamine pentamethylenophosphonic acid(DTPP) (DTPMP), hydroxyl ethane di 2 ethylhexyl phosphonic acid (HEDP), quadrol N, N '-disuccinic acid (EDDS), 2 hydroxy pyrimidine-N-oxide compound (HPNO), and/or ethylene nitrilo four (methylene phosphonic acid) N, in the pretreated fabric of the liquid composition of N-dioxide, in fact there is not loss of tensile strength, the patience that is fabric does not reduce, even said composition was for example contacted for a long time with described fabric in 24 hours.
Therefore the present invention also comprises and comprises previously described peroxygen bleach and as trimethylene diamine tetraacethyl (PDTA), methylglycine oxalic acid (MGDA), 2 hydroxy pyrimidine-N-oxide compound, ethylene nitrilo four (methylene phosphonic acid) N of the compound of chelated copper and/or iron and/or manganese, the liquid composition of N-dioxide, hydroxyl ethane di 2 ethylhexyl phosphonic acid or its mixture.
Below the description of composition is related to the composition of the composition of claim of the present invention itself, pre-treatment dirt fabric used according to the invention and the method for pre-treatment dirt fabric is applied to composition on the fabric according to the present invention.
The present composition is aqueous liquid cleaning compositions.The pH of this aqueous composition is 1-9, preferred 2-6, more preferably 3-5.The pH of said composition can regulate with organic or inorganic acid or alkali reagent.
Composition of the present invention can further comprise various optional components for example free-radical scavengers, tensio-active agent, washing assistant, stablizer, other sequestrant, soil-suspending agent, dye migration agent, solvent, whitening agent, spices, antioxidant, suds suppressor and dyestuff.
The preferred optional component is free-radical scavengers or its mixture in the present composition.Be applicable to that free-radical scavengers of the present invention comprises list and dihydroxy-benzene and its analogue, alkyl and aryl carboxylic acid salt and its mixture of known replacement.The free-radical scavengers that the present invention preferably uses comprises butylhydroxy toluene, quinhydrones, di-tert-butyl hydroquinone, a tertiary butylated hydroquinone, tertiary butyl hydroxyl, phenylmethylether (anysole), phenylformic acid, toluic acid, catechol, tert-butyl catechol, benzylamine, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane its commercial with trade(brand)name Topanol CA
Ex ICI buys, and the n-propyl hydrochlorate.When using free-radical scavengers, its content in the present invention is generally the 0.001%-2% of total composition weight, preferred 0.001%-0.5%.
The present composition can further comprise any tensio-active agent well known by persons skilled in the art, comprises nonionic, negatively charged ion, positively charged ion, zwitter-ion or amphoterics.The present composition preferably comprises any nonionogenic tenside described below or its mixture, and/or any anion surfactant described below or its mixture.Generally, the present composition can comprise and accounts for total composition weight nearly 50% tensio-active agent or its mixture.
The present composition also can comprise the liquid hydrophobic bleach activator of conduct optional components very preferably.The meaning of bleach-activating agent is the compound that generates peracid with hydroperoxidation herein.The peracid of Xing Chenging has constituted the activatory SYNTHETIC OPTICAL WHITNER like this.This paper " hydrophobic bleach activator " meaning be basically with the immiscible stable activator of water.Generally, the HLB value of this hydrophobic bleach activator is lower than 11.This suitable liquid hydrophobic bleach activator generally belongs to ester, acid amides, imide or acid anhydride class.A particularly advantageous class bleach-activating agent is disclosed among the EP624154, particularly preferably is acetyl triethyl Citrate trianion (ATC) in this class.ATC has other advantage, and promptly it is gentle to environment, and this is because its eventual degradation is citric acid and alcohol.In addition, ATC has good stability to hydrolysis in the present composition, and it is effective bleach-activating agent.It finally provides the good ability of washing that helps to composition.Can also use the mixture of the liquid hydrophobic bleach-activating agent here.But the described bleach-activating agent of the as many as 20% of present composition Bao Zhanwei total composition weight or its mixture, preferred 2%-10%, most preferably 3%-7%.
When the composition that contains peroxygen bleach as the present invention also comprises the liquid hydrophobic bleach-activating agent, in order to reach stable purpose, the present invention needs most the water miscible liquid that said composition is mixed with the tensio-active agent that contains described liquid hydrophobic bleach-activating agent, or be formulated as be in comprise water, peroxygen bleach and comprise negatively charged ion and the mixture of the hydrophilic surfactant system of nonionogenic tenside in the microemulsion of described liquid hydrophobic bleach-activating agent.
In one embodiment of the present invention, be that composition that the present invention contains peroxygen bleach is when also comprising said bleach-activating agent and being formulated as water-base emulsion, for the liquid hydrophobic bleach activator of emulsification, this emulsion that contains peroxygen bleach should comprise the emulsifying surfactant system of at least two kinds of different surfaces promoting agents, and the hydrophobic surfactant of the promptly at least a HLB of having height to 9 and at least a HLB of having are higher than 10 hydrophilic surfactant.In order to make stable milk sap, said really two kinds of different tensio-active agents must have different HLB value (hydrophilic hydrophobic balance), and preferably the difference of the HLBs of these two kinds of tensio-active agents is 1 at least, preferably is 3 at least.In other words, suitably in water, mix at least two kinds of said tensio-active agents and can be made into stable milk sap, that is, place at least two weeks, not obvious basically stratified emulsion down at 50 ℃ with different HLBs.
Emulsion according to the present invention comprises and accounts for the said hydrophilic and hydrophobic surfactant of total composition weight 2%-50%, preferred 5%-40%, more preferably 8%-30%.Emulsion of the present invention comprises at least 0.1% said hydrophobic surfactant or its mixture that accounts for total emulsion weight, preferably at least 3%, more preferably at least 5% and account at least 0.1% said hydrophilic surfactant or its mixture of total emulsion weight, preferably at least 3%, more preferably at least 6%.
What the present invention preferably used is hydrophobic non ionic surfactants and hydrophilic nonionic tensio-active agent.Have HLB height to 9 in this hydrophobic non ionic surfactants used herein, preferably be lower than 9, more preferably less than 8, this hydrophilic surfactant has HLB and is higher than 10, preferably is higher than 11, more preferably is higher than 12.Really the hydrophobic non ionic surfactants of the present invention's use has fabulous degrease performance,, has the solvent action that promotes to remove hydrophobic dirt that is.From washing, hydrophobic surfactant is loaded onto it on fabric as the carrier of hydrophobic brightener, makes this whitening agent tightly approaching and act on fabric face thus.
Be used for suitable ionic surfactant pack of the present invention and draw together alkoxy fatty alcohols, preferred fat alcohol ethoxylate and/or propoxylated glycerine.Really, many this alkoxy fatty alcohols are commercial buying, and it has very different HLB value (hydrophilic hydrophobic balance).The HLB value of this alkoxy-based non-ionic surface active agent depends primarily on the chain length of Fatty Alcohol(C12-C14 and C12-C18), oxyalkylated character and degree of alkoxylation.Hydrophilic nonionic tensio-active agent tendency has the high degree of alkoxylation and the Fatty Alcohol(C12-C14 and C12-C18) of short chain, and the hydrophobic surfactant tendency has the low degree of alkoxylation and the Fatty Alcohol(C12-C14 and C12-C18) of long-chain.The tensio-active agent catalogue is available, and it has listed the kinds of surface promoting agent, comprises nonionogenic tenside, their corresponding HLB values.
The appropriate chemical methods that preparation is used for nonionogenic tenside of the present invention comprises corresponding pure and mild alkylene oxide with required ratio condensation.This method is well known to a person skilled in the art, describes in detail in the prior art.In addition, be applicable to that multiple alcohol alcoxylates of the present invention can be buied by various suppliers commercial.
The preferred hydrophobic non ionic surfactants that the present invention uses is to have HLB height to 9 and have formula RO-(C
2H
4O)
n(C
3H
6O)
mThe tensio-active agent of H, wherein R is C
6-C
22Alkyl chain or C
6-C
28The alkylbenzene chain, n+m is 0.5-5 here, and n is 0-5, and m is 0-5; Preferred n+m is 0.5-4, and n and m are 0-4.The preferred R chain that is used for here is C
8-C
22Alkyl chain.Therefore being used for suitable hydrophobic non ionic surfactants of the present invention is Dobanol
R91-2.5 (HLB=8.1, R are C
9And C
11The mixture of alkyl chain, n are 2.5, and m is 0), or Lutensol
RTO3 (HLB=8; R is C
13And C
15The mixture of alkyl chain, n are 3, and m is 0), or Tergitol
R25L3 (HLB=7.7; R is C
12-C
15Alkyl chain, n are 3, and m is 0), or Dobanol
R23-3 (HLB=8.1; R is C
12And C
13The mixture of alkyl chain, n are 3, and m is 0), or Dobanol
R23-2 (HLB=6.2; R is C
12And C
13The mixture of alkyl chain, n are 2, and m is 0) or its mixture.This paper is Dobanol preferably
R23-3 or Dobanol
R23-2, Lutensol
RTO3 or its mixture.These Dobanol
RTensio-active agent can be buied by SHELL commercial, these Lutensol
RTensio-active agent can be buied and these Tergitol by BASF commercial
RTensio-active agent can be buied by UNION CARBIDE commercial.Be used for the oxyalkylated tensio-active agent of hydrophobic non ionic surfactants right and wrong that other is fit to of the present invention, an example is Dobanol
R23 (HLB＜3).
The preferred hydrophilic nonionic tensio-active agent that the present invention uses is to have HLB to be higher than 10 and have a formula RO-(C
2H
4O)
n(C
3H
6O)
mThe tensio-active agent of H, wherein R is C
6-C
22Alkyl chain or C
6-C
28The alkylbenzene chain, n+m is 5-11 here, and n is 0-11, and m is 0-11; Preferred n+m is 6-10, and n and m are 0-10.In this was described, n and m referred to average oxyethyl group/propoxylation degree.The preferred R chain that is used for here is C
8-C
22Alkyl chain.Therefore being used for suitable hydrophilic nonionic tensio-active agent of the present invention is Dobanol
R23-6.5 (HLB=11.9; R is C
12And C
13The mixture of alkyl chain, n are 6.5, and m is 0), or Dobanol
R25-7 (HLB=12; R is C
12To C
15The mixture of alkyl chain, n are 7, and m is 0), or Dobanol
R45-7 (HLB=11.6; R is C
14And C
15The mixture of alkyl chain, n are 7, and m is 0), or Dobanol
R91-5 (HLB=11.6; R is C
9To C
11The mixture of alkyl chain, n are 5, and m is 0), or Dobanol
R91-6 (HLB=12.5; R is C
9To C
11The mixture of alkyl chain, n are 6, and m is 0), or Dobanol
R91-8 (HLB=13.7; R is C
9To C
11The mixture of alkyl chain, n are 8, and m is 0), or Dobanol
R91-10 (HLB=14.2; R is C
9To C
11The mixture of alkyl chain, n are 10, and m is 0), or its mixture.The present invention is Dobanol preferably
R91-10, Dobanol
R45-7, Dobanol
R23-6.5 or its mixture.These Dobanol
RTensio-active agent is buied by SHELL commercial.Except these hydrophilic nonionic tensio-active agents, other hydrophilic surfactant can further be used in the emulsion of the present invention, anion surfactant for example described below.
Emulsion of the present invention can further comprise other tensio-active agent, yet they should not change the weighted mean HLB value of total emulsion significantly.
In the particularly preferred embodiment of emulsion of the present invention; wherein this emulsion comprises the acetyl triethyl Citrate trianion as bleach-activating agent, and suitable nonionic surfactant system comprises that to have HLB for example be for example Dobanol of 6 hydrophobic non ionic surfactants
R23-2 and to have HLB for example be for example Dobanol of 15 hydrophilic nonionic tensio-active agent
R91-10.Other nonionic surfactant system that is fit to comprises for example Dobanol
R(23-6.5 HLB about 12) and Dobanol
R23 (HLB is lower than 6), or Dobanol
R45-7 (HLB=11.6) and Lutensol
RTO3 (HLB=8).
In an embodiment of the present invention, be composition that the present invention contains peroxygen bleach when comprising said bleach-activating agent and being mixed with microemulsion, the microemulsion that the present invention contains peroxygen bleach comprises the hydrophilic surfactant system that contains anion surfactant and nonionogenic tenside.Mix the hydrophobic activation agent for stable, key factor is that at least a said tensio-active agent must have different HLB values with this hydrophobic activation agent.Really,, may form the single phase of successive, therefore reduce the chemical stability of bleach/bleach activator system if all said tensio-active agents have identical HLB value with the hydrophobic activation agent.The HLB difference of preferred at least a said tensio-active agent and said bleach-activating agent is at least 1.0 HLB units, preferred 2.0 HLB units.
The anion surfactant that the present invention is fit to comprises that formula is 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 that formula is 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, and it can be the ammonium cation of metallic cation (for example sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replacement for example.Alkyl ethoxylated sulfate and alkyl propoxylated sulphates are that the present invention is desired.The object lesson of the ammonium cation that replaces comprises methyl, dimethyl, trimethyl ammonium and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine father-in-law and by alkanolamine for example ethamine, diethylamine, triethylamine and its mixture deutero-positively charged ion etc.Tensio-active agent as an example 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 to wash the anion surfactant of purpose.They can comprise soap salt (ammonium salt that comprises for example sodium, potassium, ammonium and replacement for example one, two and tri ethanol ammonium salt), C
9-C
20Linear alkylbenzene sulfonate, C
8-C
22Uncle or secondary paraffin sulfonate, C
8-C
24The sulfonation poly carboxylic acid that ethylenic 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
24Alkyl polyglycol ether sulfate (containing as many as 10 moles of ethylene oxide); Alkyl ester sulfonate is C for example
14-C
16Methyl ester (methylester) sulfonate, acylglycerol sulfonate, fatty oil acylglycerol vitriol, alkyl phenol epoxy ethane ether salt, paraffin sulfonate, alkylphosphonic, isethionate be acyl isethinate, N-acyl amino esilate, amber alkyl amide salts and sulfosuccinate, sulfosuccinic acid monoesters (especially saturated and undersaturated C for example
12-C
18Monoesters), sulfosuccinic acid diesters (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 to alkyl polysaccharide vitriol
2CH
2O)
KCH
2COO
-M
+That class, wherein R is C
8-C
22Alkyl, k are the integers of 0-10, and M forms the salifiable positively charged ion of solubility.Resinous acid and hydrogenated resin acid also are fit to, for example rosin, 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 are also general is disclosed in the people's such as Laughlin that authorized on December 30th, 1975 US.3, and in 929,678,23 hurdles 58 walk to 29 hurdles, 23 row (being quoted as a reference by this paper).
The ionic surfactant pack that is applicable to microemulsion of the present invention is drawn together the hydrophilic nonionic tensio-active agent that preamble defines.
The preferred method that preparation comprises the microemulsion of the present invention of liquid hydrophobic bleach-activating agent comprises tensio-active agent and water pre-mixing, adds other component then and comprises hydrogen peroxide and said hydrophobic bleach activator.Do not consider this preferred order of addition(of ingredients), importantly in the process of blending ingredients, this microemulsion is to keep consistently stirring under high relatively whipping force, preferably stirs 30 minutes under 750rpm, most preferably stirs 30 minutes under 1000rpm.
Be configured in embodiment of the present invention of microemulsion at composition, said composition is that naked eyes are visible transparent not existing under opalizer and the dyestuff.In centrifugal detection, observe the said microemulsion of the present invention and under 6000RPM, do not show after 15 minutes and be separated.Detect at microscopically, this microemulsion shows as the dispersion of drop in matrix.This matrix is above-mentioned hydrophilic matrix, and drop is to be made of the liquid hydrophobic bleach-activating agent.We have observed this particle has general pact or is lower than 3 microns diameter dimension.
Be applicable to that composition of the present invention also can comprise the suds suppressor of conduct optional components very preferably, for example 2-alkyl alkanol or its mixture.Being specially adapted to of the present invention is following 2-alkyl alkanol: it has 6-16 carbon atom alkyl chain, the alkyl chain of preferred 8-12 carbon atom, and terminal hydroxy group, this alkyl chain is contained 1-10 carbon atom at alpha position, preferred 2-8 carbon atom, more preferably the alkyl chain of 3-6 carbon atom replaces.This suitable compound is commercial buying, for example, and at Isofol
For example Isofol is arranged in the series
12 (2-butyl octanol) or Isofol
16 (2-hexyl decyl alcohol).Generally, be applicable to that composition of the present invention comprises 2-alkyl alkanol or its mixture of the 0.05%-2% that accounts for total composition weight, preferred 0.1%-1.5%, most preferably 0.1%-0.8%.
Though the advantageous applications of the composition that the present invention describes is the laundry pre-treatment, the present composition also can be used as detergent for washing clothes or detergent for washing clothes synergistic agent and Household bathroom or kitchen cleaning agent.When as hard surface cleaner, the luminosity that said composition is easy to rinsing and provides to the crust that cleans.
Following examples further specify the present invention.A) testing data
Mix the listed following composition of component preparation in listed ratio (weight %, except as otherwise noted).Composition I II III IV V VI alkyl-sulphate 1.2 1.2 1.2 1.2 1.2 1.2Dobanol
91-10 1.6 1.6 1.6 1.6 1.6 1.6Dobanol
23.3 1.1 1.1 1.1 1.1 1.1 1.1H
2O
27.0 7.0 7.0 7.0 7.0 7.0BHT, 0.03 0.03 0.03 0.03 0.03 0.03 spices, 0.1 0.1 0.1 0.1 0.1 0.1S, S-EDDS-0.5---DTPMP--0.5---MGDA---0.5--DTPA---0.5-HEDP-----0.5 water and accessory constituent _ _ _ _ _ to 100%_____H2SO
4To 24 hours S of pH4 loss of tensile strength (%) 60 00240 every gram fabric 50ppm copper pre-treatment, S EDDS is quadrol-N, N-disuccinic acid (S, S isomer).DTPMP is with trade(brand)name DEQUIEST by Monsanto
The diethylenetriamine pentamethylenophosphonic acid(DTPP) salt of selling.MGDA is the methylglycine oxalic acid.PDTA is with trade(brand)name Trilon FS by BASF
The trimethylene diamine tetraacethyl of selling.
Composition I only comprises hydrogen peroxide and does not have the compound of chelated copper and/or iron and/or manganese.Composition I I to VI is a typical example of the present invention, and they comprise the compound of hydrogen peroxide and chelated copper and/or iron and/or manganese.Carry out following test
The composition above-mentioned with this paper carries out the tensile strength test method.This test method is to carry out on the fabric that is contaminated with metals.
By sliver fabric (size 12.5 * 5cm that 50ppm concentration copper is arranged on the every gram cotton fabric of pre-treatment of the present invention
2).In fact with each the above-mentioned liquid composition pre-treatment of 2ml this paper of these sliver fabrics.Before with water rinse, composition stays with the sliver fabric and contacts 24 hours.Afterwards, estimate promptly the damage of sliver fabric until fracture by the said sliver fabric that stretches to fabric.Under wet condition, measure the required strength of fracture sliver fabric, i.e. limit tensile stress with " stress-strain instron machine ".The required strength of this sliver fabric that ruptures is low more, and is serious more to the damage that fabric produces.Each test is repeated 5 times, and the gained result has good confidence level (standard deviation=2 ÷ 5Kg).
The above-mentioned loss of tensile strength of different subject composition is represented with percentage ratio, and will obtain the loss of tensile strength result as the tensile strength and the tensile strength comparison of press the aforementioned pretreated identical fabric of this paper of the given fabric (promptly not having pretreated fabric) of reference.
Above result clearlys show that the liquid composition that uses the present invention to comprise the peroxygen bleach and the compound of chelated copper and/or iron and/or manganese compares without any the same combination (composition I) of the compound of chelated copper and/or iron and/or manganese with use, the result who obtains is that the fabric integrity has beyond thought improvement, and promptly loss of tensile strength reduces.In fact, when with the present composition (referring to composition I I to VI) pretreating fabrics, even through long-time, promptly 24 hours contact and have high density copper at said fabric face is under the situation of every gram cotton fabric 50ppm copper, does not also observe loss of tensile strength.B) embodiment
Mix the listed following composition of component preparation in listed ratio (weight %, except as otherwise noted).Composition I II III IV V VI VII VIIIH
2O
27.0 7.0 7.0 7.0 7.0 7.0 7.O, 7.0 alkyl-sulphates (1) 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2Dobanol
R91-10 1.6 1.6 1.6 1.6 1.6 1.6 1.6 1.6 Dobanol
R23-3 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1BHT 0.03 0.03 0.03 0.03--0.09 0.092-butyl octanol 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5S, S EDDS 0.5-------PDTA-0.5------DTPMP--0.5-0.18---MGDA---0.5----HPNO-----0.1--HEDP------0.18-DTPA-------0.1 water and accessory constituent (dyestuff) _ _ _ to 100%_____H2SO
4Transfer to pH4S, S EDDS is quadrol-N, N-disuccinic acid (S, S isomer).DTPMP is with trade(brand)name DEQUEST by Monsanto
The diethylenetriamine pentamethylenophosphonic acid(DTPP) salt of selling.MGDA is the methylglycine oxalic acid.PDTA is with trade(brand)name Trilon FS by BASF
The trimethylene diamine tetraacethyl of selling.HPNO is 2 hydroxy pyrimidine-N-oxide compound.HEDP is a hydroxyl ethane di 2 ethylhexyl phosphonic acid.DTPA is a diethylene triaminepentaacetic acid(DTPA).Composition I X X XI XII XIIIH
2O
27.0 7.0 7.0 4.0 6.0 alkylsurfuric acids, 1.2 1.2 1.2 2.0-AES25-3----12.0Dobanol
R45-7---6.4 6.0Dobanol
R91-10 1.6 1.6 1.6--Dobanol
R23-3 1.1 1.1 1.1 8.6-Dobanol
R23-6.5----6.0 activator (ATC)---3.5 3.5BHT 0.03 0.03 0.03 0.05 0.05S, S EDDS 0.1----PDTA-0.1---DTPMP--0.1--HEDP---0.1 0.1 pyridine dicarboxylic acid 0.05 0.05 0.05--water and accessory constituent _ _ _ _ to 100%_____
Example I to XIII be composition of the present invention.Carry out pre-treatment with composition I-XIII by the present invention, in fact processed fabric does not have loss of tensile strength, even composition is stayed to act on said fabric 24 hours also be like this.
Claims (15)
1. the purposes of liquid composition that comprises the compound of peroxygen bleach and chelated copper and/or iron and/or manganese, before washing dirt fabric with this fabric of said composition pre-treatment, thereby the loss of tensile strength of this fabric is reduced.
2. use the method for the liquid composition pre-treatment dirt fabric of the compound that comprises peroxygen bleach and chelated copper and/or iron and/or manganese, this method may further comprise the steps: before laundering of textile fabrics, said composition is applied on the fabric with its clean form, said composition and said fabric are kept in touch, but do not make said composition on said fabric, remain to drying.
3. according to the purposes of claim 1 or according to the method for claim 2, wherein the above-claimed cpd of chelated copper and/or iron and/or manganese be selected from aromatic chelating agent that phosphine acid salt chelator, aminocarboxylate sequestrant, polyfunctional group replace, pyridine poly carboxylic acid, have the adjacent coordination position that can occupy in the metallic ion coordination district two electron-donating groups so that form sequestrant and its mixture of title complex with metal ion, each metal ion cooperates with 3 molecule sequestrants in this title complex.
4. according to the purposes and the method for any aforementioned claim, the compound of wherein said chelated copper and/or iron and/or manganese is quadrol N, N '-disuccinic acid or its basic metal, alkaline-earth metal, ammonium or its substituent ammonium salt or diethylene triaminepentaacetic acid(DTPA), methylglycine oxalic acid, diethylenetriamine pentamethylenophosphonic acid(DTPP), hydroxyl ethane di 2 ethylhexyl phosphonic acid, trimethylene diamine tetraacethyl, 2 hydroxy pyrimidine-N-oxide compound, ethylene nitrilo four (methylene phosphonic acid) N, N-dioxide or its mixture.
5. according to the purposes and the method for any aforementioned claim, wherein said liquid composition comprises the 0.005%-2% chelated copper that accounts for total composition weight and/or above-claimed cpd or its mixture of iron and/or manganese, preferred 0.01%-1%, more preferably 0.01%-0.5%.
6. according to the purposes and the method for any aforementioned claim, wherein said peroxygen bleach is hydrogen peroxide or its water-soluble sources body, preferred hydrogen peroxide.
7. according to the purposes and the method for any aforementioned claim, wherein said composition comprises the said peroxygen bleach of the 0.5%-20% that accounts for total composition weight or its mixture, preferred 2%-15%, more preferably 3%-10%.
8. according to the purposes and the method for any aforementioned claim, wherein said composition also is included as the tensio-active agent of total composition weight as many as 50%.
9. liquid detergent composition, said composition comprises peroxygen bleach and is used as methylglycine oxalic acid, trimethylene diamine tetraacethyl, 2 hydroxy pyrimidine-N-oxide compound, ethylene nitrilo four (methylene phosphonic acid) N of the compound of chelated copper and/or iron and/or manganese, N-dioxide, hydroxyl ethane di 2 ethylhexyl phosphonic acid or its mixture.
10. according to the composition of claim 9, said peroxygen bleach is hydrogen peroxide or its water-soluble sources body, preferred hydrogen peroxide, and also wherein said composition comprises the said peroxygen bleach of the 0.5%-20% that accounts for total composition weight, preferred 2%-15%, more preferably 3%-10%.
11. according to the composition of one of claim 9 or 10, wherein this liquid composition comprises 0.005%-2% chelated copper and/or above-claimed cpd or its mixture of iron and/or manganese, preferably 0.01%-1%, the more preferably 0.01%-0.5% that accounts for total composition weight.
12. according to the composition of one of claim 9-11, wherein said composition is water base, and to have pH be 1-9, preferred 2-6, more preferably 3-5.
13. according to the composition of one of claim 9-12, wherein said composition also comprises tensio-active agent or its mixture that accounts for total composition weight as many as 50%, preferred nonionic surfactants or its mixture and/or anion surfactant or its mixture.
14. the purposes of composition of the preferred claim 1 of liquid composition of compound that comprises peroxygen bleach and chelated copper and/or iron and/or manganese with this fabric of said composition pre-treatment, therefore made the color of this fabric destroy and is lowered before the band yarn dyed fabric of washing dirt.
15. the purposes of sequestrant in comprising the liquid acidic composition of peroxygen bleach, this sequestrant comprises two electron-donating groups with the adjacent coordination position that can occupy in the metallic ion coordination district so that form the sequestrant of title complex with metal ion, each metal ion cooperates with 3 molecule sequestrants in this title complex, and/or ethylene nitrilo four (methylene phosphonic acid) N, N-dioxide sequestrant, and/or hydroxyl ethane di 2 ethylhexyl phosphonic acid sequestrant, therefore the chemical stability of said composition is improved.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95870018.9 | 1995-02-28 | ||
| EP95870018 | 1995-02-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1176656A true CN1176656A (en) | 1998-03-18 |
Family
ID=8222114
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96192233A Pending CN1176656A (en) | 1995-02-28 | 1996-02-20 | Laundry pretreatment with peroxide bleaches containing chelators for iron, copper or manganese for reduced fabric damage |
Country Status (19)
| Country | Link |
|---|---|
| EP (1) | EP0812348B1 (en) |
| JP (1) | JPH11502549A (en) |
| KR (1) | KR100249610B1 (en) |
| CN (1) | CN1176656A (en) |
| AT (1) | ATE230042T1 (en) |
| AU (1) | AU711340B2 (en) |
| BR (1) | BR9607400A (en) |
| CA (1) | CA2213633C (en) |
| CZ (1) | CZ270297A3 (en) |
| DE (1) | DE69625471T2 (en) |
| ES (1) | ES2185764T3 (en) |
| FI (1) | FI973517A (en) |
| HU (1) | HUP9800073A2 (en) |
| NO (1) | NO973910L (en) |
| PL (1) | PL322021A1 (en) |
| SK (1) | SK115597A3 (en) |
| TR (1) | TR199700867T1 (en) |
| WO (1) | WO1996026999A1 (en) |
| ZA (1) | ZA961586B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103290670A (en) * | 2013-05-16 | 2013-09-11 | 辽宁腾达集团股份有限公司 | Method for removing residual oxygen of pure-cotton knitted fabric by use of heat energy after bleaching |
| CN103717725A (en) * | 2011-08-15 | 2014-04-09 | 宝洁公司 | Detergent compositions containing pyridinol-n-oxide compounds |
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| EP0752469B1 (en) * | 1995-07-05 | 2004-09-22 | The Procter & Gamble Company | Laundry pre-treatment with improved fabric/colour safety |
| GB2311537A (en) * | 1996-03-29 | 1997-10-01 | Procter & Gamble | Rinse composition for dishwashers |
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| GB2311542A (en) * | 1996-03-29 | 1997-10-01 | Procter & Gamble | Percarbonate bleach composition |
| GB2311536A (en) * | 1996-03-29 | 1997-10-01 | Procter & Gamble | Dishwashing and laundry detergents |
| GB2311538A (en) * | 1996-03-29 | 1997-10-01 | Procter & Gamble | Detergent compositions |
| ES2183929T3 (en) * | 1996-10-31 | 2003-04-01 | Procter & Gamble | BLOSSOMING WATERPROOF LIQUID COMPOSITIONS AND PRE-TREATMENT PROCEDURE. |
| US6242407B1 (en) * | 1996-11-22 | 2001-06-05 | The Procter & Gamble Company | Laundry bleaching compositions |
| US5968884A (en) * | 1997-04-07 | 1999-10-19 | Basf Corporation | Concentrated built liquid detergents containing a biodegradable chelant |
| US6692536B1 (en) | 1997-11-24 | 2004-02-17 | The Procter & Gamble Company | Use of a crystal growth inhibitor to reduce fabric abrasion |
| EP0924292B1 (en) * | 1997-11-24 | 2005-05-25 | The Procter & Gamble Company | Use of a crystal growth inhibitor to reduce fabric abrasion |
| EP0918088A1 (en) * | 1997-11-24 | 1999-05-26 | The Procter & Gamble Company | Use of a crystal growth inhibitor to reduce fabric abrasion |
| GB2333772A (en) * | 1998-01-31 | 1999-08-04 | Procter & Gamble | Complexing agents (eg ethylenediamine disuccinic acid) for use in selectively complexing copper, iron, zinc, nickel and cobalt in the presence of calcium |
| US6204233B1 (en) | 1998-10-07 | 2001-03-20 | Ecolab Inc | Laundry pre-treatment or pre-spotting compositions used to improve aqueous laundry processing |
| EP1208184A1 (en) * | 1999-09-01 | 2002-05-29 | Unilever Plc | Method of pretreating and bleaching stained fabrics |
| JP3857082B2 (en) * | 2001-07-24 | 2006-12-13 | 花王株式会社 | Laundry pretreatment composition for clothing |
| US6767881B1 (en) | 2003-03-19 | 2004-07-27 | Ecolab, Inc. | Cleaning concentrate |
| JP5401034B2 (en) * | 2007-12-19 | 2014-01-29 | ライオン株式会社 | Bleaching aid and bleaching aid particles containing the bleaching aid |
| DE102008023014A1 (en) | 2008-05-09 | 2009-11-12 | Henkel Ag & Co. Kgaa | Aqueous textile treatment agent |
| JP5544716B2 (en) * | 2009-01-13 | 2014-07-09 | 栗田工業株式会社 | Method for cleaning circulating cooling water in steel manufacturing process |
| MX2012003186A (en) * | 2009-09-15 | 2012-04-30 | Procter & Gamble | Detergent composition comprising mixture of chelants. |
| MX342989B (en) | 2009-10-30 | 2016-10-20 | Akzo Nobel Chemicals Int Bv | Use of a metal supplement in animal feed. |
| JP5850582B2 (en) * | 2010-07-27 | 2016-02-03 | クラリアント・ファイナンス・（ビーブイアイ）・リミテッド | Composition comprising hydrogen peroxide or hydrogen peroxide donating substance |
| CH703870B1 (en) * | 2010-09-29 | 2014-11-28 | Genossenschaft Coop | Disinfecting cleaning composition. |
| US10060073B2 (en) | 2013-05-23 | 2018-08-28 | Washing Systems, Llc | Method of laundering industrial garments |
| PL224478B1 (en) | 2013-06-03 | 2016-12-30 | Eko Styl Spółka Z Ograniczoną Odpowiedzialnością | Method for dressing fabrics in the process of washing |
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| FR2545854B1 (en) * | 1983-05-10 | 1985-07-26 | Ugine Kuhlmann | PROCESS FOR BLEACHING TEXTILES IN THE PRESENCE OF IRON PARTICLES OR FERROUS METALS |
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| EP0209228B2 (en) * | 1985-06-17 | 1999-06-09 | The Clorox Company | Stabilized liquid hydrogen peroxide bleach compositions |
| US4900468A (en) * | 1985-06-17 | 1990-02-13 | The Clorox Company | Stabilized liquid hydrogen peroxide bleach compositions |
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| EP0629690B1 (en) * | 1993-06-09 | 1999-11-03 | The Procter & Gamble Company | Stable aqueous emulsions of nonionic surfactants |
| ES2121983T3 (en) * | 1993-06-09 | 1998-12-16 | Procter & Gamble | STABLE AQUEOUS EMULSIONS OF NON-IONIC SURFACTANTS. |
| GB2294707A (en) * | 1994-11-05 | 1996-05-08 | Procter & Gamble | Bleaching composition |
-
1996
- 1996-02-20 DE DE69625471T patent/DE69625471T2/en not_active Expired - Lifetime
- 1996-02-20 BR BR9607400A patent/BR9607400A/en not_active Application Discontinuation
- 1996-02-20 ES ES96906534T patent/ES2185764T3/en not_active Expired - Lifetime
- 1996-02-20 KR KR1019970705972A patent/KR100249610B1/en not_active IP Right Cessation
- 1996-02-20 PL PL96322021A patent/PL322021A1/en unknown
- 1996-02-20 AT AT96906534T patent/ATE230042T1/en not_active IP Right Cessation
- 1996-02-20 AU AU49882/96A patent/AU711340B2/en not_active Ceased
- 1996-02-20 WO PCT/US1996/002219 patent/WO1996026999A1/en active IP Right Grant
- 1996-02-20 SK SK1155-97A patent/SK115597A3/en unknown
- 1996-02-20 CA CA002213633A patent/CA2213633C/en not_active Expired - Fee Related
- 1996-02-20 EP EP96906534A patent/EP0812348B1/en not_active Expired - Lifetime
- 1996-02-20 HU HU9800073A patent/HUP9800073A2/en unknown
- 1996-02-20 TR TR97/00867T patent/TR199700867T1/en unknown
- 1996-02-20 CN CN96192233A patent/CN1176656A/en active Pending
- 1996-02-20 JP JP8526295A patent/JPH11502549A/en active Pending
- 1996-02-20 CZ CZ972702A patent/CZ270297A3/en unknown
- 1996-02-28 ZA ZA961586A patent/ZA961586B/en unknown
-
1997
- 1997-08-26 NO NO973910A patent/NO973910L/en not_active Application Discontinuation
- 1997-08-27 FI FI973517A patent/FI973517A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103717725A (en) * | 2011-08-15 | 2014-04-09 | 宝洁公司 | Detergent compositions containing pyridinol-n-oxide compounds |
| CN103290670A (en) * | 2013-05-16 | 2013-09-11 | 辽宁腾达集团股份有限公司 | Method for removing residual oxygen of pure-cotton knitted fabric by use of heat energy after bleaching |
Also Published As
| Publication number | Publication date |
|---|---|
| HUP9800073A2 (en) | 1998-04-28 |
| EP0812348A4 (en) | 2000-04-12 |
| PL322021A1 (en) | 1998-01-05 |
| CA2213633C (en) | 2002-01-22 |
| AU711340B2 (en) | 1999-10-14 |
| FI973517A0 (en) | 1997-08-27 |
| FI973517A (en) | 1997-10-27 |
| ATE230042T1 (en) | 2003-01-15 |
| KR19980702566A (en) | 1998-07-15 |
| DE69625471T2 (en) | 2003-11-06 |
| CZ270297A3 (en) | 1998-01-14 |
| SK115597A3 (en) | 1998-06-03 |
| EP0812348A1 (en) | 1997-12-17 |
| NO973910D0 (en) | 1997-08-26 |
| ES2185764T3 (en) | 2003-05-01 |
| MX9706537A (en) | 1997-11-29 |
| JPH11502549A (en) | 1999-03-02 |
| WO1996026999A1 (en) | 1996-09-06 |
| KR100249610B1 (en) | 2000-03-15 |
| AU4988296A (en) | 1996-09-18 |
| TR199700867T1 (en) | 1998-01-21 |
| BR9607400A (en) | 1998-06-30 |
| EP0812348B1 (en) | 2002-12-18 |
| NO973910L (en) | 1997-08-26 |
| CA2213633A1 (en) | 1996-09-06 |
| ZA961586B (en) | 1996-09-06 |
| DE69625471D1 (en) | 2003-01-30 |
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