CN1237202A - Laundry bleaching processes and compositions - Google Patents

Laundry bleaching processes and compositions Download PDF

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Publication number
CN1237202A
CN1237202A CN97199585A CN97199585A CN1237202A CN 1237202 A CN1237202 A CN 1237202A CN 97199585 A CN97199585 A CN 97199585A CN 97199585 A CN97199585 A CN 97199585A CN 1237202 A CN1237202 A CN 1237202A
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China
Prior art keywords
composition
solvent
hydrophilic
preferred
mixture
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CN97199585A
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Chinese (zh)
Inventor
V·马索蒂
L·萨尔斯内利
S·夏拉
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Procter and Gamble Co
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Procter and Gamble Co
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Publication of CN1237202A publication Critical patent/CN1237202A/en
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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
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • 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
    • C11D3/43—Solvents
    • 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
    • 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
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/2034—Monohydric alcohols aromatic

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

本发明涉及用液体组合物漂白织物,所述组合物含有过氧漂白剂和含有亲水溶剂和疏水溶剂的溶剂体系。这些组合物提供对各种污渍,包括可漂白的污渍、油脂性污渍、酶污渍和泥浆/粘土污渍的改善的去污。This invention relates to bleaching fabrics with liquid compositions containing a peroxide bleach and a solvent system containing hydrophilic and hydrophobic solvents. These compositions provide improved stain removal for a variety of stains, including bleachable stains, greasy stains, enzyme stains, and mud/clay stains.

Description

Laundry bleaching processes and composition
Technical field
The present invention relates to the bleaching of fabric.
Background of invention
Various cleaning composition have been described in the prior art.Conventional cleaning composition is being used for laundry applications to handle various fabrics, comprise cotton and synthetic textiles, for example the problem that is run into when polyester, polymeric amide etc. be they can not provide satisfy satisfactorily that the human consumer requires to all types of spots, comprise the effective performance of oil spot, enzyme spot, mud/clay spot etc.
Therefore, the purpose of this invention is to provide provides the whole detergency ability that improves to various spots, and the outstanding performance of drifting is provided simultaneously.
We find that now this purpose can be by with containing peroxygen bleach and containing hydrophobic solvent, be hydrophilic index less than 18 solvent and hydrophilic solvent, being hydrophilic index satisfies greater than the liquid composition bleached woven fabric of the solvent system of 18 solvent, and wherein hydrophilic index is by following formula definition:
The molecular weight of the hydrophilic segment of solvent
-------------------------------------?*?100
The total molecular weight of solvent
In fact, we find to contain the liquid composition of peroxygen bleach and this solvent system when being used for laundry operations, increased various types of spots, comprised oil spot, contain mud/the clay spot, the soil removability of enzyme spot and the spot that can bleach.
Advantage of the present invention is in various laundry applications, provides outstanding performance in for example detergent for washing clothes, or laundry additive and the pretreating agent of preferably doing washing.
In a preferred embodiment of the invention, be used for liquid composition of the present invention and also contain bleach-activating agent, it will be in water-bearing media with hydroperoxidation to form corresponding peracid.People have found peracid under lower temperature, and are for example more effective under the temperature of carrying out pretreatment operation usually (20 ℃-25 ℃), thereby make the present composition that more effective bleachability is provided under the temperature of wide region.
Another advantage of specific embodiments of the present invention is to add when being mixed with the liquid-liquid composition of milk sap or microemulsion when described solvent system herein, the viscosity degradation of described composition, and no matter viscosity is how before adding described solvent system.Therefore, in one embodiment, the present invention also provides milky liquid liquid or the microemulsion that contains peroxygen bleach and solvent system as herein described, its medium viscosity can be controlled easily, and keep enough physical stabilities, and do not need to add any viscosity control agent that can improve formulation cost, and not needing to increase the volume of composition yet, this is helpless to the bleaching/scourability of described composition.
EP-A-126545 discloses the agent of liquid scrub clean, and it contains abrasive material, at least 0.1% terpenes (for example d-limonene), at least 0.1% benzylalcohol and optionally tensio-active agent, washing assistant etc.The grease of composition cleaning of hard surfaces and particulate fouling.Unexposed SYNTHETIC OPTICAL WHITNER, also unexposed laundry applications.
EP-A-216416 discloses liquid scrub clean agent (pH8-12), and it contains paraffin sulfonate and alkylbenzene sulfonate, 0.5%-10% list or sesquiterpene, and the 0.5-3% polar solvent, acrylic acid series polymeric viscosifier, abrasive material and viscosity improve compound.Unexposed SYNTHETIC OPTICAL WHITNER, also unexposed laundry applications.
EP-A-137616 discloses the laundry liquid composition that is mixed with form of emulsion, and it has 6.5 or higher pH, contains at least 5% solvent by weight.This solvent comprises terpenes and terpenoid solvent (for example firpene, d-limonene) and other solvent, as benzylalcohol, n-hexyl alcohol, paraffinic hydrocarbon.The mixture of orange terpenes and benzylalcohol is especially suitable for the spot of removing some type as dirty machine oil.Add non-polar solvent, increased stability as benzylalcohol, n-hexyl alcohol, blended Fatty Alcohol(C12-C14 and C12-C18).Disclose with pre-treatment and the whole carrying out washing treatment of said composition fabric.Unexposed SYNTHETIC OPTICAL WHITNER.
Summary of the invention
The present invention includes method with the liquid composition bleached woven fabric, described liquid composition contains peroxygen bleach and contains hydrophilic index greater than 18 hydrophilic solvent and the hydrophilic index solvent system less than 18 hydrophobic solvent, and wherein hydrophilic index is by following formula definition:
The molecular weight of solvent hydrophilic segment
--------------------------------------?*?100
The total molecular weight of solvent
Described method is included in rinsing or washs then before the rinse fabric, and described composition is applied on the described fabric with respective pure form, the step on preferred only its dirty part.
The present invention also comprises the method for bleached woven fabric, it comprises the steps: that in water-bath dilution contains the liquid composition of the respective pure form of peroxygen bleach and solvent system defined above, described fabric is contacted with the water-bath that contains described liquid composition and with post rinsing or wash the described fabric of rinsing then.
Finally, the present invention includes the liquid composition that is applicable to bleached woven fabric, it contains peroxygen bleach and contains by the hydrophilic index of general composition weight meter 0.05%-20% greater than 18 hydrophilic solvent with by the solvent system of general composition weight meter 0.05%-10% hydrophilic index less than 18 hydrophobic solvent, and wherein hydrophilic index is by following formula definition:
The molecular weight of solvent hydrophilic segment
-----------------------------------------?*100
The total molecular weight of solvent
The method of the detailed description bleached woven fabric of invention
The present invention includes the method for bleached woven fabric, begin by containing peroxygen bleach and containing the liquid bleaching composition packed that contains the solvent system of hydrophobic solvent and hydrophilic solvent as herein described.
In fact, the present invention is based on following discovery, promptly, solvent system of the present invention contains in the liquid composition of peroxygen bleach by being added, with do not have described solvent system or only contain one type solvent, be that hydrophilic solvent or hydrophobic solvent as described herein rather than the detergency ability that same combination provided that contains the described solvent system of hydrophilic solvent and hydrophobic solvent are simultaneously compared, when described composition is used to handle dirty fabric, especially in pre-treatment is used, the detergency ability that is improved.
" detergency ability " is meant various stain among the present invention, the detergency ability of for example greasy/oil-dirt and/or enzyme spot and/or mud/clay spot and the spot that can bleach.
" greasy/oil-dirt " is meant any oil dirt and the spot that can find among the present invention on fabric, as dirty motor oil, mineral oil, makeup, lipstick, vegetables oil, macaroni sauce, mayonnaise etc.In fact, to be found makeup and macaroni sauce be especially effective to liquid composition of the present invention.
The example of enzyme spot comprises grass, chocolate and blood.The example of the spot that can bleach comprises tea, coffee, grape wine etc.
For example, given composition can be by following test method evaluation to the detergency ability of dirty fabric under pretreatment condition.At first composition of the present invention is applied to the dirty part of fabric, be allowed to condition at and act on about 10 minutes of about 1-on the fabric, preferred 5 minutes, afterwards, with pretreated fabric with conventional detergent composition according to conventional wash conditions, 30 ℃-70 ℃ for some time that washing is enough to bleach described fabric.For example, the typical dirty fabric that is used for the test of this detergency ability industrial can be by EMC (Empirical Manufacturing Company), Cincinnati, Ohio, USA obtains, for example at two kinds of different dirt-carrying bodies: clay, grass, macaroni sauce, gravy, dirty motor oil, makeup, barbecue sauce, tea, blood on cotton (CW120) and poly-cotton (PCW28).
Detergency ability can for example not have the pretreated dirty fabric of same combination of solvent system of the present invention to estimate by side by side relatively with the pretreated dirty fabric of composition of the present invention and use reference substance.Can use and look the grading standard and determine difference with the 0-4 of the expert unit of scoring (psu).
The method of bleached woven fabric of the present invention comprises and fabric being contacted with the liquid bleaching composition packed that contains peroxygen bleach and solvent system as herein described of pure or dilute form and with the step of the described fabric of post rinsing.In preferred embodiments, when fabric quilt " pre-treatment ", composition is applied on the fabric with respective pure form, rinse fabric, or washing and rinsing then in normal wash(ing)cycle subsequently.We find, use compositions for use of the present invention, and when composition directly contacted with the dirty part of fabric before washing/rinsing, the improvement of detergency ability was especially significant.
As the first necessary component, the used liquid composition of the present invention contains peroxygen bleach or its mixture.This peroxygen bleach comprises hydrogen peroxide or its water-soluble sources or their mixture.In fact, have peroxygen bleach, preferred hydrogen peroxide and/or hydroperoxide and/or aliphatic diacyl peroxide help the fabulous washing and the bleaching effect of the present composition.The hydrogen peroxide cource that uses among the present invention is meant any perhydroxyl radical ionic compound that produces when described compound contacts with water.
Be used for suitable water-soluble hydrogen peroxide cource of the present invention and comprise percarbonate, persilicate, persulphate; for example single persulphate, perborate, peroxy acid, for example diperoxy dodecanedioic acid (DPDA), mistake phthalic acid magnesium, peroxybenzoic acid and alkyl peroxybenzoic acid, alkyl hydroperoxide, superoxide, aliphatic diacyl peroxide and their mixture.Hydrogen peroxide and/or alkyl hydroperoxide and/or aliphatic diacyl peroxide are preferred in the present composition.
Being used for suitable hydroperoxide of the present invention is tert-butyl hydroperoxide, cumyl hydroperoxide, 2,4,4-tri-methyl-amyl-2-hydroperoxide, diisopropyl benzene list hydroperoxide, t-amyl hydroperoxide and 2,5-dimethyl-hexane-2,5-dihydro-peroxidase.These hydroperoxide have fabric and the especially safe advantage of color when fabulous bleachability is provided.
Being used for suitable aliphatic diacyl peroxide of the present invention is two bay acyl peroxides, didecyl acyl peroxide, two myristoyl superoxide or their mixture.This aliphatic series diacyl peroxide has fabric and the especially safe advantage of color when fabulous bleachability is provided.
The present composition contains usually by the peroxygen bleach of general composition weight meter 0.01%-20% or their mixture, preferred 1%-10%, more preferably 4%-7%.
As second necessary component, the used liquid composition of the present invention contains the solvent system that comprises hydrophobic solvent and hydrophilic solvent.
" solvent " in this article refers to any hydrocarbon, and it comprises saturated or undersaturated hydrocarbon of aliphatic series or aromatic hydrocarbon, and it contains or do not contain one or more alcohol groups, one or more ether group and/or one or more ketone groups.
Be the hydrophilic or hydrophobic property of definition solvent of the present invention, use following hydrophilic index (HI):
The molecular weight of solvent hydrophilic segment
----------------------------------------?*100
The total molecular weight of solvent
" hydrophilic segment " of given solvent in this article refers to all group O, CO and OH of given solvent.
" molecular weight of solvent hydrophilic segment " in this article refers to the total molecular weight of all hydrophilic segments of given solvent.
Be used for hydrophilic solvent of the present invention and have and surpass 18, preferably surpass 25, more preferably surpass 30 hydrophilic index, have and be lower than 18, preferably be lower than 17 and more preferably less than 16 or littler hydrophilic index and be used for hydrophobic solvent of the present invention.
The mixture of these solvents to various types of spots, provides the overall detergency ability of improvement in adding the liquid composition contain peroxygen bleach the time as oil spot (for example dirty machine oil), enzyme spot (for example blood) and clay spot.In addition, when this solvent system adds in the liquid composition that contains peroxygen bleach, also provide the bleaching effect that improves.Can estimate that described solvent can be the carrier of other active ingredient of existing in the described liquid composition, helps them to infiltrate in the spot.In fact, hydrophobic solvent can be the carrier of hydrophobic active ingredient such as hydrophobic bleach agent (for example two bay acyl peroxides), and hydrophilic solvent can be the carrier of hydrophilic SYNTHETIC OPTICAL WHITNER such as hydrogen peroxide.
Be used for suitable hydrophobic solvent of the present invention and comprise paraffinic hydrocarbons, terpenes or terpene derivatives and alkoxylate aliphatic series or aromatic alcohol, aliphatic series or aromatic alcohol, glycol or alkoxylated diols and their mixture, all these solvents have the hydrophilic index less than 18.
Suitable terpenes (hydrophilic index 0) is single and two ring monoterpene, especially those hydrocarbons, and it comprises terpinene, terpinolene, limonene and firpene and their mixture.The highly preferred material of this class is d-limonene, limonene, α-Pai Xi and/or beta-pinene.For example firpene can be obtained with title Alpha Pinene P﹠F  by SCM Glidco (Jacksonville) commercial.
Hydrophilic index is less than 18 terpene derivatives, and for example alcohol, aldehyde, ester and ketone also can be used for the present invention, and this material for example can be used as commercial that the α and the beta isomer of terpinol and linalool obtain.
All types of paraffinic hydrocarbonss (hydrophilic index 0) can be used for the present invention, no matter be straight chain or be not straight chain, it contains 2-20 carbon atom, preferred 4-10 carbon atom, more preferably 6-8 carbon atom.The preferred octane of the present invention, octane can be obtained by for example BASF commercial.
Can be used for suitable hydrophobic alkoxylate aliphatic series of the present invention or aromatic alcohol and have formula: R (A) n-OH, wherein R has 1-20 carbon atom, preferred 2-15 the carbon atom and the more preferably aryl of saturated or unsaturated alkyl or alkyl replacement or the replacement of non-alkyl of the straight or branched of 2-10 carbon atom, wherein A is an alkoxyl group, preferred butoxy, propoxy-and/or oxyethyl group, with n be the integer of 1-5, preferred 1-2.Being used for suitable hydrophobic alcohol alcoxylates of the present invention is 1-methoxyl group-11-dodecanol (HI=15).
Be used for suitable hydrophobic aliphatic series or aromatic alcohol of the present invention and have formula: R-OH, wherein R has a 1-20 carbon atom, preferred 2-15 the carbon atom and the more preferably aryl of saturated or unsaturated alkyl or alkyl replacement or the replacement of non-alkyl of the straight or branched of 2-10 carbon atom.Be used for suitable fatty alcohol of the present invention and comprise straight chain alcohol, as dodecanol (HI=7).Being used for suitable aromatic alcohol of the present invention is benzylalcohol (HI=16).
Be used for suitable hydrophobic diol of the present invention and have formula: HO-CR1R2-OH, wherein R1 and R2 be independently hydrogen C2-C10 is saturated or the unsaturated aliphatic hydrocarbon chain and/ring.Being used for suitable diol of the present invention is dodecanediol (HI=16).
Can be used for suitable hydrophobic alkoxylated diols of the present invention and have formula: R (A) n-R1-OH, wherein R is H, OH, has a 1-20 carbon atom, preferred 2-15 the carbon atom and the more preferably saturated or unsaturated alkyl of straight chain of 2-10 carbon atom, R1 is H or has 1-20 carbon atom, preferred 2-15 the carbon atom and the more preferably saturated or unsaturated alkyl of straight chain of 2-10 carbon atom, wherein A is an alkoxyl group, preferably oxyethyl group, methoxyl group and/or propoxy-, with n be 1-5, preferred 1-2.Being used for suitable alkoxylated diols of the present invention is methoxyl group stearyl alcohol (HI=11).
Be used for especially preferred hydrophobic solvent of the present invention and comprise d-limonene, limonene, α-Pai Xi, beta-pinene, octane, benzylalcohol or their mixture.
Be used for suitable hydrophilic solvent of the present invention and comprise alkoxylate aliphatic series or aromatic alcohol, aliphatic series or aromatic alcohol, glycol or alkoxylated diols and their mixture, all these solvents have the hydrophilic index above 18.
Can be used for suitable hydrophilic alkoxylate aliphatic series of the present invention or aromatic alcohol and have formula: R (A) n-OH, wherein R has 1-20 carbon atom, preferred 2-15 the carbon atom and the more preferably aryl of saturated or unsaturated alkyl or alkyl replacement or the replacement of non-alkyl of the straight or branched of 2-10 carbon atom, wherein A is an alkoxyl group, preferred butoxy, propoxy-and/or oxyethyl group, with n be the integer of 1-5, preferred 1-2.Be used for specially suitable alcohol alcoxylates of the present invention and comprise methoxypropanol (HI=37), oxyethyl group propyl alcohol (HI=32), propoxy-propyl alcohol (HI=28) and/or butoxy propyl alcohol (HI-27).
Be used for suitable hydrophilic aliphatic series or aromatic alcohol of the present invention and have formula: R-OH, wherein R has a 1-20 carbon atom, preferred 2-15 the carbon atom and the more preferably aryl of saturated or unsaturated alkyl or alkyl replacement or the replacement of non-alkyl of the straight or branched of 2-10 carbon atom.Be used for specially suitable fatty alcohol of the present invention and comprise straight chain alcohol, as ethanol (HI=37) and/or propyl alcohol (HI=28).
Be used for suitable hydrophilic diol of the present invention and have formula: HO-CR1R2-OH, wherein R1 and R2 be independently hydrogen C2-C10 is saturated or the unsaturated aliphatic hydrocarbon chain and/ring.Being used for specially suitable glycol of the present invention is propylene glycol (HI=45).
Can be used for suitable hydrophilic alkoxylated diols of the present invention and have formula: R (A) n-R1-OH, wherein R is H, OH, has a 1-20 carbon atom, preferred 2-15 the carbon atom and the more preferably saturated or unsaturated alkyl of straight chain of 2-10 carbon atom, wherein R1 is H or has 1-20 carbon atom, preferred 2-15 carbon atom and more preferably saturated the or unsaturated alkyl of the straight chain of 2-10 carbon atom and A be alkoxyl group, preferably oxyethyl group, methoxyl group and/or propoxy-, with n be 1-5, preferred 1-2.Being used for specially suitable alkoxylated diols of the present invention is ethoxy ethoxy ethanol (HI=37).
Composition of the present invention contains usually by described hydrophobic solvent of general composition weight meter 0.05%-10% or their mixture, preferred 0.1%-5%, more preferably 0.25-2%, with press described hydrophilic solvent of general composition weight meter 0.05%-20% or their mixture, preferably 0.5%-15% and more preferably 1-10%.In fact, when described solvent is 1 with the weight ratio of described hydrophobic solvent and described hydrophilic solvent: 20-1: 1, more preferably 1: 14-1: 2 when existing, and can obtain various spots, comprises best total detergency ability of spot, grease spot, mud/clay spot and the enzyme spot that can bleach.
Being used for composition of the present invention must be liquid." liquid " that is used for herein comprises " paste " composition, preferably has the 1cps-10000cps that under 50rpm shearing rate and 20 ℃ of temperature, measures with liquid composition of the present invention, preferred 100cps-1000cps, the more preferably viscosity of 200cps-600cps.
It is preferably aqueous to be used for composition of the present invention.Described aqueous composition has 1-12, preferred 2-6, and more preferably the pH of 3-5 can obtain optimum chemical stability at this moment.The pH of composition can be for example by using organic or inorganic acid or alkalizing agent to regulate.
Be used for composition of the present invention and can also contain optional ingredient, for example tensio-active agent comprises nonionic, negatively charged ion, positively charged ion, zwitter-ion and/or amphoterics, washing assistant, stablizer, sequestrant, dirt suspension polyamine polymer, polymerization stain remover, dye-transfer, radical scavenger, solvent, whitening agent, catalyzer, suds suppressor, bleach-activating agent, spices and dyestuff.
In the present invention, contain peroxygen bleach and described solvent system liquid bleaching composition packed need be contacted by the fabric bleached.This can be by wherein with composition with respective pure form being applied to what is called " pretreatment mode " described fabric on by rinsing or washing before with post rinsing at fabric, or wherein at first liquid composition is diluted in water-bath, then with fabric submergence and be immersed in " immersion way " in the water-bath before rinsing, or wherein liquid composition joins by dissolving from the top or disperses " whole mode of washing " the washings that common detergent for washing clothes forms to carry out.As mentioned above, different with solid or gas, the composition that carries out the inventive method is a liquid form.
Also essentially in these methods of the present invention be, at fabric with after described composition contacts, before described composition complete drying, rinse fabric.
In pretreatment mode, we find that moisture evaporation helps to increase the concentration of fabric face radical, thereby, increased chain reaction speed.In fact, radical is normally produced by the decomposition of peroxygen bleach, and this is because the UV ray catalysis that has metal ion and/or fabric is exposed to sunlight at fabric face.Can also infer when the liquid composition that contains peroxygen bleach and stay on the fabric when dry, along with the evaporation generation automatic oxidation reaction of moisture.Described automatic oxidation reaction produces peroxy radical, and it will promote cellulosic degraded.Therefore, as described herein, in the dirty fabric process of pre-treatment, the not extremely dry tensile strength loss that helps to reduce when using the liquid composition pretreating fabrics that contains peroxygen bleach of retaining liquid composition on fabric.
In pretreatment mode, this method comprises and is applied in described fabric on its respective pure form described liquid composition or at least on the dirty part of fabric (be about to liquid composition described herein directly be applied on the described fabric and do not carry out any dilution) and with post rinsing or the washing step with the described fabric of post rinsing.In this mode, before fabric or was washed rinsing then at rinsing, pure composition is 1 minute to 1 hour time of effect on described fabric optionally, and preferred 1 minute to 30 minutes, its condition was not make composition remain to drying on described fabric.For stupid stain, suitable is further with sponge or brush friction or scrub described fabric or rub two fabrics each other.
Usually be referred to as in the mode of " immersion " at another, this method comprises the steps that the described liquid composition that promptly dilutes respective pure form in water-bath is to form dilute compositions.The dilute strength of liquid composition described in the water-bath normally at the most 1: 85, preferably at the most 1: 50, more preferably from about 1: 25 (composition: water).Fabric contacts with the water-bath that contains liquid composition and final rinsing or wash rinse fabric then then.In this embodiment, fabric preferably is immersed in the water-bath that contains liquid composition, and preferably makes fabric soak preferred 1 hour to the 24 hours time therein 30 minutes to 48 hours.
Can think that at another in mode that is commonly referred to " bleaching " in whole washing of secondary embodiment of " immersion ", liquid composition is as so-called laundry additive.In this embodiment, water-bath is by dissolving in water or disperseing conventional detergent for washing clothes to form.Liquid composition contacts with water-bath with respective pure form, and fabric contacts with the water-bath that contains liquid composition then.Final rinse fabric.Liquid composition
The present invention also comprises the liquid composition that is applicable to bleached woven fabric, it contains peroxygen bleach and contains by the hydrophilic index of general composition weight meter 0.05%-20% greater than 18 hydrophilic solvent with by the hydrophilic index of the general composition weight meter 0.05%-10% solvent system less than 18 hydrophobic solvent, and wherein hydrophilic index is by following formula definition:
The molecular weight of solvent hydrophilic segment
----------------------------------------?*?100
Described peroxygen bleach of the total molecular weight of solvent and solvent system are described hereinafter.
Liquid composition of the present invention preferably also contains tensio-active agent or their mixture.Any tensio-active agent well known by persons skilled in the art is suitable in the present invention, comprises nonionic, negatively charged ion, positively charged ion, zwitter-ion and/or amphoterics, presses general composition weight meter 50% at the most.Tensio-active agent has also further improved the detergency ability of composition of the present invention.
Because performance, nonionogenic tenside extremely is preferred among the present invention.Composition of the present invention contains 50% nonionogenic tenside or their mixture at the most usually, preferred 0.3%-30%, more preferably 0.4%-25%.Being used for suitable nonionogenic tenside of the present invention is fatty alcohol ethoxylate and/or propoxylated glycerine, and the aliphatic alcohol chain length that their commercial usefulness is different obtains with different degree of ethoxylation.In fact, the HLB value of this oxyalkylated nonionogenic tenside depends primarily on the chain length of Fatty Alcohol(C12-C14 and C12-C18), oxyalkylated character and extent of alkoxylation.Can obtain the products catalogue of tensio-active agent, wherein list many tensio-active agents, comprise nonionogenic tenside and they HLB value separately.
The appropriate chemical method that preparation is used for nonionogenic tenside of the present invention comprises the condensation with required ratio of corresponding alcohol and alkylene oxide.This method is well known by persons skilled in the art, fully describes in the prior art.Alternatively, be applicable to that various alcohol alcoxylates of the present invention can be obtained by each supplier commercial.
Especially suitable is to have to be lower than 16 as nonionogenic tenside of the present invention, preferably is lower than 15, the HLB more preferably less than 12 (hydrophile-lyophile balance) hydrophobic non ionic surfactants.These hydrophobic non ionic surfactants have been found the degrease character that provides good.
The preferred hydrophobic non ionic surfactants that is used for composition of the present invention is that HLB is lower than 16 tensio-active agent, and has formula RO-(C 2H 4O) n(C 3H 6O) mH, wherein R is C 6-C 22Alkyl chain or C 6-C 28The alkylbenzene chain and wherein n+m be 0-20, n is 0-15, m is that 0-20 and preferred n+m are 1-15, n and m are 0.5-15, being more preferably n+m is 1-10, n and m are 0-10.Being used for preferred R chain of the present invention 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 is C 9And C 11The mixture of alkyl chain, n be 2.5 and m be 0), or Lutensol RTO3 (HLB=8; R is C 13Alkyl chain, n be 3 and m be 0), or Lutensol RAO3 (HLB=8; R is C 13And C 15The mixture of alkyl chain, n be 3 and m be 0), or Tergitol R25L3 (HLB=7.7; R is C 12-C 15Alkyl chain, n be 3 and m be 0), or Dobanol R23-3 (HLB=8.1; R is C 12And C 13The mixture of alkyl chain, n be 3 and m be 0), or Dobanol R23-2 (HLB=6.2; R is C 12And C 13The mixture of alkyl chain, n be 2 and m be 0), or Dobanol R45-7 (HLB=11.6; R is C 14And C 15The mixture of alkyl chain, n be 7 and m be 0), Dobanol R23-6.5 (HLB=11.9; R is C 12And C 13The mixture of alkyl chain, n be 6.5 and m be 0), or Dobanol R25-7 (HLB=12; R is C 12And C 15The mixture of alkyl chain, n be 7 and m be 0), or Dobanol R91-5 (HLB=11.6; R is C 9And C 11The mixture of alkyl chain, n be 5 and m be 0), or Dobanol R91-6 (HLB=12.5; R is C 9And C 11The mixture of alkyl chain, n be 6 and m be 0), or Dobanol R91-8 (HLB=13.7; R is C 9And C 11The mixture of alkyl chain, n be 8 and m be 0), or Dobanol R91-10 (HLB=14.2; R is C 9-C 11The mixture of alkyl chain, n be 10 and m be 0) or their mixture.The present invention is Dobanol preferably R91-2.5 or Lutensol RTO3 or Lutensol RAO3 or Tergitol R25L3 or Dobanol R23-3 or Dobanol R23-2 or their mixture.These Dobanol RTensio-active agent is obtained by SHELL commercial.These Lutensol RTensio-active agent can be obtained and these Tergitol by BASF commercial RTensio-active agent can be obtained by UNION CARBIDE commercial.
Other is applicable to that suitable ionic surfactant pack of the present invention draws together the polyhydroxy fatty acid amide surfactant of following formula or their mixture:
R 2-C (O)-N (R 1)-Z wherein, R 1Be hydrogen or C 1-C 4Alkyl, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, or their mixture, R 2Be C 5-C 31Alkyl, Z are polyhydroxy alkyl or its alkoxy derivative with the linear hydrocarbyl chain that is connected directly to few three hydroxyls.
R 1C preferably 1-C 4Alkyl, more preferably C 1Or C 2Alkyl, most preferable; R 2It is straight chain C 7-C 19Alkyl or alkenyl, preferred straight chain C 9-C 18Alkyl or alkenyl, more preferably straight chain C 11-C 18Alkyl or alkenyl, most preferably straight chain C 11-C 14Alkyl or alkenyl or its mixture.Z is preferably obtained by reducing sugar in reductive amination process, and more preferably Z is a glycosyl.Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.As raw material, except above listed single sugar, can use high glucose maize treacle, high-fructose corn syrup and high malt sugar maize treacle.Can obtain the mixture of sugar component Z by these maize treacle.Will be appreciated that determines does not here plan to get rid of other suitable raw material.Z is preferably selected from-CH 2-(CHOH) n-CH 2OH ,-CH (CH 2OH) (CHOH) N-1-CH 2OH ,-CH 2-(CHOH) 2(CHOR ') (CHOH)-CH 2OH, wherein, n is 3 to 5 integer, comprises 3 and 5, R ' is H or cyclic or aliphatic monose and its alkoxy derivative.Most preferably wherein n is 4 glycosyl, specifically is CH 2-(CHOH) 4-CH 2OH.
At formula R 2C (O) N (R 1Among the)-Z, R 1Can be for example N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.R 2-CO-N＜can be is coconut monoethanolamide, stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitic amide, butter acid amides etc. for example.Z can be 1-deoxy-glucose base, 2-deoxidation fructosyl, 1-deoxidation malt-base, 1-deoxidation lactose base, 1-deoxy-galactose base, 1-deoxymannose base, 1-deoxidation maltotriose glycosyl etc.
Being used for suitable polyhydroxy fatty acid amide surfactant of the present invention can be obtained with trade(brand)name HOE  by Hoechst industrial.
The method for preparing polyhydroxy fatty acid amide surfactant is known in the prior art.Usually they can be by making alkylamine and reducing sugar reaction to form the corresponding N-alkyl polyhydroxy amine in reduction amination, N-alkyl polyhydroxy amine and fatty aliphatic ester or triglyceride level reacted with formation N-alkyl, N-polyhydroxy fatty acid amide amide product prepare.The method for compositions that preparation contains polyhydroxy fatty acid amide is at disclosed Thomas Hedley﹠Co. on February 18 nineteen fifty-nine for example, the GB patent specification 809060 of Ltd, the Anthony M.Schwartz US2703798 of the US2965576 of the E.R.Wilson of promulgation on December 20 nineteen sixty, promulgation on March 8 nineteen fifty-five; US1985424 and the WO92/06070 of the Piggott of promulgation on December 25th, 1934, every piece of patent is classified this paper reference as.
Except that nonionogenic tenside, liquid composition of the present invention also can contain other tensio-active agent, as anion surfactant or their mixture.Anion surfactant is in the present invention preferably as optional components, because they can play moistening agent, promptly in laundry applications, spot on their moisten fabric, especially the spot on hydrophilic fabric, thereby help peroxygen bleach to realize their bleaching action, thereby help to improve laundry performance to the spot that can bleach.In addition, anion surfactant guarantees to obtain transparent composition, even contain hydrophobic components when described composition, for example during hydrophobic surfactant.Composition of the present invention contains by the described anion surfactant of general composition weight meter 0.1%-20% or their mixture, preferred 0.2%-15%, more preferably 0.5%-13%.
Being particularly useful for of the present invention is sulfonate and sulfate surfactant.Similarly anion surfactant is as known in the art, widespread use in the commercial laundering agent.These anion surfactants comprise C8-C22 alkylbenzene sulfonate (LAS), C8-C22 alkyl-sulphate (AS), unsaturated vitriol, for example oleyl sulfate, C10-C18 alkyl alkoxy sulfate (AES) and C10-C18 alkyl alkoxy carboxylate salt.The neutralizing cation that is used for negatively charged ion synthesising sulfonate and/or vitriol represented by the positively charged ion that is widely used in the washing composition technical field of routine, for example sodium, potassium or alkanol ammonium.Preferred alkyl vitriol especially contains 6-18 carbon atom in alkyl chain in the present invention, the coconut alkyl-sulphate of preferred 8-15 carbon atom or their mixture.
Other anion surfactant that is used for washing purposes also can be used for the present invention.They can be soap salt (comprise, the ammonium salt of sodium, potassium, ammonium and replacement for example, for example single-, two-and triethanolamine salt), C 8-C 22Uncle or secondary paraffin sulfonate, C 8-C 24Alkene sulfonate, the sulfonation poly carboxylic acid, the C that prepare as the sulfonation of the pyrolysis product that pass through alkaline earth metal citrate in british patent specification 1082179, described 8-C 24Alkyl polyglycol ether sulfate (containing nearly 10 moles of ethylene oxide); Alkyl ester sulfonate, for example C 14-16Methyl ester sulfonate, acylglycerol sulfonate, fatty oil acylglycerol vitriol, alkylphenol oxyethane ether sulfate, paraffin sulfonate, alkylphosphonic, isethionate; for example, acyl isethinate, N-acyl taurine salt, amber alkyl amide salts and sulfosuccinate, sulfosuccinate monoesters (especially saturated and unsaturated C 12-C 18Monoesters) and sulfosuccinate diester (especially saturated and unsaturated C 6-C 14Diester), the vitriol of alkyl polysaccharide, for example alkyl polyglucoside vitriol (compound of nonionic non-sulfuric acidization described below).Resinous acid and hydrogenated resin acid also are suitable, for example rosin, staybelite and the resinous acid and the hydrogenated resin acid that are present in or are obtained by Yatall MA.Other example provides in " tensio-active agent and washing composition " (I and II volume, Schwartz, Perry and Berch).Various these class tensio-active agents also usually are disclosed in the people's such as Laughlin of promulgation on December 30th, 1975 US3929678, and the 23rd hurdle the 58th walks in the 29th hurdle the 23rd row (classifying this paper reference as).
Be used for other suitable anion surfactant of the present invention and also comprise the acyl sarcosinate of acid and/or salt form or their mixture, preferably have the long acyl sarcosinate of following formula:
Figure A9719958500171
Wherein M is hydrogen or cationic moiety, and wherein R is a 11-15 carbon atom, the alkyl of preferred 11-13 carbon atom.Preferred M is hydrogen and an alkali metal salt, especially sodium and potassium.Described acyl sarcosinate tensio-active agent is obtained by natural acid and amino acid sarkosine (sarcosine).They are suitable as the aqueous solution of its salt or the powder of its sour form uses.As the derivative of natural acid, described acyl sarcosinate is rapid and totally biodegradable, and the advantages of good skin consistency is arranged.
Therefore, be used for especially preferred long acyl sarcosinate of the present invention and comprise C 12Acyl sarcosinate (be the acyl sarcosinate of following formula, wherein M is that hydrogen and R are the alkyl of 11 carbon atoms) and C 14Acyl sarcosinate (be the acyl sarcosinate of following formula, wherein M is that hydrogen and R are the alkyl of 13 carbon atoms).C 12Acyl sarcosinate commercial be available, the Hamposyl L-30  that provides by Hampshire for example.C 14Acyl sarcosinate commercial be available, the Hamposyl M-30  that provides by Hampshire for example.
Liquid composition of the present invention also can contain other tensio-active agent well known by persons skilled in the art, and suc as formula the amine oxide surfactant of R1R2R3NO, wherein each R1, R2 and R3 are C independently 1-C 30, preferred C 1-C 20, C most preferably 1-C 16Hydrocarbon chain.Amine oxide can by general composition weight meter at the most 10% content have more preferably 1-3%.
Composition of the present invention also can contain other optional components, as washing assistant, stablizer, sequestrant, dye-transfer, radical scavenger, solvent, whitening agent, suds suppressor, bleach-activating agent, spices, dirt suspension polyamine polymer, polymerization stain remover, catalyzer and dyestuff.
Therefore, as preferred ingredients optionally but very, composition of the present invention contains bleach-activating agent or their mixture." bleach-activating agent " is meant the compound that forms peracid with hydroperoxidation among the present invention.So the peracid that forms constitutes active bleaching agent.Being used for especially suitable bleach-activating agent of the present invention is hydrophobic bleach activator, promptly not obvious and stably miscible with water bleach-activating agent.This hydrophobic bleach activator has and is lower than 11, preferably is lower than 10 the 2nd HLB (hydrophilic-lipophilic balance).The 2nd HLB is well known in the art, in for example " emulsion theory and put into practice ", and P.Becher, Reinhold, New York, 1957 or " emulsification science ", P.Sherman, Academic Press, London, definition in 1969.
Be used for suitable bleach-activating agent of the present invention and comprise the material that belongs to ester, acid amides, imide or acid anhydride class.The example of such suitable combination thing is open in GB1586769 and GB2l43231, and they are prepared into the method for bead form and describe in EP-A-62523.The suitable example that is used for this compound of the present invention is the tetra acetyl ethylene diamine of describing as US4818425 (TAED), 3; 5, the pelargonamide and the positive nonanoyl phenolsulfonate (NOBS) of 5-trimethyl acetyl base sodium sulfocarbolate, diperoxy dodecylic acid and the peroxide hexanodioic acid in US4259201 for example, described.Same suitable is the N-acyl caprolactam, and it is selected from and replaces or unsubstituted benzoyl caprolactam, capryloyl hexanolactam, nonanoyl hexanolactam, caproyl hexanolactam, decanoyl hexanolactam, hendecene acyl caprolactam, formyl radical hexanolactam, ethanoyl hexanolactam, propionyl hexanolactam, butyryl radicals hexanolactam, pentanoyl hexanolactam or their mixture.The particular variety of interested bleach-activating agent is open in EP624154, and especially preferred in such is CitroflexA-2 (ATC).CitroflexA-2 has advantage, because its eventual degradation becomes citric acid and alcohol, is friendly to environment promptly.In addition, CitroflexA-2 has good stability to hydrolysis when product is stored, and it is effective bleach-activating agent.At last, it provides the good ability of washing that helps to composition.
Composition of the present invention can contain by the described bleach-activating agent of general composition weight meter 0.1%-20% or their mixture, preferred 1%-10%, more preferably 2%-7%.
Composition of the present invention can be mixed with solution, milk sap or microemulsion according to existing each optional ingredient and its content separately.For example, reason for stability, usually the present composition that contains aforesaid bleach-activating agent preferably is mixed with the aqueous emulsions of described bleach-activating agent in the matrix that contains water, peroxygen bleach, solvent system and emulsifying surfactant system, or is mixed with the microemulsion of described bleach-activating agent in the matrix that contains water, peroxygen bleach, solvent system and hydrophilic surfactant system.
The milk sap that the present invention preferably contains peroxygen bleach contains the emulsifying surfactant system of at least two kinds of different surfaces promoting agents.Preferred described two kinds of different tensio-active agents should have different HLB values (hydrophilic) to form stable milk sap among the present invention, and preferably the difference of the HLB value of described two kinds of tensio-active agents is at least 1, and preferably at least 2.In fact, by at least two kinds of described tensio-active agents of suitable mixing in water, leave standstill the not obvious milk sap that is divided into different layers of at least two weeks under 40 ℃ with being formed on different HLB values.
Milk sap of the present invention also can contain other tensio-active agent except that described emulsifying surfactant system, yet it should obviously not change the weighted mean HLB value of overall milk sap.
Milk sap also contains in the especially preferred embodiment as the milk sap of the present invention of the CitroflexA-2 of bleach-activating agent therein, and it is 6 hydrophobic non ionic surfactants that suitable surfactant system will contain HLB for example, for example Dobanol R23-2 and for example HLB are 15 hydrophilic nonionic tensio-active agent, for example Dobanol R91-10.Other suitable nonionic surfactant system contains 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 Dobanol R23-3 (HLB=8.1).
Composition is mixed with in embodiment of the present invention of milk sap therein, and described composition is opaque.In centrifugal check, find that described milk sap of the present invention does not occur being separated after 6000rpm is 15 minutes.At test under microscope, described milk sap is shown as the disperse phase of drop in matrix.
Composition of the present invention therein is mixed with in the embodiment of the present invention of microemulsion, described bleaching microemulsion of the present invention contains the hydrophilic surfactant system, it contains at least two kinds of different tensio-active agents, as nonionogenic tenside and anion surfactant.The suitable hydrophilic surfactant of the present invention that is used for is those hydrophilic surfactants of the present invention.Contain therein in the embodiment of microemulsion of the present invention of peroxygen bleach and bleach-activating agent, the described tensio-active agent that is at least a hydrophilic surfactant system for the stable key factor that adds bleach-activating agent in described microemulsion must have the HLB value that is different from bleach-activating agent.In fact,, can form the single phase of successive, therefore reduce the chemical stability of bleach/bleach activator system if all described tensio-active agents have the HLB value identical with bleach-activating agent.Preferred at least a described tensio-active agent has and described bleach-activating agent difference 1.0HLB unit at least, the HLB value of preferred 2.0HLB unit.
Composition is mixed with in the embodiment of the present invention of microemulsion therein, does not exist under opalizer and the dyestuff, and described composition is that macroscopic view is transparent.In centrifugal check, find that described microemulsion of the present invention does not occur being separated after 6000rpm is 15 minutes.At test under microscope, described microemulsion is shown as the disperse phase of drop in matrix.We find that particle has general about 3 microns or be lower than the size of 3 micron diameters.
Bleaching composition of the present invention, those compositions that particularly are mixed with milk sap or microemulsion form are chemically stable." chemically stable " in this article refer to the composition that comprises peroxygen bleach of the present invention 50 ℃ in 2 weeks without undergoing the loss that surpasses 10% available oxygen.The concentration of available oxygen can be measured by chemistry titration method well known in the prior art, for example iodimetry, permanganate titration and cerimetry.The choice criteria of described method and appropriate method is at for example " hydrogen peroxide ", W.C.Schumb, C.N.Satterfield and R.L.Wentworth, Reinhold Publishing Corporation, New York, 1955 and " organo-peroxide ", Daniel Swern, Editor WileyInt.Science describes in 1970.In addition, the stability of described composition also can be estimated by the bulging test method.
Therefore, bleaching composition of the present invention can be packaged in the given deformable container/bottle, does not damage the stability of its described container/bottle of dress after leaving standstill for a long time.
Be used for suitable sequestrant of the present invention and comprise fragrant chelating agent and other sequestrant that is selected from phosphine acid salt chelator, aminocarboxylate sequestrant, polyfunctional group replacement, as the sequestrant of glycine, Whitfield's ointment, aspartic acid, L-glutamic acid, propanedioic acid or the sequestrant of their mixture.When using, to press general composition weight meter 0.001%-5%, the content of preferred 0.05%-2% by weight exists sequestrant usually.
Be used for suitable phosphonic acids sequestrant of the present invention and can comprise etidronic acid (ethydronicacid) and aminophosphonic acid salt compound, comprise that amino alkylidenyl gathers (alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate, nitrilo trimethylene phosphonic salt, ethylenediamine tetramethylene phosphonic acid salt and diethylenetriamine pentamethylenophosphonic acid(DTPP) salt.Phosphonate compounds can their sour form or the different cationic salt form on its some or all of acid functional groups exist.The phosphine acid salt chelator that preferably is used for the present invention is a diethylenetriamine pentamethylenophosphonic acid(DTPP) salt.This phosphine acid salt chelator is all obtained with trade(brand)name DEQUEST  by Meng Shan commercial.
Being used for most preferred phosphine acid salt chelator of the present invention is amino three (methylene phosphonic acids), is called ATMP herein.In fact, we find to add ATMP in liquid composition of the present invention, i.e. the compound of following formula: Obviously reduced and with containing the relevant infringement of composition pretreating fabrics of peroxygen bleach, especially those contain metal ion, for example the fabric of copper, iron, chromium and manganese.
The fragrant chelating agent that polyfunctional group replaces also can be used in the present composition.US3812044 referring to the Connor of on May 21st, 1974 promulgation etc.The preferred compound of this class acid form is the dihydroxyl disulfobenzene, for example 1, and 2-dihydroxyl-3,5-disulfobenzene.
Being used for preferred biodegradable cheating agent of the present invention is quadrol N, the ammonium salt of N '-disuccinic acid or its basic metal, alkaline-earth metal, ammonium or replacement or their mixture.Quadrol N, N '-disuccinic acid, especially (S, S) isomer is described in detail in the US4704233 of the Hartman of on November 3rd, 1987 promulgation and Perkins.Quadrol N, N '-disuccinic acid are commercial available, are for example obtained with trade(brand)name ssEDDS  by Palmer Research Laboratories.
Be used for suitable aminocarboxylate of the present invention and comprise edetate, diethylentriamine pentacetate, diethylentriamine pentacetate (DTPA), N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, ethanol-Diglycocol, trimethylenedinitrilo-tertraacetic acid (PDTA) and methylglycine oxalic acid (MGDA), both are their the sour form or the ammonium salts of their basic metal, ammonium and replacement.Especially the suitable aminocarboxylate of the present invention that is used for is diethylene triaminepentaacetic acid(DTPA), trimethylenedinitrilo-tertraacetic acid (PDTA), and it is commercial available, is for example obtained and methylglycine oxalic acid (MGDA) with trade(brand)name Trilon FS  by BASF.
Be used for another preferred sequestrant of the present invention and have following formula:
Figure A9719958500221
R wherein 1, R 2, R 3And R 4Be independently selected from-H, alkyl, alkoxyl group, aryl, aryloxy ,-Cl ,-Br ,-NO 2,-C (O) R ' and-SO 2R "; Wherein R ' be selected from-H ,-OH, alkyl, alkoxyl group, aryl and aryloxy; R " be selected from alkyl, alkoxyl group, aryl and aryloxy; And R 5, R 6, R 7And R 8Be independently selected from-H and alkyl.
Being used for especially preferred sequestrant of the present invention is ATMP, diethylenetriamine methylene phosphonic acid salt, ethylidene N, N '-disuccinic acid, diethylentriamine pentacetate, glycine, Whitfield's ointment, aspartic acid, L-glutamic acid, propanedioic acid or their mixture, highly preferred ATMP.
Be used for list and dihydroxy-benzene and their analogue, alkyl and aryl carboxylic acid salt and their mixture that suitable radical scavenger of the present invention comprises known replacement.Be used for preferred this radical scavenger of the present invention and comprise di-tert-butyl hydroxy toluene (BHT), quinhydrones, di-tert-butyl hydroquinone, single tertiary butylated hydroquinone, tertiary butyl hydroxyl anysole, phenylformic acid, toluic acid, catechol, tert-butyl catechol, benzylamine, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, gallic acid n-propyl or their mixture, highly preferred di-tert-butyl hydroxy toluene.Usually to press general composition weight meter 0.001%-2%, the amount of preferred 0.001%-0.5% by weight exists radical scavenger when using.
Have sequestrant, the present composition that especially ARMP, and/or radical scavenger helps to be fit to the dirty band yarn dyed fabric of pre-treatment is the security situation during Long contact time before the described fabric of washing.
Composition of the present invention also can contain as the dirt suspension polyamine polymer of optional components or their mixture.Any dirt suspension polyamine polymer known to the skilled in the art can be used among the present invention.Being used for especially suitable polyamine polymer of the present invention is the poly-alkoxylation polyamine.This material can be easily by the branch subrepresentation of experience structure with following repeating unit:
Figure A9719958500231
The amine form and Quaternized form wherein R is the alkyl of a common 2-6 carbon atom; R 1Can be C 1-C 20Alkyl; Alkoxyl group is that oxyethyl group, propoxy-etc. and y are 2-30, most preferably 10-20; N is at least 2 integer, preferred 2-20, most preferably 3-5; With X-is to obtain negatively charged ion by quaterisation, for example halogen ion or methylsulfate.
Being used for topnotch preferred polyamine of the present invention is so-called ethoxylation polyvinylamine, i.e. the following oxyethane of general formula and the polymeric reaction product of ethyleneimine:
Figure A9719958500233
Y=2-30 wherein.Especially being preferred among the present invention is the ethoxylation polyvinylamine, especially ethoxylation tetren and quaternized oxyethyl group hexamethylene-diamine.
We are surprised to find described dirt suspension polyamine polymer and help effect of the present invention, promptly when except that described solvent system, when adding them in the liquid composition that contains peroxygen bleach, they further improve the detergency ability of described composition, especially under the laundry pretreatment condition.In fact, they can improve the detergency ability to various spots, comprise oil spot, enzyme spot, soil property/mud spot and the spot that can bleach.
Composition contains usually by general composition weight meter 10% this dirt suspension polyamine polymer or their mixture at the most, preferred 0.1%-5%, more preferably 0.3%-2%.
Composition of the present invention also can contain other polymerization stain remover well known by persons skilled in the art.This polymerization stain remover is characterised in that to have hydrophilic segment and hydrophobic part simultaneously, and wherein hydrophilic segment makes the surface hydrophilic of hydrophobic fiber such as polyester and nylon; Hydrophobic part then is deposited on the hydrophobic fiber and after washing and rinse cycle end and adheres to thereon, and therefore is used as the point of fixity of hydrophilic segment.This can make in the spot washing process afterwards that exists after with detergent-treatment and more easily wash.
Can be used for polymerization stain remover of the present invention and especially comprise following those stain removers, it contains: (a) one or more nonionic hydrophilic components, it mainly is made up of following composition, promptly (ⅰ) polymerization degree is at least 2 polyoxyethylene part, or (ⅱ) polymerization degree is propylene oxide or the polyoxytrimethylene part of 2-10, wherein said hydrophilic segment does not comprise any propylene oxide unit, unless it is attached on the adjacent part at each tail end by ehter bond, or (ⅲ) comprise the mixed cell of the oxyalkylene units of about 30 propylene oxide units of ethylene oxide and 1-, wherein said mixed cell comprises the ethylene oxide unit of q.s, hydrophilic like this component has enough big wetting ability to improve the wetting ability of normal polyester synthon surface to sedimentary stain remover on this surface, described hydrophilic parts preferably comprises at least about 25% ethylene oxide unit and more preferably, particularly for this component of the propylene oxide unit with about 20-30%, the ethylene oxide unit at least about 50%; Or (b) one or more hydrophobic components, it comprises (ⅰ) terephthalic acid C3 oxyalkylene ester moiety, wherein, if described hydrophobic components also comprises terephthalic acid oxygen ethylidene ester, terephthalic acid oxygen ethylidene ester so: terephthalic acid C 3The ratio of oxyalkylene ester units is about 2: 1 or lower, (ⅱ) C 4-C 6Alkylidene group or C 4-C 6Oxyalkylene part or its mixed form (ⅲ) have poly-(vinyl ester) part that is at least 2 the polymerization degree, preferred poly-(vinyl-acetic ester), or (ⅳ) C 1-C 4Alkyl oxide or C 4Hydroxyalkyl ether substituting group, or its mixed form, wherein said substituting group is with C 1-C 4Alkyl oxide or C 4Hydroxyalkyl ether derivatived cellulose, and composition thereof form exist, and this derivatived cellulose is amphipathic, thereby they have the C of q.s 1-C 4Alkyl oxide and/or C 4The hydroxyalkyl ether unit to be being deposited on the normal polyester synthon surface, and keeps the hydroxyl of q.s, in case adhere on this conventional synthon surface, just increases the fiber surface wetting ability, or (a) and mixture (b).
Although can use the higher polymerization degree, (a) to be preferably 3-about 150 for the polyoxyethylene of (ⅰ) the part polymerization degree that generally has about 1-about 200, and more preferably 6-about 100.Suitable oxygen C 4-C 6The alkylidene group hydrophobic part includes, but not limited to end-blocking unit such as the MO as disclosed polymerization stain remover among the US4721580 of the Gosselink of promulgation on January 26th, 1988 3S (CH 2) nOCH 2CH 2O-, wherein M is that sodium and n are the integer of 4-6.
Be used for polymerization stain remover of the present invention and also comprise derivatived cellulose, as the hydroxy ethers cellulose polymer compound, the copolymerization block of ethylene glycol terephthalate or propylene glycol ester terephthalate and polyethylene oxide or poly(propylene oxide) terephthalate etc.This stain remover is commercial available, and comprises cellulosic hydroxy ethers such as METHOCEL (Dow).Being used for Mierocrystalline cellulose stain remover of the present invention also comprises and is selected from C 1-C 4Alkylcellulose and C 4Those materials of hydroxy alkyl cellulose are referring to the US4000093 of the Nicol of on December 28th, 1976 promulgation etc.
The stain remover that it is characterized in that gathering (vinyl ester) hydrophobic part comprises the graft copolymer such as the C of poly-(vinyl ester) 1-C 6Vinyl acetate is preferably and is grafted to the polyalkylene oxide skeleton, as poly-(vinyl-acetic ester) on the polyethylene oxide skeleton.EP0219048 referring to disclosed Kud on the 22nd etc. April in 1987.Commercial available this stain remover comprises the SOKALAN class material that derives from BASF (West Germany), as SOKALAN HP-22.
A kind of preferred stain remover is the multipolymer with ethylene terephthalate and terephthalic acid polyethylene oxide (PEO) ester random block.The molecular weight of this polymerization stain remover is in the scope of about 25000-about 55000.US3893929 referring to the Basadur of the US3959230 of the Hays of on May 25th, 1976 promulgation and promulgation on July 8th, 1975.
Another kind of preferred polymerization stain remover is that repeating unit is the unitary polyester of ethylene terephthalate, its comprise the ethylene terephthalate unit of 10-15% by weight and by weight 90-80% be the terephthalic acid polyoxyethylene ester units that the polyoxyethylene enediol of 300-5000 obtains by molecular-weight average.The example of this polymkeric substance comprises commercial available material ZELCON 5126 (deriving from Dupont) and MILEASE T (deriving from ICI).In addition referring to the US47021857 of the Gosselink of on October 27th, 1987 promulgation.
Another kind of preferred polymerization stain remover is a kind of sulfonated products of substantial linear ester oligomer, and this oligopolymer contains terephthaloyl and multiple unitary oligopolymer ester skeleton of oxyalkylene oxygen basic weight and the terminal portions that is covalently bound on the skeleton.The J.J.Scheibel of promulgation on November 6 nineteen ninety and the US4968451 of E.P.Gosselink have fully described these stain removers.Other suitable polymerization stain remover comprises the terephthalate polyester among the US4711730 of the Gosselink of on December 8th, 1987 promulgation etc., the end capped oligopolymer ester of negatively charged ion among the US4721580 of the Gosselink of promulgation on January 26th, 1988, and the block polyester oligopolymer among the US4702857 of the Gosselink of promulgation on October 27th, 1987.
Preferred polymerization stain remover also comprises the stain remover among the US4877896 of the Maldonado of promulgation on October 31st, 1989 etc., this Patent publish negatively charged ion, the particularly end capped terephthalate of sulphur aroyl.
Another preferred polymerization stain remover is that a kind of repeating unit is terephthaloyl unit, the different terephthaloyl of sulfo group unit, oxygen ethyleneoxy group unit and the unitary oligopolymer of oxygen-propylene.Repeating unit on the oligopolymer skeleton preferably stops with the isethionate end-blocking unit of modification.A kind of particularly preferred this class stain remover comprises about 1 sulfo group isophthaloyl base unit; 5 terephthaloyl unit; ratio is oxygen ethyleneoxy group unit and oxygen-propylene unit and 2 2-(2-the hydroxyl-oxethyl)-ethyl sulfonic acid sodium end-blocking unit of about 1.7-about 1.8.Described stain remover comprises that also it is preferably selected from xylenesulfonate, cumene sulfonate, tosylate and composition thereof by the stablizer of the degree of crystallinity reduction of the about 0.5-of oligopolymer weight about 20%.US5415807 referring to the Gosselink of May 16 nineteen ninety-five promulgation etc.
If use, it is about 10.0% that stain remover is generally about 0.01-of detergent composition weight of the present invention, and it is about 5% to be generally about 0.1-, is preferably about 0.2-about 3.0%.
Composition of the present invention can also contain one or more and effectively suppress dyestuff is transferred to another kind of fabric from a kind of DYED FABRICS material in washing process.Such dye transfer inhibitor generally includes multipolymer, manganese phthalocyanine, peroxidase and their mixture of polyvinylpyrrolidonepolymers polymers, polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.If use, it is about 10% that these inhibitor account for about 0.01%-of composition weight, and preferably about 0.01%-is about 5%, and more preferably from about 0.05%-about 2%.
More particularly, be preferred for polyamine N-oxide pllymers of the present invention and contain the unit with following structural formula: R-A x-P; Wherein P can connect the polymerizable unit of N-O group or the N-O group forms the polymerizable unit part or the N-O group can be connected in two kinds of unit; A is one of following structure :-NC (O)-,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; With R be aliphatic series, aliphatic, the aromatics of ethoxylation, heterocycle or alicyclic group or their any combination, its nitrogen or N-O group that can connect the N-O group is the part of these groups.Preferred polyamine N-oxide compound is that wherein R is a heterocyclic group, for example the material of pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines and their derivative.
The N-O group can be represented by following general structure: R wherein 1, R 2, R 3Be aliphatic series, fragrance, heterocycle or alicyclic group or their combination; X, y and z are 0 or 1; Can be connected in or form the part of above-mentioned any group with the nitrogen of N-O group.The unitary pKa of the amine oxide of polyamine N-oxide＜10, preferred pKa＜7, more preferably pKa＜6.
Can use any polymer backbone, as long as the amine oxide polymers that forms is water miscible and has the dye transfer inhibition activity.Suitable polymeric skeleton is polyethylene, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylate and their mixture.These polymkeric substance comprise random or segmented copolymer, and wherein a kind of monomer type is an amine n-oxide, and another kind of monomer type is the N-oxide compound.The ratio that the amine n-oxide polymkeric substance has amine and amine n-oxide usually is 10: 1 to 1: 1000000.Yet the number of the amine oxide group that exists in the polyamine oxide polymer can change by suitable copolymerization or suitable N-oxidisability.The polyamine oxide compound almost can any polymerization degree obtain.Molecular-weight average is generally 500-1000000; 1000-500000 more preferably; Most preferably be 5000-100000.The material of preferred class can be described as " PVNO ".The most preferred polyamine N-oxide that is used for detergent composition of the present invention is poly-(4-vinylpridine-N-oxide compound), and its molecular-weight average is about 50000, and amine and amine n-oxide ratio are about 1: 4.
The multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole polymkeric substance (being called " PVPVI ") also is preferred among the present invention.The molecular-weight average of PVPVI is preferably 5000-1000000, more preferably 5000-200000, most preferably 10000-20000.(average molecular weight range is by light scattering determining, and at " chemical analysis ", volume 113, described in " modernism of polymer characterization ", its content is listed this paper in as a reference as Barth etc.).The mol ratio that the PVPVI multipolymer has N-vinyl imidazole and N-vinyl pyrrolidone usually is 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1, and most preferably 0.6: 1 to 0.4: 1.These multipolymers can be straight or brancheds.
Composition of the present invention also can use molecular-weight average about 400000 for about 5000-, and preferably about 5000-is about 200000, more preferably from about the Polyvinylpyrolidone (PVP) of 5000-about 50000 (" PVP ").PVP is the known to the skilled of detergent applications, referring to for example EP-A-262897 and EP-A-256696, classifies this paper reference as.It is about 100000 for about 500-that the composition that contains PVP also can contain molecular-weight average, the polyoxyethylene glycol of preferably about 1000-about 10000 (" PEG ").PEG that provides in washing soln and the ratio of PVP are preferably about 2: 1 to about 50: 1 in ppm, more preferably from about 3: 1 to about 10: 1.
High if desired foam then can add as C in composition 10-C 16The suds booster of alkanolamide is generally the content of 1%-10%.C 10-C 14Monoethanolamine and diglycollic amide are the representative instances of such suds booster.With this class suds booster and high bubble cosurfactant, as above-mentioned amine oxide, it also is favourable that trimethyl-glycine and sultaine use together.If desired, also can add as MgCl with the content of 0.1%-2% 2, MgSO 4Deng the solubility magnesium salts additional foam to be provided and to strengthen the degreasing performance.
When being used for fabric treating or washing, any white dyes well known in the prior art or other brightener or whitening agent generally can mix in the present composition by the content of about 0.05%-1.2% (weight).Commercially available white dyes of the present invention can be used for and following group can be divided into, it comprises, but be not necessarily limited to derivative, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanines, the dibenzothiophene-5 of stilbene, 5-dioxide, pyrroles, 5-and 6-unit heterocycle whitening agent are listed them and are used to illustrate rather than limit.The example of these whitening agent is disclosed in " production of white dyes and application ", M.Zahradnik, and John Wiley﹠Sons publishes, in New York (1982).
The specific examples of available white dyes is those disclosed among the US4790856 of Wixon of on December 13rd, 1988 promulgation in the present composition.These whitening agent comprise the PHORWHITE series whitening agent of Verona.Disclosed other whitening agent comprise in this reference: the Tinopal UNPA that can obtain from Ciba-Geigy, Tinopal CBS and Tinopal5BM; Can be from being positioned at Arctic White CC and the Artic White CWD that gondola Hilton-Davis obtains; 2-(4-styryl phenyl)-2H-naphthols [1,2-d] triazole; 4,4 '-two (1,2,3-triazoles-2-yl) stilbene; 4,4 '-two (styryl) biphenyl and aminocoumarin.The specific examples of these whitening agent comprises: 4-methyl-7-diethyl amino coumarin; 1, the two (ethene of benzimidazolyl-2 radicals-yl) of 2-; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-styryl-naphthalene-[1,2-d] oxazole and 2-(stilbene-4-yl)-2H-naphtho-[1,2-d] triazole.In addition referring to the US3646015 that issued on February 29th, 1972 to Hamilton.General in the present invention preferred anionic whitening agent.
If necessary, composition of the present invention also can additionally add catalyzer or accelerator with further improvement bleaching or decontamination.Any suitable bleaching catalyst can use.For the detergent composition that uses with the total content of the about 5000ppm of about 1000-in water, composition provides about 0.1ppm-about 700ppm usually in washings, more preferably from about about 50ppm of 1ppm-or lower catalyst substance.
Bleaching catalyst also can be used for the present invention.Typical bleaching catalyst contains transition metal complex, and for example wherein metal ligand is quite anti-mutability, it under alkaline washing condition usually not depositing metal oxide or oxyhydroxide to any degree that can see.This class catalyzer comprises manganese-based catalyst, and it is disclosed among US5246621, US5244594, US5194416, US5114606 and EP Nos.549271A1,549272A1,544440A2 and the 544490A1.The preferred embodiment of these catalyzer comprises Mn IV 2(3 (TACN) of μ-O) 2-(PF 6) 2, Mn III 2(μ-O) 1(u-OAc) 2(TACN) 2(ClO 4) 2, Mn IV 4(μ-O) 6(TACN) 4(ClO 4) 4, Mn IIIMn IV 4-(μ-O) 1(u-OAc) 2-(TACN) 2-(ClO 4) 3, Mn IV-(TACN)-(OCH 3) 3(PF 6) and their mixture, wherein TACN is a trimethylammonium-1,4,7-7-triazacyclononane or suitable big ring.Though other metal ligand and mononuclear coordination compound also are fine, monometallic and two and the title complex of multi-metal complex and other metal such as iron or ruthenium all within the scope of the invention.The bleach catalysts of other metal matrix is included in those disclosed among US4430243 and the US5114611.Use manganese in following United States Patent (USP), to report with various compound title complexs: 4728455 to improve bleachability; 5284944; 5246612; 5256779; 5280117; 5274147; 5153161 and 5227084.
But transition metal its pre-mated or cooperate on the spot with suitable donor ligands, described donor ligands is selected according to the denticity of selected metal, its oxidation state and ligand.Other can be used for the title complex that title complex of the present invention is the U. S. application series number 08/210186 of application on March 17th, 1994.
According to desired end-use, composition of the present invention can be packaged in the various containers, comprises conventional bottle, has the bottle or the atomizer of ball, sponge, brush or nozzle.
Although the advantageous applications of liquid composition described herein is a laundry applications, as detergent for washing clothes or as laundry additive with especially as pretreating agent, said composition is also available with cleaning crust.
The present invention will be further specified by following embodiment.
EXAMPLE Example 1
Prepare a kind of liquid composition, it contains:
Weight %)
Hydrogen peroxide 6%
ATC 2％
Benzylalcohol (HI=16) 2%
Firpene (HI=0) 1%
Ethoxy ethoxy ethanol (HI=37) 4%
Dobanol23.3 8.6％
Dobanol45.7 6.4％
C12 alkyl-sulphate 2%
Water and minor component reach 100%
PH=4 regulates with sulfuric acid
In pretreatment mode, said composition is used the dirty part of fabric with respective pure form, make it on fabric, act on 5 minutes.Use conventional detergent washing fabric and rinsing then.To various spots, but comprise that oil spot, enzyme spot, clay spot and bleach spot obtain fabulous decontamination.Embodiment 2
Prepare a kind of liquid composition, it contains:
(weight %)
Hydrogen peroxide 4.0%
ATC 3.5％
Benzylalcohol (HI=16) 2%
Methoxypropanol (HI=37) 5%
Limonene (HI=0) 1%
Dobanol23.3 8.6％
Dobanol45.7 6.4％
C12 alkyl-sulphate 2%
Water and minor component reach 100%
PH=4 regulates with sulfuric acid
In pretreatment mode, said composition is used the dirty part of fabric with respective pure form, make it on fabric, act on 5 minutes.Use conventional detergent washing fabric and rinsing then.To various spots, but comprise that oil spot, enzyme spot, clay spot and bleach spot obtain fabulous decontamination.Embodiment 3
Be prepared as follows liquid composition:
(weight %)
Hydrogen peroxide 6.0%
ATC 3.5％
Benzylalcohol (HI=16) 1%
Firpene (HI=0) 0.5%
Propoxy-propyl alcohol (HI=28) 5%
Dobanol45.7 6.0％
Dobanol23.6,5 6.0％
C25-AE2.5-S (ethoxylated alkyl sulfates) 12.0%
Water and minor component reach 100%
PH=4 regulates with sulfuric acid
In the mode of in whole washing process, bleaching, composition is contacted with the water-bath that forms by the conventional washing composition of dissolving in water.Then fabric is contacted with the water-bath that contains liquid washing agent, and rinse fabric.Said composition also can be used for pretreatment mode, wherein it is poured on the fabric with respective pure form, makes its effect 5 minutes, and laundering of textile fabrics.To various spots, but comprise that oil spot, enzyme spot, clay spot and bleach spot obtain fabulous decontamination.Embodiment 4
Be prepared as follows liquid composition:
(weight %)
Tert-butyl hydroperoxide 5%
Ethoxy ethoxy ethanol (HI=37) 8%
Limonene (HI=0) 2%
Dobanol91.10 1.6％
Dobanol23.3 1.5％
C10 alkyl-sulphate 1.7%
Isofol?12 0.5％
Water and minor component reach 100%
PH=4 regulates with sulfuric acid
Said composition can be used for the mode of bleaching in pretreatment mode described in above-mentioned embodiment or the whole washing process.Said composition also can be used for immersion way, wherein the 100ml liquid composition is diluted in 10 premium on currency.Fabric contacts with the water-bath that contains composition subsequently, and it was soaked 24 hours therein, final rinse fabric.To various spots, but comprise that oil spot, enzyme spot, clay spot and bleach spot obtain fabulous decontamination.Embodiment 5
Be prepared as follows liquid composition:
(weight %)
Tert-butyl hydroperoxide 5%
Ethoxy ethoxy ethanol (HI=37) 8%
Firpene (HI=0) 2%
Dobanol91.10 1.6％
Dobanol23.3 1.5％
C10 alkyl-sulphate 1.7%
Isofol?12 0.5％
Water and minor component reach 100%
PH=4 regulates with sulfuric acid
Said composition can be used for the mode of bleaching in pretreatment mode described in above-mentioned embodiment or the whole washing process.Said composition also can be used for immersion way, wherein the 100ml liquid composition is diluted in 10 premium on currency.Fabric contacts with the water-bath that contains composition subsequently, and it was soaked 24 hours therein, final rinse fabric.To various spots, but comprise that oil spot, enzyme spot, clay spot and bleach spot obtain fabulous decontamination.Embodiment 6
Be prepared as follows liquid composition:
(weight %)
Hydrogen peroxide 7%
Ethoxy ethoxy ethanol (HI=37) 1%
Limonene (HI=0) 0.2%
Dobanol91.10 1.6％
Dobanol23.3 1.5％
C10?AS 1.7％
Isofol?12 0.5％
Water and minor component reach 100%
PH=4 regulates with sulfuric acid
Said composition can be used for the mode of bleaching in pretreatment mode described in embodiment 1 and 2 or the whole washing process.Said composition also can be used for immersion way, wherein the 100ml liquid composition is diluted in 10 premium on currency.Fabric contacts with the water-bath that contains composition subsequently, and it was soaked 24 hours therein, final rinse fabric.To various spots, but comprise that oil spot, enzyme spot, clay spot and bleach spot obtain fabulous decontamination.Embodiment 7
Be prepared as follows liquid detergent composition:
(weight %)
Cumyl hydroperoxide 10%
Ethoxy ethoxy ethanol (HI-37) 4.0%
Benzylalcohol (HI=16) 15%
Dobanol23.3 8.6％
Dobanol45.7 6.4％
C12AS 2％
Water and minor component reach 100%
PH=6 regulates with sulfuric acid
Described in above-mentioned embodiment, composition is used for pretreatment mode.To various spots, but comprise that oil spot, enzyme spot, clay spot and bleach spot obtain fabulous decontamination.Embodiment 8
Be prepared as follows liquid composition:
(weight %)
2,5-dimethyl-hexane-2,5-dihydro-peroxidase 5%
Propoxy-propyl alcohol (HI=28) 8%
Firpene (HI=0) 1.0%
Dobanol23.3 8.6％
Dobanol45.7 6.4％
C25-2.5EO-S 2％
Water and minor component reach 100%
PH=5 regulates with sulfuric acid
Be used for pretreatment mode described in said composition such as the above-mentioned embodiment.To various spots, but comprise that oil spot, enzyme spot, clay spot and bleach spot obtain fabulous decontamination.Embodiment 9
Be prepared as follows liquid composition:
(weight %)
Two bay acyl peroxides 2.0%
Methoxypropanol (HI=37) 4.0%
Benzylalcohol (HI=16) 1.0%
Dobanol23.3 8.6％
Dobanol45.7 6.4％
C12 alkyl-sulphate 1.0%
Water and minor component reach 100%
PH=4 regulates with sulfuric acid
Be used for pretreatment mode described in said composition such as the above-mentioned embodiment.To various spots, but comprise that oil spot, enzyme spot, clay spot and bleach spot obtain fabulous decontamination.Embodiment 10
Be prepared as follows liquid composition:
(weight %)
Two bay acyl peroxides 0.5%
Hydrogen peroxide 4.0%
ATC 2.0％
Methoxypropanol (HI=37) 5.0%
Benzylalcohol (HI=16) 2.0%
Limonene (HI=0) 0.5%
Dobanol23.3 8.6％
Dobanol45.7 6.4％
C25-2.5EO-S 2％
Water and minor component reach 100%
PH=5 regulates with sulfuric acid
ATC represents acetyl triethyl citrate in the above-described embodiments.
Be used for pretreatment mode described in said composition such as the above-mentioned embodiment.To various spots, but comprise that oil spot, enzyme spot, clay spot and bleach spot obtain fabulous decontamination.Embodiment 11
Be prepared as follows liquid composition:
(weight %)
Didecyl acyl peroxide 0.5%
Hydrogen peroxide 7.0%
Oxyethyl group propyl alcohol (HI=32) 1.0%
Limonene (HI=0) 0.2%
Dobanol91.10 1.5％
C10 alkyl-sulphate 1.7%
Water and minor component reach 100%
PH=4 regulates with sulfuric acid
The mode that is used for pretreatment mode or bleaches described in said composition such as the above-mentioned embodiment at whole washing process.To various spots, but comprise that oil spot, enzyme spot, clay spot and bleach spot obtain fabulous decontamination.

Claims (13)

1. method with the liquid composition bleached woven fabric, described liquid composition contain peroxygen bleach and contain hydrophilic index greater than 18 hydrophilic solvent and the hydrophilic index solvent system less than 18 hydrophobic solvent, and wherein hydrophilic index is by following formula definition:
The molecular weight of solvent hydrophilic segment
---------------------------------------?*100,
The described method of the total molecular weight of solvent is included in rinsing or washs then before the rinse fabric, and described composition is applied on the described fabric with its respective pure form, the step on preferred only its dirty part.
2. make described pure composition contact 1 minute to 1 hour with described fabric according to the process of claim 1 wherein, preferred 1 minute to 30 minutes.
3. the method for a bleached woven fabric, it comprises the steps: the liquid composition of dilution respective pure form in water-bath, described composition contains peroxygen bleach and contains hydrophilic index greater than 18 hydrophilic solvent and the hydrophilic index solvent system less than 18 hydrophobic solvent, and wherein hydrophilic index is by following formula definition:
The molecular weight of solvent hydrophilic segment
------------------------------------?*100,
The total molecular weight of solvent contacts described fabric and with post rinsing or wash the described fabric of rinsing then with the water-bath that contains described liquid composition.
4. according to the method for claim 3, fabric was soaked 30 minutes to 48 hours in the described water-bath that contains described liquid composition, preferred 1 hour to 24 hours.
5. according to the method for claim 3 or 4, wherein said water-bath is by dissolving in water or disperse conventional detergent for washing clothes preparation.
6. liquid composition that is suitable for bleached woven fabric, it contains peroxygen bleach and contains by the hydrophilic index of general composition weight meter 0.05%-20% greater than 18 hydrophilic solvent with by the solvent system of general composition weight meter 0.05%-10% hydrophilic index less than 18 hydrophobic solvent, and wherein hydrophilic index is by following formula definition:
The molecular weight of solvent hydrophilic segment
-------------------------------------------?*?100。
The total molecular weight of solvent
7. require the method for 1-5 or the composition of claim 6 according to arbitrary aforesaid right, wherein said pure composition contains by the peroxygen bleach of general composition weight meter 0.01%-20% or their mixture, preferred 1%-10%, more preferably 4%-7%.
8. method or the composition that requires according to arbitrary aforesaid right; wherein said peroxygen bleach is selected from percarbonate; persilicate; persulphate; perborate; peroxy acid; alkyl hydroperoxide; superoxide; aliphatic series diacyl peroxide and their mixture; hydrogen peroxide preferably; tert-butyl hydroperoxide; the cumyl hydroperoxide; 2; 5-dimethyl-hexane-2; the 5-dihydro-peroxidase; 2; 4,4-tri-methyl-amyl-2-hydroperoxide; diisopropyl benzene list hydroperoxide; t-amyl hydroperoxide; the didecyl acyl peroxide; two bay acyl peroxides and/or two myristoyl superoxide.
9. method or the composition that requires according to arbitrary aforesaid right, wherein said hydrophilic solvent is that hydrophilic index surpasses that 18 alkoxylate aliphatic series or aromatic alcohol, hydrophilic index surpass 18 aliphatic series or aromatic alcohol, hydrophilic index surpasses 18 glycol or alkoxylated diols or their mixture, preferably ethanol, propyl alcohol, methoxypropanol, oxyethyl group propyl alcohol, propoxy-propyl alcohol, butoxy propyl alcohol, propylene glycol, oxyethyl group-oxyethyl group-ethanol or their mixture.
10. method or the composition that requires according to arbitrary aforesaid right, wherein said hydrophobic solvent is a hydrophilic index less than 18 paraffinic hydrocarbons, terpenes or terpene derivatives, hydrophilic index less than 18 alkoxylate aliphatic series or aromatic alcohol, hydrophilic index less than 18 aliphatic series or aromatic alcohol, hydrophilic index less than 18 glycol or alkoxylated diols or their mixture, preferably d-limonene, limonene, α--firpene, beta-pinene, octane, benzylalcohol or their mixture.
11. method or composition according to arbitrary aforesaid right requirement, wherein said composition contains by general composition weight meter 0.1%-5%, the hydrophobic solvent of preferred 0.2-2% or their mixture, with press general composition weight meter 0.5%-15%, the hydrophilic solvent of preferred 1-10% or their mixture.
12. method or composition according to arbitrary aforesaid right requirement, wherein composition also contains at the most 50%, preferred 0.3%-30%, the more preferably nonionogenic tenside of 0.4%-25% or their mixture, wherein said nonionogenic tenside is that HLB is lower than 16 hydrophobic non ionic surfactants or their mixture, is more preferably formula RO-(C 2H 4O) n(C 3H 6O) mThe alkoxy-based non-ionic surface active agent of H or their mixture, wherein R is C 6-C 22Alkyl chain or C 6-C 28The alkylbenzene chain and wherein n+m be 0-20, n is 0-15, m is 0-20, preferred n+m is 1-15, n and m are 0.5-15, more preferably n+m is 1-10, n and m are 0-10.
13. according to method or composition that arbitrary aforesaid right requires, wherein said composition has 1-12, preferred 2-6, the more preferably pH of 3-5.
CN97199585A 1996-09-13 1997-09-10 Laundry bleaching processes and compositions Pending CN1237202A (en)

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EP1001008A1 (en) * 1998-11-10 2000-05-17 The Procter & Gamble Company Liquid aqueous bleaching compositions comprising a sulphonated anionic surfactant
WO2001094685A1 (en) * 2000-06-05 2001-12-13 The Procter & Gamble Company Bleaching in conjunction with a lipophilic fluid cleaning regimen
DE60133815T2 (en) * 2000-06-05 2009-05-20 The Procter & Gamble Company, Cincinnati USE OF WATER VAPOR AND A LIPOPHILIC LIQUID TO CLEAN TEXTILE PRODUCTS
US8871807B2 (en) 2008-03-28 2014-10-28 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
CN103146507B (en) * 2013-03-22 2014-07-16 于文 Environment-friendly faintly acid washing-free stain-removing liquor and preparation method thereof
CN105765046A (en) * 2013-12-05 2016-07-13 罗门哈斯公司 Cleaning composition with rapid foam collapse
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GB8810195D0 (en) * 1988-04-29 1988-06-02 Unilever Plc Liquid cleaning products
DE4030850A1 (en) * 1990-09-29 1992-04-02 Henkel Kgaa Pasty bleaching agent compsn. - comprising perborate mono:hydrate in liq. medium comprising addn. prod. of ethylene oxide with long chain satd. alcohol
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US5492540A (en) * 1994-06-13 1996-02-20 S. C. Johnson & Son, Inc. Soft surface cleaning composition and method with hydrogen peroxide

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