CN1239984A - Alkoxylated quaternized diamine detergent ingredients - Google Patents

Alkoxylated quaternized diamine detergent ingredients Download PDF

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Publication number
CN1239984A
CN1239984A CN97180357A CN97180357A CN1239984A CN 1239984 A CN1239984 A CN 1239984A CN 97180357 A CN97180357 A CN 97180357A CN 97180357 A CN97180357 A CN 97180357A CN 1239984 A CN1239984 A CN 1239984A
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group
composition
alkyl
unit
washing
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Inventor
J·I·卡恩
K·普拉莫德
J·A·勒平
D·S·康纳
大谷良平
R·K·帕南蒂克
F·德布扎卡里尼
J·L·港－陈
E·P·古塞林克
安田绢子
C·K·高希
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Procter and Gamble Co
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Procter and Gamble Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C11D3/37—Polymers
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D3/37—Polymers
    • C11D3/3792—Amine oxide containing polymers
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618—Protease or amylase in liquid compositions only
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase

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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)
  • Detergent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Quaternized alkylene diamines, and mixtures thereof, are used in detergent compositions.

Description

Alkoxylated quaternized diamine detergent ingredients
Technical field
The present invention relates to contain the component of selection, comprise the detergent composition of the quaternized ethoxylation Alkylenediamine compound of selection.
Background of invention
There are many challenges in the prescription of detergent for washing clothes and other cleaning composition, and this is because modern composition need satisfy from different dirt-carrying bodies and remove various dirts and spot.Therefore, detergent for washing clothes, hard surface cleaner, shampoo and other human body cleaning composition, detergent for washing dishware with hand and the detergent composition that is applicable to the automatic tableware washing machine all need to select suitably and combination partner to work effectively.Usually, this class detergent composition will contain being used for loose and removing the tensio-active agent of some dirt and spot of one or more types.Yet in the dirt and spot demonstration optimum performance to some type, they in fact can reduce the performance to other dirt at some washing composition auxiliary component and tensio-active agent.For example, the tensio-active agent of removing greasy/oily soil from fabric is a suboptimum for removing particulate fouling sometimes.In addition, the dirt of removing from carrier should be dispersed or suspended in the washing mother liquor to reduce their depositions again on the dirt-carrying body at once.
Therefore, effectively removing particulate fouling may be problematic with this dirt that suspends.The most important particulate fouling that causes this class problem may be the loam mould dirt.The clay soil particle contains the negative charge layer and the positive charge positively charged ion (for example calcium) of silico-aluminate usually, and it links together between the negative charge layer and with them.
To having the compound of removing clay soil character various patterns can be proposed.A kind of pattern needs compound to have two kinds of different characteristics.At first being that compound is adsorbed on the ability on the clay particle negative charge layer, secondly is compound in case after the absorption, push away the ability of (expansion) negative charge, makes clay particle lose adhesive power and also can remove in washing water.
Except clay soil was removed, the dirt that also needs to keep removing suspended in laundry processes.The dirt of removing from fabric He be suspended in the washing water can deposit on the surface of fabric again.This sedimentary again dirt causes delustring or " becoming ash " effect, and this is especially tangible for white fabrics.For reducing this problem, can in detergent composition, add anti redeposition agent.For example EP-B-111 965 discloses and used cation compound in washing composition, and it has clay soil simultaneously and removes and antiredeposition character.
Although do not plan to be limited to theory, but the pattern that anti-redeposition proposed to positively charged antiredeposition compound is as follows: positive charge molecules is adsorbed on washing water medium clay soil particulate surface makes particle have molecular dispersion character, along with increasing such compound is adsorbed on the clay soil particle of suspension, the latter becomes and wraps in the hydrophilic layer, the dirt of hydrophilic like this parcel has been avoided being deposited on the fabric again in laundry processes, especially on the hydrophobic fabric, polyester for example.
People have carried out a large amount of research to find out the compound of effectively removing dirt and avoiding soil redeposition.Therefore, although see the extensive selection that can obtain tensio-active agent and other component for the washing composition makers-up from document, in fact many these components are expensive chemical, and it is not suitable in the low unit cost product, for example the household laundry washing composition.May remain most of household product on the reality for consideration economically, for example detergent for washing clothes still mainly contains one or more conventional surfactants and washing assistant and conventional auxiliary agent.People need prepare the composition that contains additional adjuvants, and it is had an effect for various dirts and spot and various fabric.
Therefore, people constantly study to improve washing composition, especially laundry and dishwashing detergent and hard surface cleaner.Yet the washing composition makers-up explores the difficulty of improving performance to be increased by many factors.For example, some nonbiodegradable component begins to stop using, and effectively phosphate builder is forbidden with legal form in many countries.Influenced their purposes with some compound cost related.As a result, the makers-up is selecting effectively sometimes, more restricted than the document suggestion during component popularized.The human consumer still constantly expects the composition of high quality and high character, even works as washing operation under suboptimal conditions, and for example laundering of textile fabrics carries out in cold or cold water.
Document advises that various nitrogenous compounds can be used in the various cleaning combinations, and this material is generally amino, amido or quaternary ammonium or imidazolium compounds form, is generally used for special purpose.For example various amino and quaternary ammonium surfactant are proposed to be used in shampoo composite, and being considered to provides aesthetic effect for hair.Other nitrogen-containing surfactants is used for some detergent for washing clothes so that fabric sofetening and antistatic effect to be provided.Yet for great majority, the industrial application of this material is quite limited.
We find that now some alkoxy quaternary ammonium diamines (AQD) compound can be used for various detergent composition to increase effect, especially for particulate fouling be used for the suspension of dirt at washing liq.Importantly, we find further that also these AQD compounds of low levels provide fabulous scourability when known with other or conventional component is used in combination.Therefore, the invention provides the improvement of scourability, and do not need to develop new, expensive surfactant materials.
In addition, concerning ingredients teacher, more known other dispersion agent provides tangible advantage than so far to be used for AQD decontamination/dispersion agent of the present invention.For example, AQD dispersion agent of the present invention and preferred alkyl-sulphate, alkyl ethoxy sulfate are compatible with amido propyl group amine detergent surfactant, in addition, the AQD dispersion agent can be prepared in the wide pH scope of 5-12, different with other quaternary ammonium compound well known in the prior art is that the AQD dispersion agent is also compatible with various perfume compositions.
Except above-mentioned advantage, the AQD dispersion agent show to reduce or avoids returning at lipid acid/oily material that moisture laundry mother liquor exists and be deposited on the fabric of before having been made dirty by the health dirt again.Therefore, we find that now AQD dispersion agent of the present invention avoided polar lipid to deposit to by laundry processes again and removed on the fabric of health dirt from the aqueous cleaning water-bath.In other words, in the laundry mother liquor, the AQD dispersion agent is removed polar lipid, keeps them to be suspended in the water-bearing media, rather than they are deposited on the washed fabric again.
Except above-mentioned characteristic, the AQD dispersion agent unexpectedly with polyanionic materials, for example provide the polyacrylic ester and the vinylformic acid/maleic acid of washing assistant and/or dispersion agent effect compatible with many conventional detergent surfactants.In addition, we also are surprised to find AQD dispersion agent of the present invention and molecular weight and combine less than about 5000 special ethoxylation polymine collaborative washing effect is provided.
Other advantage of AQD dispersion agent of the present invention comprises that they can improve enzyme washing and fabric nursing character in the laundry mother liquor.Although do not plan to be limited to theory, can estimate that enzyme can be by conventional anion surfactant partially denaturing, also further expectation AQD dispersion agent and anion surfactant react to each other to suppress degraded.Another kind of theoretical suggestion, even when enzyme is used to degrade dirt and spot, the residue of degraded must be removed from fabric face, can estimate that the soil suspension properties of the improvement that the AQD dispersion agent provides is being removed good effect the residue from washing mother liquor and fabric face.
Except above-mentioned advantage, to compare with conventional detergent mixture, AQD dispersion agent of the present invention provides the significant washing improvement of removing the clay soil aspect from fabric.Equally,, can estimate that conventional cats product and clay have an effect in " closely parcel " mode, make that clay more is difficult to remove although do not plan to be limited to theory.In contrast, alkoxylate AQD dispersion agent is considered to provide combining of more open and clay, and this makes it be easier to remove from fabric face.For this reason, the composition of the AQD of containing dispersion agent of the present invention is especially in the performance that improvement is provided than conventional dispersion agent aspect the clay soil removal.
Other advantage of AQD dispersion agent of the present invention is found, for example containing the bleach activator bleaching composition of (as open) herein, shows that the peracid that discharges with bleach activator forms some ion pair or other relevant title complex.Can estimate that this ion pair more effectively is brought into dirt as new hydrophobizing agent, thereby improve and use bleach activator, for example nonanoyl oxygen benzene sulfonate (NOBS), tetra acetyl ethylene diamine (TAED) or the relevant bleachability of peracid.Quite the AQD dispersion agent of low levels has produced these results.
In addition, in not having the composition of SYNTHETIC OPTICAL WHITNER, the makers-up can select to use high-load slightly AQD dispersion agent so that the impact of performance of improvement to be provided.These effects may with the conventional anion surfactant of AQD dispersion agent modification, for example the dissolution characteristics of alkyl-sulphate or alkyl ethoxy sulfate so that more surfactant can be used to play their ability of cleaning function relevant.This is especially such in the following occasion that the makers-up faces, wherein detergent composition for calcium and/the magnesium water hardness ions is " a little less than help wash ".
The mixture of AQD dispersion agent can mix and be used for various dirts and spot and the scourability of wide region is provided under the working conditions of wide region.This combination of AQD dispersion agent representational, but non-limiting instance is open among the embodiment hereinafter.
Various other advantages that the AQD dispersion agent is better than other dispersion agent of the prior art are described in more detail below.From herein description as can be seen, use the AQD dispersion agent to solve many and the relevant problem of preparation modern high performance detergent composition in mode of the present invention.These dispersion agents especially can be prepared effective laundry composition, and it is used under the working conditions of wide region and removes various dirts and spot.
These and other advantage of the present invention will be by finding out in the following description.
Background technology
US4659802 and US4664848 have described positively charged ion (quaternized) amine compound with clay soil removal and antiredeposition character.
Summary of the invention
The present invention relates to contain the detergent composition that some alkoxylate (especially ethoxylation) quaternized polyamine dispersion agent following compositions or by mixing significant quantity and one or more washings (comprising fabric nursing) auxiliary component prepare, as described below.Be used for alkoxylated quaternized diamine of the present invention (AQD) dispersion agent and have following general formula:
Figure A9718035700101
Wherein R is selected from straight or branched C 2-C 12Alkylidene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy, C 8-C 12Dialkyl group arylidene, [(CH 2CH 2O) qCH 2CH 2]-and-CH 2CH (OH) CH 2O-(CH 2CH 2O) qCH 2CH (OH) CH 2]-, wherein q is about 1-about 100; Each R 1Be selected from C respectively 1-C 4Alkyl, C 7-C 12Alkylaryl or A.A has following formula:
Figure A9718035700102
R wherein 3Be selected from H or C 1-C 3Alkyl, n are that about 5-is about 100, and B is selected from H, C 1-C 4Alkyl, acetyl or benzoyl base; X is a water soluble anion.
In preferred embodiments, R is selected from C 4-C 8Alkylidene group, R 1Be selected from C 1-C 2Alkyl or C 2-C 3Hydroxyalkyl and A are: R wherein 3Being selected from H or methyl and n is about 10-about 50.
In another preferred embodiment, R is straight or branched C 6, R 1Be methyl, R 3Be that H and n are about 20-about 50.
AQD can synthesize according to the method or the additive method well known by persons skilled in the art of USP4664848 narration.
The content of AQD dispersion agent that is used to prepare final laundry detergent composition is about 10% for about 0.1%-by weight, is generally about 0.4%-about 5%.
The present invention includes and use above-mentioned AQD dispersion agent to contain the overall scourability of the detergent composition of other known component with raising.We find that now the overall scourability of this detergent composition can be by adding the AQD dispersion agent improvement of relatively small amount.Surprisingly, not only improved, and improved laundry scourability the responsive dirt of health dirt, washing assistant, the responsive dirt of SYNTHETIC OPTICAL WHITNER and food soil and socks dirt to greasy dirt.Certainly, the use content of the AQD dispersion agent in various types of detergent formulation and use pattern will depend on makers-up's needs.This prescription representational, but that non-restrictive example comprises is as follows.
Detergent composition, it contains conventional detergent component, AQD dispersion agent and special surface promoting agent, comprises alkyl-sulphate (AS) and alkyl alkoxy, especially ethoxylated sulfate (AES).In other preferred embodiment, the composition that contains AQD dispersion agent and these tensio-active agents does not have (promptly contain and be less than 5%, preferably be less than 1%) linear alkylbenzene sulfonate (LAS) basically.In another embodiment, in non-aqueous liquid detergent compositions, AQD mixes with linear alkylbenzene sulfonate.
Detergent composition, it contains the amine tensio-active agent of conventional detergent component, AQD dispersion agent and selection, for example amido propyl-dimethyl amine.
Detergent composition, it contains conventional detergent component, AQD dispersion agent and polyester or oligomer ester stain remover, especially is non-cotton soil release polymers or stain remover.
Detergent composition, it contains conventional detergent component, AQD dispersion agent and molecular weight less than about 5000, preferably less than about 2000, more preferably from about the polyethoxylated polyvinylamine polymers of 600-about 1000 or ethoxylation polymine (PEI) polymkeric substance.
Detergent composition, it contains conventional detergent component, AQD dispersion agent and amylase or lipase or their mixture.
In another embodiment, this prescription comprises following example:
Detergent composition, it contains conventional detergent component, AQD dispersion agent and sequestrant, especially ethylenediamine disuccinate (EDDS) sequestrant.
Detergent composition, it contains conventional detergent component, AQD dispersion agent and cellulase or proteolytic enzyme, or their mixture.
Detergent composition, it contains conventional detergent component, AQD dispersion agent and alkyl poly glucoside or polyhydroxy fatty acid amide surfactant.
Detergent composition, it contains conventional detergent component, AQD dispersion agent and on-aqueous liquid carrier matrix.
Detergent composition, it contains conventional detergent component, AQD dispersion agent and tap density is 650g/L or bigger detergent particles.
Detergent composition, it contains conventional detergent component, AQD dispersion agent and magnesium ion, calcium ion source or their mixture.
Detergent composition, it contains conventional detergent component, AQD dispersion agent and dye transfer inhibitor.
Detergent composition, it contains conventional detergent component, AQD dispersion agent and manganese, cobalt or iron bleaching catalyst.
Detergent composition, it contains conventional detergent component, AQD dispersion agent and zeolite P or " MAP " washing assistant.
Detergent composition, it contains conventional detergent component, AQD dispersion agent and mineral washing assistant.
Detergent composition, it contains conventional detergent component, AQD dispersion agent and oxygen bleaching agent, for example percarbonate bleach.
Detergent composition, it contains conventional detergent component, AQD dispersion agent and one or more bleach activators.
Detergent composition, it contains conventional detergent component, AQD dispersion agent and optical white.
The AQD dispersion agent that is used for mode of the present invention also provides removing and the method for suspend following dirt and spot from fabric of improving: greasy food spot, particle spot, health dirt (comprise a spot of, but the fabric that perceptible stain causes " gloomy ") and other above-mentioned spot.This spot and dirt are from fabric, and for example cotton, polyester/cotton mixture (P/C) and two the volume on the polyester (DKPE) are removed.This method comprises the fabric that needs are removed this dirt in the presence of water, preferably under agitation contacts with the composition of the present invention of significant quantity.Following discussion various suitable use content and methods.
Particularly for the fabric washing field, AQD compound of the present invention have commercial available and with the various detergent components that are used for high-quality full preparation detergent for washing clothes of many modern times, for example compatible advantage such as washing assistant, detergent enzyme.In addition, the AQD compound is being generally used for showing gratifying stability in the presence of the bleaching components of composition that detergent for washing clothes adds SYNTHETIC OPTICAL WHITNER.Importantly, AQD dispersion agent of the present invention is being removed health dirt and daily dirt, and for example socks dirt aspect shows fabulous performance.In brief, composition of the present invention comprises the responsive spot of the health dirt from collar and cuff, greasy dirt and enzyme/SYNTHETIC OPTICAL WHITNER to washing various dirts and spot, and for example spinach and coffee provide the performance of improvement.Composition of the present invention also provides the spot to the washing assistant sensitivity, and therefore for example fabulous washing of clay is particularly useful for without phosphorus aspect.
In addition, AQD dispersion agent of the present invention provides the fabric washing performance of improving in the presence of SYNTHETIC OPTICAL WHITNER.Find out that by the consumption that in the laundry mother liquor, is low to moderate the AQD of 3ppm this is considered to relevant with the mistake hydrolytic action that increases in the improvement aspect the washing.
In addition, AQD dispersion agent of the present invention provides amylase, especially Duramyl  and lipase, the especially improved performance of Lipolase Ultra  enzyme (even collaborative).This improvement is especially found out under the situation that does not have SYNTHETIC OPTICAL WHITNER.
All percentage ratios, ratio and ratio herein is the weight that is used to prepare the component of final composition, except as otherwise noted.All documents of quoting at relevant portion are classified this paper reference as herein.
The detailed description of invention
In one of aspect some, the invention provides by mixing the method that greasy/oily soil is removed in lipase and the raising of AQD dispersion agent.Greasy/oil " daily " dirt is the mixture of Witepsol W-S 55, liposome, complicated polysaccharide, inorganic salt and proteinaceous substances.When dirty clothes was deposited before washing, some Witepsol W-S 55 was converted into lipid acid by bacteriological action; Lipase can be used for the triglyceride level of any remnants is converted into lipid acid in washing process.Usually for the prescription that depends on by diffusion washing assistant (for example layered silicate) control hardness, have the false non-condition of washing that helps at first at washing process, it plays the effect of a large amount of absorption cold water.In this initial several minutes, lipid acid in dirt and non-helping are washed hardness and are interacted and to be not dissolved in the calcium soap of water with formation, and this has hindered decontamination subsequently and has caused being retained on the fabric at dirt residue after the washing.Help in the prescription of washing non-, not dissolving of greasy/oily spot will cause more serious problem.When successive dress/washing, residual substance accumulates, and causes yellow and entrained particles foul.Final clothes deepening sensuously can not be worn again, and is dropped usually.
We compare washing and the whitening performance that provides fabulous by the present detergent composition that contains AQD dispersion agent and lipase of finding with the product that contains any one independent technology.Suitable lipase comprises the microorganism of Rhodopseudomonas, the lipase that Situ Ci Shi Rhodopseudomonas ATCC 19.154 disclosed in GB1372034 mentions.Suitable lipase comprises the lipase that shows positive immunological cross-reaction with lipase antibody, and it is produced by microorganism Pseudomonas fluorescens IAM 1057.This lipase can be by Amano Pharmaceutical Co.Ltd.Nagoya, and Japan has bought, and commodity are called lipase P " Amano ", hereinafter are referred to as " Amano-P ".Other suitable lipase is lipase, for example M1 Lipase RAnd Lipomax R(Gist-Broxades).Other suitable commercial lipases comprises from thickness look bacillus, as derives from the Amano-CES lipase of lipolyticum thickness look bacillus mutation NRRLB 3673 of the Toyo Jozo Co. of Japanese Tagata; Derive from the thickness look bacillus lipase of the Disoynth of U.S. U.S.Biochemical Corp. and Holland; And the lipase that derives from high calamus Rhodopseudomonas.Plant by corruption that Pseudomonas fetal hair bacterium derives and the commercial LIPOLASE  enzyme (in addition referring to EP341947) that can be obtained by Novo is to be used for a kind of preferred lipase of the present invention.Lipase and the amylase mutation stable to peroxidase have description in the WO9414951A of Novo.In addition referring to WO9205249 and RD94359044.
Very preferred lipase is to be the D96L lipolytic enzyme mutation of the natural lipase that is produced by Humicola fetal hair bacterium described as US series № 08/341826.(also referring to patent application WO92/05249, wherein the natural lipase that is obtained by Humicola fetal hair bacterium 96 aspartic acid (D) residue put on the throne is changed and is leucine (L).According to nomenclature, above-mentioned aspartic acid and leucic replacement procedural representation at 96 is D96L) preferably use Humicola fetal hair bacteria strain DSM4106.
Although a large amount of publications is arranged aspect lipase, only plant Pseudomonas fetal hair bacterium and be found the additive that is widely used as the fabric washing product as the lipase that the host produces so far at Aspergillus oryzae by corruption.It can be as mentioned above by Novo Nordisk with trade name Lipolase TMObtain.Be the detergency ability of optimizing Lipolase, Novo Nordisk has prepared various mutation.Described in WO92/05249, the D96L mutation that Pseudomonas fetal hair bacterium lipase is planted in natural corruption has improved 4.4 times than wild-type lipase (enzyme that compares) in removal lard spot efficient in every liter of proteinic quantitative range of 0.075-2.5mg.Disclose lipase mutation (D96L) at disclosed Research Disclosure № 35944 on March 10th, 1994 (Novo Nordisk) and can be equivalent to every liter of amount adding of washing mother liquor 0.001-100mg (5-500000LU/l).
Lipase adds in the composition of the present invention with the content of every liter of washing soln 50LU-8500LU.Mutation D96L preferably exists with the content of every liter of washing soln 100LU-7500LU, more preferably the content of every liter of washing soln 150LU-5000LU.
Lipase and/or at add in the detergent composition in the content by detergent composition weight 0.0001%-2% organized enzyme usually.
That same suitable is at [EC 3.1.1.50], and it is considered to the lipase of particular variety, does not promptly need the lipase of interface activation.Adding in detergent composition describes in for example WO-A-88/09367 (Genencor).
Amylase-remove very hydrophobic " daily " fully or " health " dirt is difficult, common residual low levels of residual dirt after washing.These residue build-up get up and as amorphous glue between fabric, work entrained particles dirt and cause fabric jaundice.We find to contain the water-soluble AQD dispersion agent of the present invention now and compare washing and the whitening performance that provides fabulous with diastatic detergent composition with the composition that contains independent above-mentioned any component.
The amylase of describing among the application PCT/DK96/00056 when this amylase is included in WO/95/26397 and Novo Nordisk.These enzymes are to press the pure enzyme of general composition weight meter 0.00018%-0.060%, and the content of more preferably pressing the pure enzyme of general composition weight meter 0.00024%-0.048% adds in the detergent composition.
Therefore, the special amylase that is used for detergent composition of the present invention comprises: (a) α-Dian Fenmei, it is characterized in that, by the test determination of Phadebas  alpha-amylase activity, have under its pH in 25 ℃-55 ℃ temperature range and at 8-10 than the ratio of Termamyl  high at least 25% ratio alive and live, this Phadebas  alpha-amylase activity test is described in WO95/26397 9-10 page or leaf.(b) according to the α-Dian Fenmei of (a), it contains the amino sequence that is presented at the SEQ ID in the above-mentioned document of listing or at least 80% and be shown in the amino sequence homologous α-Dian Fenmei of SEQ ID.(c) according to the α-Dian Fenmei of (a), it contains the following amino sequence at the N end: His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp.
If the aminoacid sequence of finishing through algorithm more separately, for example Lipman and Pearsin described in 1985,1435 pages, confirm that X% is identical at Science227, and then polypeptide is considered to X% with coming from parent amylase.(d is according to the α-Dian Fenmei of (a-c), and wherein α-Dian Fenmei is obtained by close alkali bacillus genus, is especially obtained by any bacterial strain NCIB 12289, NCIB 12512, NCIB 12513 and DSM 935.
In content of the present invention, term " can by ... obtain " not only be meant by Bacillaceae and produce amylase, and be meant and use by amylase this bacillus separated DNA sequence encoding and that in this dna sequence dna host transformed biology, produce.(e) α-Dian Fenmei shows the antibody positive immune cross-reactivity that produces by the α-Dian Fenmei that has respectively corresponding to the α-Dian Fenmei aminoacid sequence in (a-d).(f) mutation of following parent α-Dian Fenmei, it (i) has respectively a kind of corresponding to the aminoacid sequence of α-Dian Fenmei shown in (a-e), or (ii) demonstration at least 80% and one or more described amino acid sequence homologous, and/or show positive immune cross-reactivity to the antibody that produces by α-Dian Fenmei with one of above-mentioned aminoacid sequence, and/or by dna sequence encoding, it is hybridized with the same probe of the dna sequence dna of the α-Dian Fenmei that has one of described aminoacid sequence as coding; Wherein mutation: 1. at least one amino-acid residue of described parent α-Dian Fenmei is removed; And/or at least one amino-acid residue of 2. described parent α-Dian Fenmei is replaced by different amino-acid residues; And/or 3. insert at least one amino-acid residue with respect to described parent α-Dian Fenmei; Described mutation has alpha-amylase activity, show at least a following character with respect to described parent α-Dian Fenmei: the thermostability of increase, the calcium ion dependency of the oxidative stability of increase, reduction, in the iso-electric point (pI) of the stability of neutrality increase to the higher pH value and/or Alpha-starch degrading activity, the Alpha-starch degrading activity that under higher temperature, increases and increase or decline so that make the pI value of α-Dian Fenmei mutation be adapted to the pH of medium better.
Described mutation is described in patent application PCT/DK96/00056.
Be appropriate to other amylase of the present invention and comprise the α-Dian Fenmei of for example in the GB1296839 of Novo, describing; International Bio-Synthetic, the RAPIDASE  of Inc and the TERMAMYL  of Novo, the FUNGAMYL  that is obtained by Novo is useful especially.Being used to improve the stability of enzyme, is known as the method for oxidative stability.Referring to, J.BiologicalChem for example, Vol.260, on June 11st, 1985,6518-6521 page or leaf.Some preferred embodiment of the present invention can be used at washing composition, the stability that for example has improvement in the automatic tableware wash type is especially with respect to the amylase of the oxidative stability of the improvement of measuring in the reference point of the TERMAMYL of commercial use  from 1993.These the present invention preferred amylase has " stability increases " diastatic feature, and its feature is oxidative stability at least, as in the buffered soln of pH=9-10 to the oxidative stability of hydrogen peroxide/tetra acetyl ethylene diamine; As the thermostability under normal wash temperature such as about 60 ℃; Or as under the pH of about 8-11 value, contrasting the alkaline stability that above-mentioned reference point amylase is measured.In these stability one or more have the improvement that can measure.Stability can be measured by the test of using any prior art, referring to the disclosed content of for example WO9402597.The amylase that stability increases can be obtained by Novo or GenencorInternational.Preferred a kind of amylase of the present invention has following common ground: from one or more bacillus amylases, particularly deriving from the bacillus α-Dian Fenmei obtains by site-directed mutagenesis, and with a kind of, two or more amylase strains whether be that direct precursor is irrelevant.The preferred amylase that increases with respect to above-mentioned reference enzyme oxidative stability that uses especially for to bleach detergent compositions of the present invention, more preferably is different from the oxygen bleaching of chlorine bleaching.This preferred amylase comprises that (a) is according to the WO9402597 of the above Novo that has mentioned, described amylase in 3 days February in 1994, it can further be illustrated with a mutant, wherein use L-Ala or Threonine, preferably be positioned at the lichenoid form bacillocin that is called TERMANYL  with Threonine is alternative, or 197 methionine residues of the even position mutation of similar ative starch enzyme such as starch anaerobic bacillus(cillus anaerobicus), Bacillus subtilus or stereoisomerism thermophilic bacteria; (b) amylase that increases of the stability of Genencor International described in the paper of delivering to the 207th american chemical association annual meeting by C.Mitchinson 13-17 day in March, 1994 that is entitled as " oxidation resistant α-Dian Fenmei ".Wherein mentioned SYNTHETIC OPTICAL WHITNER inactivation α-Dian Fenmei in automatic dishwashing detergent, but Genencor has been prepared the amylase of the oxidative stability of improving by lichens shape bacillus NCIB8061.Methionine(Met) (Met) is proved to be the residue of easy modification.Met replaces simultaneously at 8,15,197,256,304,366 and 438, can obtain specific mutation, particularly importantly M197L and M197T, and wherein the M197T mutation is the best mutation of stability.Stability is measured in CASCADE  and SUNLIGHT ; (c) especially preferred amylase of the present invention comprises the amylase mutation that additional modification is arranged described in WO9510603A in the intermediate parent, is obtained with trade(brand)name DURAMYL  by Novo.The amylase that other particularly preferred oxidative stability increases comprises the enzyme described in the WO9402597 of the WO9418314 of Genencor International and Novo.The amylase that can use any other oxidative stability to increase, for example deriving from available diastatic known chimeric, hybrid or simple mutant parent by site-directed mutagenesis obtains.Can carry out other preferred enzyme-modified, referring to the WO9509909 of Novo.
Alkyl alkoxy sulfate and/or alkyl-sulphate-alkyl alkoxy sulfate tensio-active agent is formula RO (A) mSO 3The water-soluble salt of M or acid, wherein R is unsubstituted C 10-C 24Alkyl or contain C 10-C 24The hydroxyalkyl of moieties, preferred C 12-C 18Alkyl or hydroxyalkyl, more preferably C 12-C 15Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is greater than zero, usually between about 0.5 to about 6, more preferably from about between 0.5 to about 3, M is H or positively charged ion, and it can be the ammonium cation of metallic cation (for example sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replacement for example.The present invention thinks over alkyl ethoxy sulfate and alkyl propoxy-vitriol.The specific examples of the ammonium cation that replaces comprise ethanol-, three ethanol-, methyl-, dimethyl-, trimethylammonium-ammonium cation and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine positively charged ion and by alkylamine, for example ethamine, diethylamine, triethylamine, the positively charged ion that their mixture obtains etc.The tensio-active agent of illustrative is C 12-C 15The many ethoxylations of alkyl (1.0) vitriol (C 12-C 15E (1.0) M), C 12-C 15The many ethoxylations of alkyl (2.25) vitriol (C 12-C 15E (2.25) M), C 12-C 15The many ethoxylations of alkyl (3.0) vitriol (C 12-C 15E (3.0) M) and C 12-C 15The many ethoxylations of alkyl (4.0) vitriol (C 12-C 15E (4.0) M), wherein M is selected from sodium and potassium usually.
Alkyl sulfate surfactant is formula ROSO 3The water-soluble salt of M or acid, wherein R C preferably 8-C 18Alkyl preferably contains C 10-C 18The alkyl of moieties or hydroxyalkyl, more preferably C 12-C 15Alkyl or hydroxyalkyl, M is H or positively charged ion, for example be alkali metal cation (for example sodium, potassium, lithium) or ammonium or replacement ammonium (methyl-, dimethyl-and trimethylammonium-ammonium cation and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine positively charged ion and by alkylamine, for example ethamine, diethylamine, triethylamine, the quaternary ammonium cation that their mixture obtains etc.).
The coml alkyl alkoxy sulfate contains the mixture of the compound of different extent of alkoxylation.For example, Shell Chemical Company, Horston, C12-15 polyoxyethylene (3) vitriol of Tx contains from 0 ethoxylate to 5 or more, and average degree of ethoxylation is 3 molecule.Degree of ethoxylation is low more in certain sample, and the content of the alkyl-sulphate that then exists in mixture (EO=0) is high more.
In the present invention, the total amount of the alkyl-sulphate that exists in detergent composition not only comprises the alkyl-sulphate that adds in the composition, also comprises any alkyl-sulphate that is present in the alkyl alkoxy sulfate surfactant mixture.
In another embodiment of the present invention, we are surprised to find in liquid washing agent, and the effect relevant with the combination of AQD dispersion agent and it and ethoxylation polymine (PEI) improved when the surfactant system of washing composition contains alkyl ethoxylated sodium sulfate (AES) and no alkyl-sulphate and alkylbenzene sulfonate greatly." nothing " is meant and is lower than 5%, preferably be lower than 1%.
In another embodiment of the present invention, we are surprised to find in non-aqueous liquid detergent, and the effect relevant with the AQD dispersion agent improved when the surfactant system of washing composition contains linear alkylbenzene sulfonate greatly.
Amine-the be used for amine that suitable amine tensio-active agent of the present invention comprises following formula:
R 1-X-(CH 2) n-N (R 3R 4) R wherein 1Be C 6-C 12Alkyl; N is that about 2-is about 4, and X is that the abutment or the X that are selected from NH, CONH, COO or O are non-existent; And R 3And R 4Be selected from H, C respectively 1-C 4Alkyl or (CH 2-CH 2-O (R 5)), R wherein 5Be H or methyl.
These preferred amine comprise as follows:
R 1-(CH 2) 2-NH 2
R 1-O-(CH 2) 3-NH 2
R 1-C(O)-NH-(CH 2) 3-N(CH 3) 2
R 1-N[CH 2-CH (OH)-R 5] 2R wherein 1Be C 6-C 12Alkyl and R 5Be H or CH 3
In preferred embodiment, amine is described by following formula:
R 1-C (O)-NH-(CH 2) 3-N (CH 3) 2R wherein 1Be C 8-C 12Alkyl.
Especially preferred amine comprises and is selected from octylame, hexylamine, decyl amine, amino dodecane, C 8-C 12Two (hydroxyethyl) amine, C 8-C 12Two (hydroxyl sec.-propyl) amine and C 8-C 12Amido propyl-dimethyl amine and their mixture.
The present invention also provides detergent composition, and it provides effectively greasy/oiliness daily dirt washing by the AQD dispersion agent that uses percarbonate bleach and the present invention to describe.Percarbonate is in the suds provides peroxide bleaching agent, is the basic technology of modern super dense granule laundry detergent formulations.Peroxide bleaching agent is very hydrophilic, although it is not as the bleaching effect of peracid (for example being formed by superoxide and TAED reaction), but it is being effectively aspect the decolouring of pigment (for example particle and beverage spot), the color that can also help to remove the organic residue relevant with the health dirt.Unexpectedly, we find that now the composition that contains AQD dispersion agent and percarbonate bleach provides fabulous washing and whitening performance.
The present invention also provides detergent composition, and it provides effectively greasy/oily daily dirt washing by being used in combination hydrophobic bleach and water-soluble AQD dispersion agent of the present invention.The daily dirt washing and the whitening effect of hydrophobic bleach and peracid are proved, and this material can be with limited degree infiltration title complex/greasy oily soil.We find that now the washing composition and the bleaching composition that contain AQD and hydrophobic bleach (comprising preformed peracid) provide fabulous washing and whitening effect.
The present invention also provides detergent composition, and it provides effectively greasy/oil " daily " dirt (with unexpected dirt) washing by using polyethoxylated-polyamine polymer (PPP) and AQD dispersion agent of the present invention.As mentioned above, greasy/oil " daily " dirt (for example at collar, on the pillowcase) is the mixture of triglyceride level, liposome, complicated glycan glycosides, inorganic salt and proteinaceous substances.It is difficult removing these very hydrophobic dirts fully, in residual low levels of residual spot on fabric usually after the washing.For improving performance, various soil dispersion polymkeric substance have been developed at key position.The feature of these materials comprises: (1) suitably low-molecular-weight " hydrophobic " polyamine backbone (it is cationic slightly in nature, and the avidity to dirt and fabric is provided); (2) incidental " hydrophilic " polyethoxylated group, it provides spatial stability and greasy dirt to suspend.In washing process, these polymkeric substance are had an effect on the interface at spot/washing mother liquor.
We are surprised to find, and the detergent composition that contains AQD dispersion agent of the present invention and polyethoxylated polyamine polymer provides fabulous washing and whitening effect than the composition that only contains any independent component.The effect of mixed system is considered to be formed by following result: (1) AQD is at any calcium soap of stained surface work in order to avoid calcium soap to form and to disperse to exist, thus the polymer deposition that helps improving; (2) AQD provides the solublization that is deep to dirt, and polymkeric substance scrapes off the spot component of solubilising as " greasy removal shuttle ", and it is dispersed in the washing mother liquor.
Be used for preferred polyethoxylated polyamine of the present invention normally polyalkenes amine (PAA), polyalkenes imines (PAI), preferably polyethylene amine (PEA), polymine (PEI), or by having PEA or the PEI that the R unit longer than parent PAA, PAI, PEA or PEI connects.Usually polyalkenes amine (PAA) is four butylidenes, five amine.PEA by relating to the reaction of ammonia and ethylene dichloride, obtains with aftercut usually.Usually the PEA that obtains is Sanya second tetramine (TETA) and tetren (TEPA).Surpass five amine, i.e. hexamine, seven amine, eight amine and nine possible amine, the mixture that generally obtains by fractionation by distillation, can not comprise other material, for example cyclammonium, especially piperazine.The cyclammonium that can also have the side chain of being with nitrogen atom.Referring to the US2792372 of the Diclinson that issues May 14 nineteen fifty-seven, it has described the preparation method of PEA.
Preferred amine polymer skeleton is included as C 2The unitary R of alkylidene group (ethylidene) unit also is called polymine (PEI).Preferred PEI contains medium side chain, and promptly the ratio of m and n is less than 4: 1, yet the ratio that most preferably has m and n is 2: 1 PEI.Preferred skeleton has following general formula before modification:
Figure A9718035700201
Wherein the definition of m and n as mentioned above.Preferred PEI has the about 200 daltonian molecular weight of surpassing before modification.
In polyamine backbone, especially under the situation of PEI, primary, the second month in a season and the unitary relative proportion of tertiary amine will change according to the preparation method.Be connected that each hydrogen atom on each nitrogen-atoms of polyamine backbone chain is represented to be used for to replace subsequently, the potential site of quaternized or oxidation.
These polyamine can be for example by at catalyzer, carbonic acid gas for example, polymerising ethylene imines preparation under the existence of sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetate etc.The concrete grammar for preparing these polyamine backbone is all classified this paper reference as at the US2553696 of the Wilson of the US2806839 of the Crowther of the US2208095 of US3033746, the Esselmann of promulgation on July 16th, 1940 etc. of US2182306, the Mayle of promulgation on May 8th, 1962 etc. of the Ulrich of promulgation on December 5 nineteen thirty-nine etc., promulgation on September 17 nineteen fifty-seven and promulgation on May 21 nineteen fifty-one.
The example that contains the cotton stain remover polymkeric substance of modification of the present invention of PEI illustrates with formula I-IV:
Formula I has narrated the cotton stain remover polymkeric substance that contains the PEI skeleton, and wherein all commutable nitrogen are by using polyoxy alkylidene oxygen unit ,-(CH 2CH 2O) 7H replaces the hydrogen modification, and it has following formula: this is all with the example of one type group modified cotton stain remover polymkeric substance.
Figure A9718035700211
Formula I
Formula II has narrated the cotton stain remover polymkeric substance that contains the PEI skeleton, and wherein all commutable primary amine nitrogen are by using polyoxy alkylidene oxygen unit ,-(CH 2CH 2O) 7H replaces the hydrogen modification, and by all oxidable primary and secondary nitrogen are oxidized to the N-oxide modifying, described cotton stain remover polymkeric substance has following formula to molecule subsequently:
Figure A9718035700212
Formula II
Formula III has been narrated the cotton stain remover polymkeric substance that contains the PEI skeleton, and wherein all skeleton hydrogen are substituted, and some skeleton amine unit is by quaternized.Substituting group is polyoxy alkylidene oxygen unit ,-(CH 2CH 2O) 7H or methyl.The cotton stain remover polymkeric substance of the PEI of modification has following formula:
Figure A9718035700221
Formula III
Formula IV has narrated the cotton stain remover polymkeric substance that contains the PEI skeleton, wherein skeleton nitrogen by replace (promptly-(CH 2CH 2O) 7H or methyl), quaternized, be oxidized to N-oxide compound or their combination modification, the cotton stain remover polymkeric substance that obtains has following formula:
Figure A9718035700222
Formula IV
In as above example, the nitrogen of not all unit classification contains identical modification.The present invention allows the makers-up to make the ethoxylation of a part of secondary amine nitrogen, and other secondary amine nitrogen is oxidized to the N-oxide compound.This also is applicable to primary amine nitrogen, at this moment, the makers-up can be chosen in oxidation or quaternized before with one or more substituting group modifications all or a part of primary amine nitrogen.Any possible combination of E group can be replaced in primary and secondary amine nitrogen, except above-mentioned restriction.
The present invention adopts the AQD dispersion agent of " significant quantity " to contain the performance of the cleaning composition of other auxiliary component with improvement." significant quantity " of AQD dispersion agent and auxiliary component is meant directionally or is enough to improve cleaning composition significantly to the quantity of the washing usefulness of some target dirt and spot at least with 90% confidence level among the present invention.Therefore, comprise the composition of some food stains for target, the makers-up will use enough AQD at least directionally to improve the scourability to this dirt.Equally, comprise the composition of clay soil for target, the makers-up will use enough AQD at least directionally to improve the scourability to this dirt.Importantly, in the detergent for washing clothes of full preparation, as the data that hereinafter provide as can be seen, the AQD dispersion agent can provide at least at the content that the orientation of the scourability of various dirts and spot is improved and use.
As mentioned above, the AQD dispersion agent is used in combination at the content that the orientation aspect the scourability is improved with effective acquisition at least with detergent surfactant in detergent composition.Aspect fabric cleaning composition, the type and the severity of dirt and spot not only depended in the change of being somebody's turn to do " use content ", also depends on the temperature of washing water, the volume of washing water and the type of washing machine.
As seen from the above, be used to the to machine-wash number change of AQD dispersion agent of clothes aspect can be depending on user's custom and puts into practice, washs type of machine etc.Yet in this respect, an advantage that does not obtain appreciating of AQD dispersion agent is that they can provide at least the orientation of various dirts and spot usefulness aspect is improved.
Various other cleaning composition also can use the AQD dispersion agent of significant quantity to prepare by mode of the present invention.This composition comprises, but is not restricted to manual dishwashing product (especially liquid and gel), hard surface cleaner, shampoo, human body cleaning block, laundry piece etc.Because the user's of said composition custom and practice show little difference, it is about 5% to contain about by weight 0.25%-in said composition, and the AQD dispersion agent of preferably about 0.45%-about 2% is gratifying.
The non-limitative example of detergent surfactant-be used for anion surfactant of the present invention with the content that is generally about 1%-about 55% by weight comprises uncle position, side chain and random C 10-C 20Alkyl-sulphate (" AS "), structural formula are CH 3(CH 2) x(CHOSO 3 -M +) CH 3And CH 3(CH 2) y(CHOSO 3 -M +) CH 2CH 3C 10-C 18Secondary (2,3) alkyl-sulphate, x and (y+1) be wherein at least about 7, preferably at least about 9 integer, and M is water miscible positively charged ion, especially sodium, unsaturated vitriol such as oleyl sulfate, C 10-C 18α-sulfonated fatty acid ester, C 10-C 18Sulfation alkyl poly glucoside, C 10-C 18Alkyl alkoxy sulfate (" AE xS "; And C EO1-7 ethoxy sulfate particularly), 10-C 18Alkyl alkoxy carboxylate salt (particularly EO1-5 ethoxy carboxylate).C 12-C 18Trimethyl-glycine and sultaine (" sultaines "), C 10-C 18Amine oxide and analogue also can be included in the total composition.Also can use conventional C 10-C 20Soap.High if desired foam can use side chain C 10-C 16Soap.The useful tensio-active agent of other routine is listed in the standard article.
Composition of the present invention does not preferably have C basically 11-C 18Alkylbenzene sulfonate (" LAS ".)
The limiting examples of nonionogenic tenside-be used for nonionogenic tenside of the present invention with the content of about 1%-about 55% by weight comprises alcohol alcoxylates (AE) and alkylphenol, polyhydroxy fatty acid amide (PFAA), alkyl poly glucoside (APG), C 10-C 18Glyceryl ether etc.
More particularly, the condensation product of the oxyethane (AE) that primary and secondary fatty alcohol and about 1-are about 25 moles is suitable as nonionogenic tenside of the present invention.The alkyl chain of fatty alcohol can be a straight or branched, and uncle or secondary contains about 22 carbon atoms of the 8-that has an appointment usually.Preferably have and contain about 20 carbon atoms of about 8-, it is about 10 more preferably to contain the alcohol of alkyl of about 18 carbon atoms of about 10-and the about 1-of every mol of alcohol, preferred 2-7, the most preferably condensation product of 2-5 moles of ethylene oxide.The example of commercial available such nonionogenic tenside comprises Tergitol TM15-S-9 (C 11-C 15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Tergitol TM24-L-6NMW (C with narrow molecular weight distributions 12-C 14The condensation product of primary alconol and 6 moles of ethylene oxide), sell by Union Carbide Corp; Neodol TM45-9 (C 14-C 15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Neodol TM23-3 (C 12-C 13The condensation product of straight chain alcohol and 3 moles of ethylene oxide), Neodol TM45-7 (C 14-C 15The condensation product of straight chain alcohol and 7 moles of ethylene oxide), Neodol TM45-5 (C 14-C 15The condensation product of straight chain alcohol and 5 moles of ethylene oxide), by the sale of shell chemical company, Kyro TMEOB (C 13-C 15The condensation product of alcohol and 9 moles of ethylene oxide), by P ﹠amp; G sells; With Genapol LA 030 or 050 (C 12-C 14The condensation product of alcohol and 3 or 5 moles of ethylene oxide), sell by Hoechst.The preferred HLB scope of these AE nonionogenic tensides is 8-11, most preferably 8-10.Also can use with the condenses of propylene oxide and butylene oxide ring.
Another kind of nonionogenic tenside preferred for the present invention is the polyhydroxy fatty acid amide surfactant of following formula:
R 2-C (O)-N (R 1)-Z is R wherein 1Be H, or R 1Be C 1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R 2Be C 5-31Alkyl and Z have at least 3 these polyhydroxy alkyls with the direct-connected hydroxyl of diameter chain, or their alkoxy derivative.Preferred R 1Be methyl, R 2It is straight chain C 11-15Alkyl or C 15-17Alkyl or alkenyl, for example Oleum Cocois alkyl or their mixture and Z are by reducing sugar, for example glucose, fructose, maltose, lactose obtain in reduction amination.Representative instance comprises C 12-C 18And C 12-C 14The N-methyl glucose amide referring to US5194639 and 5298636, also can use N-alkoxyl group polyhydroxy fatty acid amide, referring to US5489393.
The nonionogenic tenside that also can be used as surfactant system of the present invention is a disclosed alkyl polysaccharide in the US4565647 of the Llenado of promulgation on January 21st, 1986, it contains about 30 carbon atoms of the 6-that has an appointment, hydrophobic grouping and a polysaccharide of preferred about 16 carbon atoms of about 10-, for example the polysaccharide glycosides promptly contains the 1.3-that has an appointment about 10, preferred about 1.3-is about 3, most preferably from about the hydrophilic radical of about 2.7 sugar units of 1.3-.Can use any recuding sugars that contains 5 or 6 carbon atoms, glucose for example, semi-lactosi and galactosyl can be used for substituting glucosyl (hydrophobic group optionally is connected positions such as 2-, 3-, 4-, thereby obtains glucose or semi-lactosi with respect to glucoside or galactoside).In sugared key can be between 2-, 3-, 4-and/or the 6-position of position of the sugar unit that for example adds and previous sugar unit.
Preferred APG has following formula:
R 2O (C nH 2nO) t(glycosyl) xR wherein 2Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and their mixture, wherein to contain the 10-that has an appointment about 18 for alkyl, about 14 carbon atoms of preferably about 12-; N is 2 or 3, preferred 2; T is that 0-is about 10, and is preferred 0, and x is that about 1.3-is about 10, and preferably about 1.3-is about 3, and most preferably from about 1.3-about 2.7.Glycosyl is preferably obtained by glucose.For preparing these compounds, at first form the many ethoxy alcohols of alcohol or alkyl, form glucoside (being connected the 1-position) with glucose or source of glucose reaction subsequently.Other glycosyl can be connected between its 1-position and previous sugar unit 2-, 3-, 4-and/or the 6-position, preferably mainly in the 2-position subsequently.
The polyoxyethylene of alkylphenol, polyoxypropylene and polyoxy croton condensation thing are suitable as the nonionogenic tenside of surfactant system of the present invention, wherein preferred polyoxyethylene condenses.These compounds comprise having and contain about 14 carbon atoms of about 6-, the alkylphenol of the alkyl of the straight or branched configuration of about 14 carbon atoms of preferably about 8-and the condensation product of alkylene oxide.In preferred embodiments, oxyethane equals about 25 moles of about 2-with every mole of alkylphenol, and more preferably from about the amount of about 15 moles of ethylene oxide of 3-exists.Commercial available such ionic surfactant pack is drawn together the Igepal that is sold by GAF company TMCO-630 is by Rohm ﹠amp; The Triton that Haas company sells TMX-45, X-114, X-100 and X-102.These tensio-active agents are commonly referred to alkylphenol alcoxylates (for example alkyl phenol ethoxylate).
Oxyethane also is suitable as additional nonionogenic tenside of the present invention with the condensation product of the hydrophobic grouping that forms by condensed epoxy propane and propylene glycol.The hydrophobic grouping of these compounds preferably has about 1500 to about 1800 molecular weight, and shows the water insoluble.Adding polyoxyethylene group in this hydrophobic grouping will increase the water-soluble of branch subpopulation, and it is the about 50% of condensation product gross weight that the fluid characteristics of product is retained to polyoxyethylene content, and this is equivalent to condensation up to about 40 moles oxyethane.Such examples for compounds comprises some commercially available Pluronic TMTensio-active agent is sold by BASF.
The nonionogenic tenside that is suitable as nonionic surfactant system of the present invention equally is an oxyethane and the condensation product of the product that obtains by propylene oxide and reacting ethylenediamine.The hydrophobic grouping of these products is made up of the reaction product of quadrol and excessive propylene oxide, 2500 to about 3000 the molecular weight of having an appointment usually.This hydrophobic grouping and ethylene oxide condensation are to making condensation product contain the polyoxyethylene of about by weight 40%-about 80% and having the degree of the molecular weight of about 5000-about 11000.The example of such tensio-active agent comprises some commercially available Tetronic TMCompound is sold by BASF.
Following explanation can be used for other auxiliary component of composition of the present invention, but is not in order to limit.Use routine techniques that the final product of forms such as liquid, gel, piece can be provided when AQD combines with these auxiliary composition components, the preparation granular laundry detergent needs some material processing technology to obtain optimum performance.Therefore, makers-up for convenience, the preparation of laundry particulate is described granules preparation part hereinafter individually.
Washing assistant-detergent builders optionally but be preferably included in the composition of the present invention, to help to control the mineral in the washing water, especially calcium and/or magnesium hardness or to help to remove particulate fouling from the surface.Washing assistant can be operated by all means, comprise form water-soluble with hardness ions or the water-insoluble title complex, by ion-exchange with by the surface that more helps depositing hardness ions than the surface of being washed is provided.The consumption of washing assistant can be made wide variation according to the end-use and the physical form of composition.The washing composition that adds washing assistant generally comprises the washing assistant at least about 1%.It is about 50% that liquid formulations generally contains about by weight 5%-, more generally is the washing assistant of 5%-35%.Granular recipe generally contains by the about 10%-of composition weight meter about 80%, more generally is the washing assistant of 15%-50%.Yet this does not also mean that the washing assistant of the lower or high level of eliminating.For example some detergent additives or high level of surfactant prescription do not help and to wash.
Be applicable to that washing assistant of the present invention can be selected from phosphoric acid salt and polyphosphate, especially sodium salt; Silicate comprises water-soluble and hydration solid type, comprises chain, stratiform or three-dimensional structure and amorphous solid or non-structured liquids type; Carbonate, supercarbonate, sesquicarbonate and the carbonate minerals except that yellow soda ash or concentrated crystal soda; Silico-aluminate; Organic single, two, three and the water-soluble nonsurfactant carboxylate salt of tetracarboxylic acid hydrochlorate, especially acid, sodium, potassium or alkanol ammonium salts form; And oligomerisation or water-soluble low molecular weight polymeric carboxylates, comprise aliphatic series and aromatic series type; And phytinic acid.These can pass through borate, for example are used for borate or vitriol, the especially sodium sulfate of pH buffering purposes and any other filler or carrier and replenish, and they are favourable to surface of stability promoting agent and/or the engineering that contains the detergent composition of washing assistant.
Can use the washing assistant mixture, be sometimes referred to as " builder system ", they contain two or more conventional washing assistants usually, optionally replenish with sequestrant, pH buffer reagent or filler, although some materials of back are normally mentioned separately when describing the quality of material.About the relative mass of tensio-active agent in washing composition of the present invention and washing assistant, preferred builder system is about 60 with the weight ratio of tensio-active agent and washing assistant usually: 1-preparation in about 1: 80.Some preferred detergent for washing clothes has 0.90: 1.0-4.0: 1.0, more preferably 0.95: 1.0-3.0: 1.0 described ratio.
When law allowed, usually preferred phosphorus-containing detergent washing assistant included, but not limited to basic metal, ammonium and the alkanol ammonium salts of polyphosphate (tri-polyphosphate, pyrophosphate salt and vitreous state polymer metaphosphate are specifically arranged) and phosphonate.
Suitable silicate-like builder comprises alkalimetal silicate, particularly those SiO 2: Na 2The O ratio is 1.6: 1-3.2: liquid in 1 scope and solid silicate, comprise, be particularly useful for automatic tableware washing purposes, by PQ Corp with trade name BRITESIL , the metaborate monohydrate 2-ratio silicate sold of BRITESIL H2O for example; And layered silicate, as the material of in the US4664839 of the H.P.Rieck of on May 12nd, 1987 promulgation, describing.NaSKS-6 is abbreviated as " SKS-6 " sometimes, is the crystalline layered no aluminium δ-Na that is sold by Hoechst 2SiO 5Form silicate especially is preferred for the granular laundry composition.Referring to the preparation method who describes among DE-A-3417649 and the DE-A-3742043.Also can or use other this class layered silicate in addition, as have general formula NaMSi xO 2x+1.yH 2The silicate of O, wherein M is sodium or hydrogen, x is the number between the 1.9-4, is preferably 2, and y is the number between the 0-20, is preferably 0.The layered silicate that is obtained by Hoechst also comprises NaSKS-5, NaSKS-7 and the NaSKS-11 that is respectively α, β and γ layered silicate form.Also can use other silicate, Magnesium Silicate q-agent for example, it can be used as crisp dose in the particulate state prescription, as the stablizer of SYNTHETIC OPTICAL WHITNER, and as the component in the foam control system.
Being equally applicable to of the present invention is the component with hydrate forms of being represented by following general formula of describing among the synthetic crystallization ion exchange material of chain-like structure or its hydrate and the US5427711 as the Sakaguchi of promulgation on June 27 nineteen ninety-five etc.: xM 2O.ySiO 2.zM ' O, wherein M is sodium and/or potassium, M ' is calcium and/or magnesium; Y/x is that 0.5-2.0 and z/x are 0.005-1.0.
Suitable carbonate builders comprises alkaline-earth metal and alkali-metal carbonate, this describes in the German patent application № 2321001 that is disclosed on November 15th, 1973, though also can use sodium bicarbonate, yellow soda ash, concentrated crystal soda and other carbonate material, for example urao or any conventional yellow soda ash and lime carbonate double salt for example have formula 2Na when anhydrous 2CO 3.CaCO 3Composition and even lime carbonate, comprise calcite, aragonite and vaterite, especially have the form of high surface area with respect to fine and close calcite, they can be for example as crystal seed or be used for the synthetic detergent piece.
The silico-aluminate washing assistant is particularly useful for granulated detergent, but also can add liquid, in paste or the gel.Be applicable to that of the present invention is those materials of the formula of seeing service: [M z(AlO 2) z. (SiO 2) v] .xH 2O, wherein z and v are at least 6 integer, and the mol ratio of z and v is in the 1.0-0.5 scope, and x is the integer of 15-264.Silico-aluminate can be a crystalline or unformed, and can be primary silico-aluminate or synthetic.The US3985669 of the Krummel of promulgation on October 12nd, 1976 etc. has described a kind of method of producing silico-aluminate.Being used for the so-called Zeolite MAP that preferred synthetic crystallization silico-aluminate ion exchange material of the present invention can be used as Zeolite A, Zeolite P (B), Zeolite X and be different from Zeolite P to a certain extent obtains.Can use natural type, comprise clinoptilolite.ZeoliteA has following formula: Na 12[(AlO 2) 12(SiO 2) 12] .xH 2O, wherein x is 20-30, particularly 27.Can also use dehydration zeolite (x=0-10), silico-aluminate preferably has the particle size that diameter is the 0.1-10 micron.
Suitable organic detergent washing assistant comprises multi-carboxylate's compound, comprises the dicarboxylate and the tricarboxylate of water-soluble nonsurfactant.More common washing assistant multi-carboxylate has many carboxylate groups, is preferably at least 3 carboxylate groups.The carboxylate salt washing assistant is generally with acid form, and part neutralization, neutralization or excessive alkaline form are prepared.When using with the form of salt, basic metal, as the salt of sodium, potassium and lithium, or the alkanol ammonium salt is preferred.The multi-carboxy acid salt washing agent comprises the ether carboxylate washing assistant, and oxygen di-succinate for example is referring to the US3635830 of the US3128287 of the Berg of promulgation on April 7th, 1964 and the Lamberti of promulgation on January 18th, 1972 etc.; " TMS/TDS " washing assistant among the US4663071 of the Bush of promulgation on May 5th, 1987 etc.; With other ether carboxylate, comprise ring-type and alicyclic compound, as those compounds described at US3923679,3835163,4158635,4120874 and 4102903.
Other suitable detergent builders comprises ether hydroxypolycarboxylic acid salt, the multipolymer of maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid; The carboxymethyl oxysuccinic acid; Various basic metal, ammonium and the substituted ammonium salt of polyacetic acid such as ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA); And mellitic acid, succsinic acid, More Malay acid, benzene 1,3,5-tricarboxylic acid, carboxymethyl oxysuccinic acid, and water-soluble salt.
Because the Citrate trianion washing assistant is obtained and biodegradable by renewable resources as citric acid and water-soluble salt thereof, for the efficient liquid detergent formulation, they are multi-carboxy acid salt washing agents of particularly important.Citrate trianion also can be used in the particulate composition, particularly mixes use with zeolite and/or layered silicate washing assistant.Oxygen di-succinate also is useful especially in this composition and mixture.
When allowing, especially, can use alkali metal phosphate, for example tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate being used for the piece prescription of hand clothes washing operation.Also can use the phosphonate washing assistant, ethane-1-hydroxyl-1 for example, 1-diphosphonate and other known phosphonate, the material described in the US3159581,3213030,3422021,3400148 and 3422137 for example, they will have required antiscale character.
Some detergent surfactant or its short chain analogue also have the washing assistant effect.Be clearly prescription metering, when they had Action of Surfactant, these materials were summarised as detergent surfactant.The preferred washing assistant of this class comprises: disclosed 3 in the US4566984 of the Bush of on January 28th, 1986 promulgation, and 3-dicarboxyl-4-oxa--1,6-adipic acid ester and related compound.The succsinic acid washing assistant also comprises C 5-C 20Alkyl and alkenyl succinic and salt thereof.The succinate washing assistant also comprises: lauryl succsinic acid, tetradecyl succsinic acid, hexadecyl succsinic acid, 2-dodecenyl succinic succsinic acid (preferably), 2-15 carbene base succsinic acids etc.The lauryl succsinic acid was described in the disclosed european patent application 86200690.5/0200263 on November 5th, 1986.Lipid acid, for example C 12-C 18Monocarboxylic acid also can add in the composition so that additional washing assistant activity to be provided as tensio-active agent/builder material individually or with above-mentioned washing assistant, especially Citrate trianion and/or succinate washing assistant together.Describe among the US3308067 of the Diehl of the US4144226 of the Crutchfield that other suitable multi-carboxylate issued on March 13rd, 1979 etc. and promulgation on March 7th, 1967.In addition referring to the US3723322 of Diehl.
The inorganic builders material of operable other type has following general formula: (M x) iCa y(CO 3) z, wherein x and i are the integers of 1-15, and y is the integer of 1-10, and z is the integer of 2-25, M iBe positively charged ion, at least a is water-soluble cationic, satisfies the equation ∑ i=1-15 (x iMultiply by M iValence mumber)+2y=2z, make general formula have the electric charge of neutrality or " balance ".These washing assistants are called " mineral washing assistant " in the present invention.The water of hydration or other negatively charged ion except that carbonate can add, as long as total charge balance or neutralization.This anionic electric charge or valency effect should add the right side of aforesaid equation.The preferred water-soluble cationic that is selected from hydrogen, water-soluble metal, boron, ammonium, silicon or their mixture that exists more preferably is selected from sodium, potassium, hydrogen, lithium, ammonium and their mixture, very preferred sodium and potassium.The anionic non-limiting instance of noncarbonate comprises the negatively charged ion that is selected from muriate, sulfate radical, fluorochemical, oxygen, hydroxide radical, silicon-dioxide, chromate, nitrate radical, borate and their mixture.The simple form of such preferred washing assistant is selected from Na 2Ca (CO 3) 2, K 2Ca (CO 3) 2, Na 2Ca 2(CO 3) 3, NaKCa (CO 3) 2, NaKCa 2(CO 3) 3, K 2Ca 2(CO 3) 3With their mixture.Especially preferred material as washing assistant of the present invention is any crystalline modified Na 2Ca (CO 3) 2The following suitable washing assistant that further specifies above-mentioned define styles, it comprises any natural or synthesized form or their mixture: the Afghanite of following material, Ander sonite, AshcroftineY, Beyerite, Borcarite, Burbankite, Butschliite, Cancrinite, Carbocernaite, Carletonite, Davyne, DonnayiteY, Fairchi ldite, Ferrisurite, Franzinite, Gaudefroyite, Gaylussite, Girvasite, Gregoryite, Jouravskite, KamphaugiteY, Kettnerite, Khanneshite, Leper sonniteGd, Liottite, MckelveyiteY, Microsommite, Mroseite, Natrofairchildite, Nyerereite, RemonditeCe, Sacrofanite, Scdrockingerite, Shor tite, Surite, Tunisite, Tuscanite, Tyrolite, Vishnevite and Zemkorite.Preferred mineral forms comprises Nyererite, Fairchildite and Shortite.
Enzyme-can comprise various enzymes in the present composition, it has various uses, comprises, carbohydrate-based protein-based from removing as the dirt-carrying body or triglycerin ester group dirt, shifts in the fabric washing process in order to prevent dyestuff, and is used for the fabric reformation.Suitable enzyme comprises proteolytic enzyme, amylase, lipase, cellulase, peroxidase and mixed enzyme thereof, and they have suitable source, as vegetables, animal, bacterium, fungi and yeast.Preferred selection to them is subjected to factor, as the active and/or stable optimum regime of pH-, thermostability with to the influence of the stability of activated detergent, washing assistant etc.In this respect, bacterium or fungal enzyme are preferred, as bacillary amylase and proteolytic enzyme and fungoid cellulase.
" detersive enzyme " used herein is meant any enzyme that has washing, decontamination or other beneficial effect in laundry, hard surface cleaning and Personal hygiene detergent composition.Preferred detersive enzyme is lytic enzyme such as proteolytic enzyme, amylase and lipase.The preferred enzyme of purpose of being used to do washing is, but is not limited to proteolytic enzyme, cellulase, lipase and peroxidase.What more preferably be used for the automatic tableware washing is amylase and/or proteolytic enzyme, comprise current commercially available kind and improved kind, for improved kind, although be suitable for more and more being fit to SYNTHETIC OPTICAL WHITNER, although constantly improve, it still has certain bleaching deactivation personality sensitivity.
Enzyme adds in the detergent composition with the content that is enough to formation " effectively flushing dose " usually.Term " effectively flushing dose " is meant can produce cleaning, decontamination, de-sludging on dirt-carrying body such as fabric, tableware etc., brighten, deodorizing or improve any amount of freshness effect.Concerning the commercially available preparation of reality, the typical amounts (by weight) of organized enzyme in every gram detergent composition is up to about 5mg, and more typical is 0.01mg-3mg.In addition, this composition comprises 0.001%-5% by weight usually, is preferably the commercially available zymin of 0.01%-1%.The quantity of proteolytic enzyme in this commercially available zymin generally should be enough to make every gram composition to produce the activity of 0.005-0.1Anson unit (AU).For some washing composition, for example in the automatic tableware washing, can need to increase the organized enzyme content of commercial formulation, with the total amount of minimizing on-catalytic active substance, thereby improve into spot/film forming or other net result.Greater activity content is desirable equally in highly spissated detergent formulation.
The suitable example of proteolytic enzyme is the subtilysin that derives from the special Pseudomonas of Bacillus subtilus and lichens shape bacillus.A kind of suitable proteolytic enzyme gets the Novo Industries A/S exploitation of free Denmark, and the Bacillaceae of selling with ESPERASE , and hereinafter referred to as " Novo ", it has maximum activity in the whole pH scope of 8-12.The preparation of this kind of enzyme and similar enzyme has description in the English Patent 1243784 of Novo.Other suitable proteolytic enzyme comprises ALCALASE  and the SAVINASE  that derives from Novo and derives from Dutch International Bio-Synthetic, the MAXATASE  of Inc; And on January 9th, 1985 protease A described among the disclosed EP130756A and on April 28th, 1987 disclosed EP303761A and the proteolytic enzyme B that described among the disclosed EP130756A on January 9th, 1985.Also can be referring to the high pH proteolytic enzyme that derives from bacillus NCIMB40338 described in the WO9318140A of Novo.The enzyme-containing detergent that comprises proteolytic enzyme, one or more other enzymes and a kind of reversible protease inhibitors has been described among the WO9203529A of Novo.Other preferred proteolytic enzyme comprises Procter ﹠amp; Enzyme among the WO9510591A of Gamble.If desired, can obtain having the absorptivity of reduction and the water-disintegrable proteolytic enzyme of increase, as Procter ﹠amp; The WO9507791 of Gamble is described.A kind of suitable proteolytic enzyme that is used for the recombinant chou trypsinase shape of this washing composition has been described among the WO9425583 of Novo.
More particularly, the especially preferred proteolytic enzyme that is called " Protease D " is the carbonylic hydrolase mutation with undiscovered aminoacid sequence in natural, it by by be equivalent in above-mentioned carbonylic hydrolase with different aminoacid replacement+amino-acid residue of 76 positions obtains by the precursor carbonylic hydrolase, it preferably as the US series number of on October 13rd, 1994 application be 08/322676 name to be called the A.Baeck of " cleaning composition that contains proteolytic enzyme " and US series number be that 08/322677 name is called described in the patent application of the C.Ghosh of " bleaching composition that contains proteolytic enzyme " etc., the numbering of bacillus subtilisin is equivalent to be selected from separate with fixed attention according to starch+99, + 101, + 103, + 104, + 107, + 123, + 27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, + 204, + 206, + 210, + 216, + 217, + 218, + 222, + 260, + 265 and/or+274 one or more amino-acid residue combinations.
The used cellulase of the present invention comprises bacterium and fungi type, preferably has the optimal ph of 5-9.5.Barbesgoard etc. have disclosed at the US4435307 on March 6th, 1984 and have derived from the insolens corruption and plant and belong to or rottenly plant the suitable fungal cellulase that the cellulase 212-that belongs to DSM1800 or belong to Aeromonas generates fungi, and the cellulase that extracts from the liver pancreas of shipworm Dolabella AuriculaSolander.GB-A-2075028, GB-A-2095275 and DE-OS-2247832 have also disclosed suitable cellulase.CAREZYME  and CELLUZYME  (Novo) are useful especially.Also referring to the WO9117243 of Novo.
Peroxidase can be used in combination with oxygen source such as percarbonate, perborate, hydrogen peroxide etc., is used for " solution bleaching ", or in washing process, prevents to transfer on other dirt-carrying body that is present in the washing lotion from dyestuff or pigment that the dirt-carrying body spins off.Known peroxidase comprises horseradish peroxidase, lignoenzyme, haloperoxidase such as chloro-or bromine peroxide enzyme.The detergent composition that contains peroxidase October in 1989 disclosed Novo on the 19th WO89099813A and the WO8909813A of Novo in describe.
The WO9307263A of Genencor International and WO9307260A, the US3553139 of the McCarty of the WO8908694A of Novo and promulgation on January 5th, 1971 etc. has also disclosed the scope of proenzyme material and the method in their adding synthetic detergent compositions.The US4507219 of the US4101457 of the Place of promulgation on July 18th, 1978 etc. and the Hughes of promulgation on March 26th, 1985 further discloses enzyme.The US4261868 of the Hora of on April 14th, 1981 promulgation etc. has disclosed the proenzyme material that is used for the liquid scrubbing prescription and they and has added method in this prescription.The enzyme that is used for washing composition can in all sorts of ways and be stablized.The US3600319 of the Gedge of on August 17th, 1971 promulgation etc. and October in 1986 Venegas on the 29th EP200586 the enzyme stabilization technique is disclosed and enumerates.The enzyme stabilising system is also for example in US3519570.The WO9401532A of Novo has described the bacillus sp.AC13 that can access proteolytic enzyme, zytase and cellulase.
Enzyme stabilising system-the present invention contains enzyme composition, and optionally to contain about by weight 0.001%-about 10%, preferred about 0.005% pact-8%, most preferably from about the enzyme stabilising system of 0.01%-about 6%.The enzyme stabilising system can be any stabilising system compatible with detersive enzyme.This system itself can be provided by other prescription active constituent, or for example adds separately by the makers-up or by producers.This stabilising system can, for example comprise calcium ion, boric acid, propylene glycol, short chain carboxy acid, boric acid and composition thereof, and according to the type of detergent composition and physical form with solving stable problem of different nature.
Producing stable a kind of approach is to use to provide water miscible calcium of its ionic and/or magnesium ion source to enzyme in final composition.Calcium ion is more effective than magnesium ion usually, and therefore, if only use a kind of cationic words, then it is preferred.Typical detergent composition, liquid particularly, it is about 30 to contain the 1-that has an appointment at every liter of final detergent composition, preferably about 2-about 20, the calcium ion of about 12 mmoles of 8-more preferably from about is although the factor of enzyme-added kind, type and content might change according to comprising.Preferred water miscible calcium or the magnesium salts of using comprises for example calcium chloride, calcium hydroxide, calcium formiate, calcium malate, calcium maleate, calcium hydroxide and lime acetate; More in general, can use the corresponding magnesium salts of calcium sulfate or listed calcium salt.Certainly the content that further improves calcium and/or magnesium may be useful, for example improves the delipidation of some kind tensio-active agent.
Produce stable another kind of approach and be to use the borate family material, referring to the US4537706 of Severson.Borate stablizer content in use can up to composition 10% or more, but the content that generally is suitable for the boric acid of liquid washing agent or other borate compound such as borax or ortho-borate is for up to about 3 weight %.Can use the boric acid of replacement, as phenyl-boron dihydroxide, fourth boric acid, right-bromophenyl boric acid etc. substituting boric acid, although and used this replacement boron derivative, total the boron content that reduces in the detergent composition is still possible.
Some detergent composition, for example the stabilising system of automatic dishwashing detergent composition can further contain 0-about 10% by weight, the chlorine bleaching scavenging agent of preferred about 0.01%-about 6%, its adding can prevent to be present in the chlorine bleaching class material attack enzyme in many water sources and reduce its activity, especially under alkaline condition.Although the cl content in the water can be seldom, generally at about 0.5ppm-1.75ppm, for example in the washing process of tableware or fabric, the chlorine that can contact with enzyme in all water can be considerable; Therefore, in the occasion of using chlorine, the stability of enzyme is in-problem sometimes.Owing to can be present in some this composition with perborate or the percarbonate that the chlorine bleaching material reacts, its quantity is separated metering with stabilising system, in general, use other chlorine stablizer possibility dispensable, although their use may increase effect.Suitable chlorine scavenger negatively charged ion be as you know and be easy to obtain, and if you are using, can be the sulphite that contains ammonium cation, hydrosulphite, thiosulfite, thiosulphate, iodide etc.Can use antioxidant in addition, as carbamate, xitix etc., organic amine is as ethylenediamine tetraacetic acid (EDTA) (EDTA) or its an alkali metal salt, monoethanolamine (MEA) and composition thereof.In addition, can add special enzyme inhibition system, so different enzymes have maximum consistency.If desired, can use other conventional scavenging agent such as hydrosulfate, nitrate, muriate, hydrogen peroxide cource is as four water sodium perborate, monohydrate sodium stannate and SPC-D, and phosphoric acid salt, condensed phosphate, acetate, benzoate, Citrate trianion, formate, lactic acid salt, malate, tartrate, salicylate etc., and composition thereof.In general, owing to be considered to the function that composition (as hydrogen peroxide cource) that function better lists separately can be brought into play chlorine scavenger, needn't require to add different chlorine scavenger, unless performing to the compound of required degree, the sort of function is not present in of the present invention containing in the enzyme embodiment, even scavenging agent also only adds for best effect like that.Also have, the makers-up can use the general technology as chemist, in the hope of avoiding using inconsistent basically any enzyme trapping agent or stablizer when allocating with other activeconstituents (if you are using).For the use of ammonium salt, this salt can be simply and detergent composition carry out premix, but it is easy to suction and/or discharges ammonia in storage process.Therefore, if present, preferably this raw material is protected among the particle, as the US4652392 of Baginski etc. is described.
Polymerization stain remover-known polymerization stain remover, hereinafter referred to as " SRA " optionally is used for detergent composition of the present invention.If use, SRA is generally the 0.01%-10.0% that accounts for composition by weight, is generally 0.1%-5%, preferred 0.2%-3.0%.
SRA preferably contains hydrophilic segment makes hydrophobic fiber, as the surface hydrophilic of polyester and nylon; SRA contain also that hydrophobic part is deposited on the surface of hydrophobic fiber and in whole washing, rinse cycle all the time attached to fiber surface on, therefore hydrophilic segment is played fixed action.This feasible spot easier cleaning in washing process thereafter that after SRA handles, produces.
SRA can comprise various charged, for example negatively charged ion or even cationic substance (referring to US4956447) and uncharged monomeric unit, their structure can be straight chain, side chain or star.They can comprise capping group, and it is being especially effective aspect control molecular weight or change physics or the surface-active property.For being applied to different fibers or weaving type and different washing composition or detergent additives products, can change structure and charge distribution.
Preferred SRA comprises the oligomerisation terephthalate, by at least a esterification transfer/oligomerisation process preparation, uses metal catalyst usually, for example titanium alkoxide (IV) usually.This ester can use and can prepare and do not form closely crosslinked integrally-built additional monomer by one, two, three, four or a plurality of position adding ester structure.
Suitable SRA comprises the sulfonated products of the ester oligomer of straight chain basically; it is made up of with the allyl group deutero-sulfonation end group that is covalently attached to skeleton terephthaloyl and the multiple unitary oligomer ester skeleton of oxyalkylene oxygen basic weight, for example referring to the J.J.Scheibel of promulgation on November 6 nineteen ninety and the US4968451 of E.P.Gosselink.This ester can prepare by the following method: (a) ethoxylation allyl alcohol; (b) make product and dimethyl terephthalate (DMT) (" DMT ") and 1 of (a), 2-propylene glycol (" PG ") reacts in two-stage esterification transfer/oligomerisation process; The product and the sodium metabisulfite of (b) are reacted in water; The nonionic end capped 1 of the US4711730 of the Gosselink of promulgation on December 8th, 1987 etc., 2-propylene glycol/polyoxyethylene terephthalate polyester, it is by the esterification transfer/oligomerization preparation of for example poly-(ethylene glycol) methyl ether, DMT, PG and poly-(ethylene glycol) (" PEG "); The end capped oligomer ester of part or all of negatively charged ion of the US4721580 of the Rosselink of promulgation on January 26th, 1988, for example by ethylene glycol (" EG "), PG, DMT and 3, the oligopolymer that the hot sodium sulfonate of 6-two oxa-s-8-hydroxyl obtains; The end capped block polyester oligopolymer of nonionic compound among the US4702857 of the Gosselink of promulgation on October 27th, 1987, for example by PEG and the EG and/or the PG of DMT, methyl blocking, or DMT, EG and/or the end capped PEG of PG, Me and dimethyl-5-sulfonation m-phthalic acid sodium preparation; Maldonado with promulgation on October 31st, 1989; the negatively charged ion of the US4877896 of Gosselink etc.; especially the end capped terephthalate of sulfonation aroyl; the latter is the SRA typical types that is used to wash with the fabric-conditioning product; the example is the ester composition by m-sulfosalicylic acid list sodium salt, PG and DMT preparation; optionally, but preferably also contain the PEG of adding, for example PEG3400.
SRA also comprises the simple copolymer block of ethylidene terephthalate or propylidene terephthalate and polyethylene oxide or poly(propylene oxide) terephthalate, referring to the US3893929 of the Basadur of the US3959230 of the Hays of on May 25th, 1976 promulgation and promulgation on July 18th, 1975; Derivatived cellulose, the METHOCEL that obtains by Dow for example, hydroxy ethers cellulose polymer compound; C 1-4Alkyl and C 4Hydroxy alkyl cellulose; United States Patent (USP) 4000093 referring to the Nicol of on December 28th, 1976 promulgation etc.Poly-(vinyl ester) hydrophobic fragment is that the suitable SRA of feature comprises that poly-(vinyl ester) is as, C 1-6The graft copolymer of vinyl ester preferably grafts on poly-(vinyl-acetic ester) on the polyoxyalkylene skeleton.European patent application 0219048 referring to disclosed Kud on the 22nd etc. April in 1987.This commercially available class polymerization stain remover comprises SOKALAN SRA, and for example SOKALAN HP-22 is obtained by BASF (Germany).Other SRA is the polyester that has repeating unit, wherein repeating unit contains the ethylidene terephthalate of 10-15% (weight) and the polyoxyethylene terephthalate of 80%-90% (weight), and it is that the polyoxyethylene glycol of 300-5000 obtains from molecular-weight average.Commercial embodiments comprises ZELCON 5126 that is obtained by Dupont and the MILEASE T that is obtained by ICI.
Another kind of preferred SRA is that empirical formula is (CAP) 2(EG/PG) 5(T) 5(SIP) 1Oligopolymer; it contains terephthaloyl (T), sulfo group isophthaloyl (SIP), ethylene oxide oxygen base and Oxy-1; 2-propylene (EG/PG) unit; it is preferably by end group (CAP) end-blocking; end group is the isethionate of modification preferably; for example; oligopolymer contains a sulfo group isophthaloyl unit, 5 terephthaloyl unit, limits the ethylene oxide oxygen base and the Oxy-1 of ratio; 2-propenyloxy group unit; preferred about 0.5: 1 to about 10: 1 and two are by end group unit that 2-(2-hydroxyl-oxethyl)-ethyl sulfonic acid sodium obtains.The degree of crystallinity that described SRA preferably also contains by oligopolymer weight 0.5% to 20% reduces stablizer, anion surfactant for example, as linear alkyl benzene sulphonate or be selected from dimethylbenzene-, cumene-and toluene-sulfonate or their mixture, these stablizers or properties-correcting agent are added in the synthesising container, all these are at the Gosselink of promulgation on May 16 nineteen ninety-five, Pan, open among the US5415807 of Kellett and Hall.The suitable monomer that is used for above-mentioned SRA comprises 2-(2-hydroxyl-oxethyl)-ethyl sulfonic acid sodium, DMT, dimethyl-5-sulfoisophthalate sodium, EG and PG.
Another kind of preferred SRA is the oligopolymer ester, it contains: (1) skeleton, it contains, and (a) is at least a to be selected from following unit, thereby the ester bond of dihydroxyl sulphonate, poly-hydroxy sulphonate, trifunctional formation at least produces the unit of branched oligomer skeleton and their mixture; (b) at least a is the unit of terephthaloyl group; (c) unit of at least one unsulfonated, it is 1,2-oxygen alkylene oxide group part; (2) one or more end-blocking unit; it is selected from nonionic end-blocking unit, negatively charged ion end-blocking unit; alkoxylate for example, preferred ethoxylation isethionic acid ester, alkoxylate propanesulfonic acid ester, alkoxylate third disulfonate, alkoxylate sulfophenylate, sulfo group aromatic acyl derivative and their mixture.Be preferably as follows the ester of empirical formula:
{ (CAP) x(EG/PG) Y '(DEG) Y "(PEG) Y (T) z (SIP) Z '(SEQ) q(B) mCAP wherein, EG/PG, PEG, T and SIP are as defined above, (DEG) expression two (ethylene oxide) oxygen base unit, (SEG) unit and relevant group unit that obtain by glycerine sulfo group ethyl ether of expression, (B) an expression chain unit, it is at least three functional groups, thereby the ester bond that forms produces the branched oligomer skeleton, x is about 1 to about 12, and y ' is about 0.5 to about 25, y " be 0 to about 12; y is 0 to about 10; y " + y "+y adds up to about 0.5 to about 25, and z is about 1.5 to about 25, and z ' is 0 to about 12; z+z ' adds up to about 1.5 to about 25, and q is about 0.05 to about 12; M be approximately O.01 to about 10 and x, y ', y ", y , z, z ', q and m represent have an appointment 500 to about 5000 molecular weight of the average mol of every mole of above-mentioned ester corresponding units, above-mentioned ester.
The preferred SEG of above-mentioned ester and CAP monomer comprise 2-(2-, 3-dihydroxyl propoxy-) ethyl sulfonic acid sodium (" SEG "), 2-{2-(2-hydroxyl-oxethyl) oxyethyl group } ethyl sulfonic acid sodium (" SE3 ") and its homologue and their mixture and ethoxylation and sulfonated allyl alcohol.Preferred SRA ester comprises 2-{2-(2-hydroxyl-oxethyl) oxyethyl group in this class } ethyl sulfonic acid sodium and/or 2-[2-{2-(2-hydroxyl-oxethyl) oxyethyl group } oxyethyl group] ethyl sulfonic acid sodium, DMT, 2-(2,3-dihydroxyl propoxy-) ethyl sulfonic acid sodium, EG and PG use the esterification transfer and the oligomerization product of suitable Ti (IV) catalyzer, can be described as (CAP) 2(T) 5(EG/PG) 1.4(SEG) 2.5 (B) 0.13, wherein CAP is (Na +-O 3S[CH 2-CH 2O] 3.5)-and B be the unit that glycerine obtains, the EG/PG mol ratio is about 1.7: 1, after complete hydrolysis by conventional gas chromatography determination.
Another kind of SRA comprises: (I) use the vulcabond coupler to connect polyester construction nonionic terephthalate, referring to the US4240918 of the US4201824 of Violland etc. and Lagasse etc.; (II) by trimellitic acid 1,2-anhydride being added to the SRA that has the carboxylicesters end group that among the known SRA end hydroxyl is changed into the trimellitate preparation.By selecting catalyst suitably, trimellitic anhydride is by the independent carboxylicesters of trimellitic anhydride and the end Cheng Jian of polymkeric substance, rather than opens the acid anhydride key.Nonionic or negatively charged ion SRA all can be used as starting material, as long as have can esterified hydroxyl end groups for they, referring to the US4525524 of Tung etc.; (III) urea alkane connects the SRA of the negatively charged ion terephthalic acid ester group of kind, referring to the US4201824 of Violland etc.; (IV) poly-(caprolactam) and and monomer, for example the related copolymers of vinyl pyrrolidone and/or dimethyl amino ethyl methacrylate comprises nonionic and cationic polymers, referring to the US4579681 of Ruppert etc.; (V) except the SOKALAN type that obtains by BASF, by the graft copolymer of the preparation of grafted propylene acid mono on sulfonated polyester.These SRA have the active and antiredeposition activity of decontamination of the plain ether of the known fiber of being similar to undoubtedly: referring to the EP279134A of Rhone-Poulenc Chemie, 1988; (VI) for example vinylformic acid and vinyl-acetic ester are at protein for vinyl monomer, and the grafts on the casein for example is referring to the EP457205A (1991) of BASF; (VII), be particularly useful for handling polyamide fabric, referring to the DE2335044 (Unilever N.V.) (1974) of Bevan etc. by the polyester-polyamide of condensation hexanodioic acid, hexanolactam and polyoxyethylene glycol preparation.Other useful SRA describes in US4240918,4787989,4525524 and 4877896.
Non-cotton soil release polymers
The non-cotton soil release polymers that is used for laundry detergent composition of the present invention is as follows.
Preferred non-cotton stain remover-A is applicable to that laundry detergent composition of the present invention is preferred non-cotton soil release polymers, and it contains: a) skeleton, and it contains: i) at least one has the group of following formula:
Figure A9718035700371
Ii) at least one has the group of following formula: R wherein 9Be C 2-C 6Straight-chain alkyl-sub-, C 3-C 6Branched alkylidene, C 5-C 7Ring alkylidene group and their mixture; R 10Be selected from respectively H or-LSO 3 -M +, wherein L is the pendant moiety that is selected from alkylidene group, oxyalkylene, alkyleneoxyalkylene group, arylidene, oxygen arylidene, alkylene oxide group arylidene, poly-(oxyalkylene), oxygen alkylene oxide group arylidene, poly-(oxyalkylene) oxygen arylidene, alkylidene group poly-(oxyalkylene) and their mixture; M is H or salt-forming cation; I is 0 or 1; Iii) at least one trifunctional forms a chain portion of ester; Iv) at least one 1,2-oxygen alkylene oxide group; And b) one or more end-blocking unit, it contains: i) formula (MO 3S) (CH 2) m(R 11O) n-ethoxylation or propoxylation hydroxyethyl sulphonate or ethoxylation or propoxylation hydroxypropyl sulphonate unit, wherein M is a salt-forming cation, for example sodium or tetra-allkylammonium, R 11Be ethylidene or propylidene or their mixture, m be 0 or 1 and n be 1-20; Ii) C (the C of formula-(O) 6H 4) (SO 3 -M +) the sulfo group aroyl, wherein M is a salt-forming cation; Iii) formula R 12O (CH 2CH 2O) k-modification poly-(oxygen ethylidene) oxygen monoalky lether unit, wherein R 12Contain 1-4 carbon atom, k is about 3-about 100; Iv) formula MO 3S (C 6H 4) (OR 13) nThe ethoxylation of O-or propoxylation sulfophenylate end-blocking unit, wherein n is 1-20; M is a salt-forming cation; And R 13Be ethylidene, propylidene and their mixture.
The preferred non-cotton soil release polymers of this class of the present invention can be represented by the formula: [(Cap) (R 4) t] [(A-R 1-A-R 2) u(A-R 1-A-R 3) v(A-R 1-A-R 5) w-A-R 1-A-] [(R 4) t(Cap)] wherein A is the carboxyl connection portion with following formula: R1 is an arylidene, 1 of preferred following formula, and the 4-phenylene: Make as A unit and R 1The unit is at formula A-R 1When linking together among-the A, form the following formula terephthalate units,
Figure A9718035700383
R 2The unit is inferior ethoxyl or 1, the inferior propoxy-of 2-, R 2The unit can be connected with the terephthalic acid ester moiety to form (the A-R of following formula 1-A-R 2) unit: Wherein R ' and R " be H or methyl, its prerequisite is R ' and R " not methyl simultaneously.
R 3The unit is the trifunctional of following formula, forms a chain portion of ester: Preferred R 3The unit contains the glycerine part, and it is arranged in the soil release polymer skeleton so that the side chain point to be provided.Work as R 3The unit when being connected to form the polymer backbone unit with the terephthalic acid ester moiety, (A-R for example 1-A-R 3)-A-R 1During-A unit, there is following formula these unit:
Figure A9718035700393
Or
Figure A9718035700394
One of them terephthalate residues accounts for (A-R 1-A-R 3) a unitary part, and second terephthalate units constitutes the part of other skeleton unit, for example (A-R 1-A-R 2) unit, (A-R 1-A-R 5) unit ,-A-R 1-A-[(R 4) t(Cap)] unit or second (A-R 1-A-R 3) a unitary part.Be positioned at the trifunctional group that side chain begins, also connect terephthalate residues usually, it is (A-R 1-A-R 2) unit, (A-R 1-A-R 5) unit ,-A-R 1-A-[(R 4) t(Cap)] unit or another (A-R 1-A-R 3) a unitary part.
Contain and wherein contain glycerine unitary " trifunctional becomes ester to prop up chain portion " R 3The example of the part of unitary soil release polymer has following formula:
Figure A9718035700401
R 4The unit is R 2, R 3Or R 5The unit.R 5The unit is a unit of following formula: R wherein 9Be C 2-C 6Straight-chain alkyl-sub-, C 3-C 6Branched alkylidene and their mixture; R 10Be preferably selected from respectively H or-LSO 3 -M +, wherein L is the pendant moiety that is selected from alkylidene group, oxyalkylene, alkyleneoxyalkylene group, arylidene, oxygen arylidene, alkylene oxide group arylidene, poly-(oxyalkylene), oxygen alkylene oxide group arylidene, poly-(oxyalkylene) oxygen arylidene, alkylidene group poly-(oxyalkylene) and their mixture; M is H or salt-forming cation; I is 0 or 1;
Each R 9On carbon atom by R 10Replace, it be selected from respectively H or-LSO 3 -M +, its prerequisite is no more than one-LSO 3 -M +Be connected in R 9On the unit; L is the pendant moiety that is selected from alkylidene group, oxo alkylidene group, alkyleneoxyalkylene group, arylidene, oxygen arylidene, alkylene oxide group arylidene, poly-(oxyalkylene), oxygen alkylene oxide group arylidene, poly-(oxyalkylene) oxygen arylidene, alkylidene group poly-(oxyalkylene group) and their mixture.
M is the cationic moiety that is selected from lithium, sodium, potassium, calcium and magnesium, preferred sodium and potassium.
Preferred R 5Part mainly is R 10The C that replaces 2-C 6Alkylidene chain.R 5The unit contains one by one or more R that selects respectively 10The C that part replaces 2-C 6Alkylidene chain (preferably) or two C 2-C 6Alkylidene chain, described alkylidene group connects by ether-oxygen bond, and each alkylidene chain is by one or more R that selects respectively 10Part replaces, i.e. R 5Can contain two R that separate 9The unit, each is by one or more R that selects respectively 10Part replaces.Preferred each R 9Only carbon atom of part is by one-LSO 3 -M +The unit replaces, all the other R 10Substituting group contains hydrogen atom.When the numerical value of coefficient i equals 1 (two R 9The unit contains R 5The unit) time, preferred formula is:
Figure A9718035700411
Each R wherein 9Contain C 2Alkylene moiety, a preferred R 10Be-LSO 3 -M +, preferred C 2Carbon quilt-LSO 3 -M +Part replaces, and all the other are hydrogen atoms, therefore has following formula:
Figure A9718035700412
Wherein L is the polyethylene oxide methyl substituents, and x is 0-about 20.
Term " the R that is used for this paper 5Part mainly equals 0 form as lower unit by coefficient i:
Figure A9718035700413
R wherein 10The unit is hydrogen and a R 10The unit equals-LSO 3 -M +, L is the side chain connection portion that is selected from alkylidene group, alkenylene, alkoxyl group alkylidene group, oxyalkylene, arylidene, alkyl arylene, alkoxyl group arylidene and their mixture " and be meant preferred compound of the present invention, wherein R 10Part is by one-LSO 3 -M +Part is formed, all the other R 10Part is a hydrogen atom, for example It can be used as-A-R 5-A-skeleton segment is included in the polymeric skeleton of soil release polymer of the present invention.This unit easily adds in oligopolymer or the polymer backbone by the starting material that uses following general formula: For L part of the present invention, wherein x is 0-20.
As R 5Other proper monomer that part can be included in the skeleton of the non-cotton soil release polymers of type A of the present invention comprises following general formula monomer (containing poly-(oxyalkylene group) oxo arylidene of alkylidene group): Wherein x is 0-20.Produce the preferred R that i wherein equals 0 5Other example of unitary preferred monomers is poly-(oxyethane) methyl isophthalic acid of the sodium sulfo group of following formula, the 2-propylene glycol:
Figure A9718035700422
Wherein x is 2-about 20; Be more preferably following monomer:
Figure A9718035700423
Or
Figure A9718035700424
Except above-mentioned R 1, R 2, R 3, R 4And R 5Outside, preferred non-cotton soil release polymers of the present invention also comprises one or more capping groups-(Cap).Capping group is selected from formula (MO respectively 3S) (CH 2) m(R 11O) n-ethoxylation or propoxylation hydroxyethyl and propyl sulfonic acid ester, wherein M is aforesaid salt-forming cation, for example sodium or tetra-allkylammonium, R 11Be ethylidene or propylidene or their mixture, m be 0 or 1 and n be 1-20, preferred n is 1-4; C (the C of formula-(O) 6H 4) (SO 3 -M +) the sulfo group aroyl, wherein M is aforesaid salt-forming cation; Formula R 12O (CH 2CH 2O) k-modification poly-(oxyethane) oxo monoalky lether unit, wherein R 12Contain 1-4 carbon atom, preferable methyl, k is about 3-100, preferably about 3-50 is more preferably about 3-about 30; With formula MO 3S (C 6H 4) (OR 13) nThe ethoxylation of O-or propoxylation sulfophenylate end-blocking unit, wherein n is-20; M is a salt-forming cation; And R 13Be ethylidene, propylidene and their mixture.
Most preferred end-blocking unit is isethionic acid type end-blocking unit, and it is the hydroxyl ethane group, (MO 3S) (CH 2) m(R 11O) n-, preferred R 11Be ethyl, m be 0 and n be 2-4.
T is 0 or 1, and u is about 0-about 60; V is about 0-about 35; W is 0-35.
Has following formula [(Cap) (R 4) t] [(A-R 1-A-R 2) u(A-R 1-A-R 3) v(A-R 1-A-R 5) w-A-R 1-A-] [(R 4) t(Cap)] of the present invention preferred non-cotton soil release polymers can be represented with following general structural formula easily:
Figure A9718035700431
Following structure is the example of preferred non-cotton soil release polymers of the present invention.
Above-mentioned preferred non-cotton stain remover is intactly described in the US series number 08/545351 of application on November 22 nineteen ninety-five, and this application is the part continuation application of the US series number 08/355938 of application on December 14th, 1994, and they all classify this paper reference as.Further describe other the non-cotton soil release polymers that is applicable to composition of the present invention below.
Preferred non-cotton SRA further describes as the oligopolymer ester, it contains: (1) skeleton, it contains, and (a) is at least a to be selected from following unit, thereby the ester bond of dihydroxyl sulphonate, poly-hydroxy sulphonate, trifunctional formation at least produces the unit of branched oligomer skeleton and their mixture; (b) at least a is the unit of terephthaloyl group; (c) unit of at least one unsulfonated; it is 1; 2-oxygen alkylene oxide group part and (2) one or more end-blocking unit; it is selected from nonionic end-blocking unit, negatively charged ion end-blocking unit; alkoxylate for example, preferred ethoxylation isethionic acid ester, alkoxylate propanesulfonic acid ester, alkoxylate third disulfonate, alkoxylate sulfophenylate, sulfo group aromatic acyl derivative and their mixture.Be preferably as follows the ester of empirical formula:
{ (CAP) x(EG/PG) Y '(DEG) Y "(PEG) Y (T) z(SIP) Z '(SEQ) q(B) mCAP wherein, EG/PG, PEG, T and SIP are defined as terephthaloyl (T), sulfo group isophthaloyl base (SIP), oxygen oxyethyl group and oxygen-1,2-propylidene (EG/PG) unit, end-blocking unit (CAP), gather (ethylene glycol) (PEG), (DEG) expression two (oxygen ethylidene) oxygen base unit, (SEG) unit that obtains by glycerine sulfo group ethyl ether and relevant group unit of expression, (B) an expression chain unit, it is at least three functional groups, thereby the ester bond that forms produces the branched oligomer skeleton, x is about 1 to about 12, y ' is about 0.5 to about 25; y " be 0 to about 12, y is 0 to about 10, y '+y "+y adds up to about 0.5 to about 25; and z is about 1.5 to about 25; z ' is 0 to about 12, and z+z ' adds up to about 1.5 to about 25, and q is about 0.05 to about 12; M be about 0.01 to about 10 and x, y ', y ", y , z, z ', q and m represent have an appointment 500 to about 5000 molecular weight of the average mol of every mole of above-mentioned ester corresponding units, above-mentioned ester.
The preferred SEG of above-mentioned ester and CAP monomer comprise 2-(2-, 3-dihydroxyl propoxy-) ethyl sulfonic acid sodium (" SEG "), 2-{2-(2-hydroxyl-oxethyl) oxyethyl group } ethyl sulfonic acid sodium (" SE3 ") and its homologue and their mixture and ethoxylation and sulfonated allyl alcohol product.Preferred SRA ester comprises 2-{2-(2-hydroxyl-oxethyl) oxyethyl group in this class } ethyl sulfonic acid sodium and/or 2-[2-{2-(2-hydroxyl-oxethyl) oxyethyl group } oxyethyl group] ethyl sulfonic acid sodium, DMT, 2-(2,3-dihydroxyl propoxy-) ethyl sulfonic acid sodium, EG and PG use the esterification transfer and the oligomerization product of suitable Ti (IV) catalyzer, can be described as (CAP) 2(T) 5(EG/PG) 1.4(SEG) 2.5(B) 0.13, wherein CAP is (Na +-O 3S[CH 2-CH 2O] 3.5)-and B be the unit that glycerine obtains, the EG/PG mol ratio is about 1.7: 1, after complete hydrolysis by conventional gas chromatography determination.
Second preferred kind of the SRA that preferred non-cotton stain remover-B is suitable comprises the sulfonated products of the ester oligomer of straight chain basically, and it partly is made up of with the allyl group deutero-sulfonation end group that is covalently attached to skeleton the ester oligomer skeleton of terephthaloyl and oxygen alkylene oxide group repeating unit.This ester oligomer is by (a) ethoxylation allyl alcohol; (b) make product and dimethyl terephthalate (DMT) (" DMT ") and 1 of (a), 2-propylene glycol (" PG ") reacts in two-stage esterification transfer/oligomerisation process; (c) make product and sodium metabisulfite prepared in reaction in water of (b).
What be applicable to laundry detergent composition of the present invention is preferred non-cotton soil release polymers, and it contains: a) one or two terminal units, and it is selected from: i)-(CH 2) q(CHSO 3M) CH 2SO 3M, ii)-(CH 2) q(CHSO 2M) CH 2SO 3M, iii)-CH 2CH 2SO 3M and iv) their mixture, wherein q is the numerical value of 1-about 4, M is a water-soluble cationic, preferred sodium; B) skeleton, it contains: i) arylene units preferably has the terephthalate units of following formula:
Figure A9718035700451
The inferior ethoxyl unit that ii) has following formula :-O (CH 2CH 2O) nCH 2CH 2O-wherein n is that numerical value is about 1-about 20; Iii) have 1 of following formula, the inferior propoxy-of 2-unit:
-O (CH 2CH (CH 3) O) nCH 2CH (CH 3) O-wherein n be about 1-about 20, wherein the further preferred skeleton of this preferred non-cotton soil release polymers contains skeleton, it contains arylene repeat units, it and inferior ethoxyl and 1, the inferior propoxy-units alternately of 2-, inferior ethoxyl and 1 like this, the unitary mol ratio of the inferior propoxy-of 2-is 0: about 0.9: 0.1 of 1-, preferred about 0: about 0.4: 0.6 of 1-, more preferably arylene units is basically with 1, the inferior propoxy-units alternately of 2-.
Yet other combination of above-mentioned different units also can be used for forming the non-cotton soil release polymers that is applicable to composition of the present invention.These are combined among the US4968451 of Scheibel etc. of November 6 nineteen ninety promulgation and more completely describe, and classify this paper reference as.
What preferred non-cotton stain remover-C was applicable to laundry detergent composition of the present invention is the preferred non-cotton soil release polymers of following formula:
(Cap) [(A-R 1-A-R 2) u(A-R 3-A-R 2) v-A-R 4-A-] (Cap) wherein A is the carboxyl connection portion, preferred A is the carboxyl connection portion of following formula: Or R 1Be the arylidene part, preferably have 1 of following formula, the 4-phenylen moiety: Wherein for R 1, remove 1, the degree that the arylidene outside the 4-phenylene partly replaces should make to the soil removability of the compound disadvantageous effect without any big degree.Usually, admissible part replaces the skeleton length that will depend on compound.
R 2Part is the ethylidene part or contains C 1-C 4The ethylidene part of the replacement of alkyl or alkoxy substituent.Term " R used herein 2Part mainly is the ethylidene part or contains C 1-C 4The ethylidene part of the replacement of alkyl or alkoxy substituent " be meant compound of the present invention, wherein R 2Part all replaces or the ethylidene part of replacement partly by ethylidene or with other compatible part.The example of these other parts comprises trimethylene, tetramethylene, pentamethylene or hexamethylene, 1,2-hydroxy alkylidene and oxyalkylene.
For R 2, the degree that partly replaces with other parts should make to the soil removability of the compound disadvantageous effect without any big degree.For example, with Diethylene Glycol (CH 2CH 2OCH 2CH 2-) with the mol ratio of ethylene glycol (ethylidene) be that the polyester of the present invention of preparation in 75: 25 has enough decontamination activity.
For R 3Part, the C of suitable replacement 2-C 18The alkylene part can comprise the C of replacement 2-C 12Alkylidene group, alkenylene, arylidene, alkarylene etc.Alkylidene group that replaces or alkenylene part can be straight chain, side chain or cyclic.R 3(for example all being the arylidene that replaces) or mixture (for example mixture of the alkylidene group of arylidene of Qu Daiing and replacement) that in addition can be all identical.Preferred R 3Part is 1 of replacement, 3-phenylene, preferred 5-sulfo group-1,3-phenylene.R 3Part can also be-A-[(R 2-A-R 4)]-Cap, wherein R 4Be R 1, R 3With their mixture.
Preferably (Cap) part contains unit of following formula:
-[(R 5O) m(CH 2CH 2O) n] X R wherein 5Be C 1-C 4Alkylidene group or-R 2-A-R 6-, R wherein 6Be C 2-C 12Alkylidene group, alkenylene, arylidene or alkarylene part, X is C 1-C 4Alkyl, preferable methyl; Coefficient m and n make part-CH 2CH 2O-accounts for as by weight at least 50% of lower section:
-[(R 5O) m(CH 2CH 2O) n] its prerequisite of X is to work as R 5Be-R 2-A-R 6In-time, m is 1 at least; Each n is about 10 at least, and coefficient u and v should make u+v's and be about 3-about 25; Coefficient w is 0 or at least 1; When w was at least 1, coefficient u, v and w made that the summation of u+v+w is the numerical value of about 3-about 25.
The example of the non-cotton decontamination block polyester of this class has following formula:
Figure A9718035700461
R wherein 2Mainly be ethylidene part, propylene part and their mixture; R 3Part all is potassium or preferred sodium 5-sulfo group-1, the 3-phenylen moiety; R 4Part is R 1Or R 3Part or their mixture; Each X is ethyl, methyl, preferable methyl; Each n is about 12-about 43; When w was 0, u+v was about 3-about 10; When w was at least 1, u+v+w was about 3-about 10.
The above-mentioned non-cotton soil release polymers of following formula:
(Cap) [(A-R 1-A-R 2) u(A-R 3-A-R 2) v-A-R 4-A-] (Cap) in the US4702857 of the Gosselink of on October 27th, 1987 promulgation, describe in detail.
Except above-mentioned non-cotton soil release polymers, be applicable to that other soil release polymer of liquid laundry detergent compositions of the present invention further describes hereinafter.
Except carboxymethyl cellulose (CMC) can not use separately, the non-cotton stain remover of any other negatively charged ion was applicable in the composition of the present invention with mixing individually or.If the makers-up selects the anionic detergent of CMC as laundry detergent composition of the present invention, carboxymethyl cellulose must exist with the quantity that surpasses by composition weight meter 0.2%.2-[2-(2-hydroxyl-oxethyl) oxyethyl group] oligopolymer synthetic of ethylsulfonic acid sodium, dimethyl terephthalate (DMT), 2-(2,3-dihydroxyl propoxy-) ethylsulfonic acid sodium, ethylene glycol and propylene glycol
Be equipped with magnetic stirring bar, improved Claisen head, condenser (being used for distillation), thermometer and temperature regulator (Therm-O-Watch  I 2R) add 2-[2-(2-hydroxyl-oxethyl) oxyethyl group in the 250ml three neck round-bottomed flasks] ethylsulfonic acid sodium (7.0g, 0.030mol), dimethyl terephthalate (DMT) (14.4g, 0.074mol), 2-(2,3-dihydroxyl propoxy-) ethylsulfonic acid sodium (6.6g, 0.030mol), ethylene glycol (Baker, 14.0g, 0.0225mol), propylene glycol (Fisher, 18.3g, 0.0240mol) and titanium propanolate (IV) (0.01g is by reactant gross weight 0.02%).With mixture heating up to 180 ℃, under this temperature, in argon gas, keep spending the night, simultaneously distillating carbinol from reaction vessel.With this substance transfer to the single neck round-bottomed flask of 500ml, in about 20 minutes, be heated to 240 ℃ at Kugelrohr device (Aldrich) under about 0.1mmHg by ashamed, and kept 110 minutes, reaction flask is cooled to rapidly under vacuum in air near room temperature (about 30 minutes).Reaction obtains the required oligopolymer of 24.4g, is brown glass shape material. 13C-NMR (DMSO-d 6) demonstration-C (O) OCH 2CH 2O (O) C-the response of about 63.2ppm (diester) and-C (O) OCH 2CH 2OH is in the response of about 59.4ppm (monoesters), and the ratio at diester peak and monoesters peak is 8.Also exist in the expression sulfo group oxyethyl group (CH of about 51.5ppm and about 51.6ppm 2SO 3Na) response. 1H-NMR (DMSO-d 6) be presented at the response of the expression terephthalate fragrance hydrogen of about 7.9ppm.The ratio of the hydrolysis-ethylene glycol that GC analysis demonstration adds and the propylene glycol of adding is 1.6: 1.By the small amount of matter of in phial, weighing, add enough distilled water to obtain 35% solution and vigorous stirring phial test solvability by weight, this material is Yi Rong under these conditions.
Bleaching compounds-SYNTHETIC OPTICAL WHITNER and bleach activator-detergent composition of the present invention optionally contains SYNTHETIC OPTICAL WHITNER or contains SYNTHETIC OPTICAL WHITNER and the bleaching composition of one or more bleach activators.If exist, during in particular for fabric washing, it is about 30% that the content of SYNTHETIC OPTICAL WHITNER is generally about 1%-of detergent composition, and more commonly used is about 5%-about 20%.If present, it is about 60% that the quantity of bleach activator is generally about 0.1%-of the bleaching composition that contains SYNTHETIC OPTICAL WHITNER and bleach activator, more generally is about 0.5%-about 40%.
Be used for SYNTHETIC OPTICAL WHITNER of the present invention and can be known or will known washing use any SYNTHETIC OPTICAL WHITNER useful to detergent composition at fabric washing, hard surface cleaning or other.These comprise oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.The present invention can use perborate bleach, as Sodium peroxoborate (as single-or four-monohydrated sodium perborate).
The SYNTHETIC OPTICAL WHITNER of another kind that can use without restriction comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The suitable example of this SYNTHETIC OPTICAL WHITNER comprises magnesium salts, 4-amino in the ninth of the ten Heavenly Stems-4-oxygen base peroxidation butyric acid and the diperoxy dodecanedioic acid of six water monoperoxyphthalic acid magnesium, inclined to one side chlorine peroxybenzoic acid.The US4483781 of the Hartman of promulgation on November 20th, 1984, Burns equals the U.S. Patent application 740446 of application on June 3rd, 1985, February in 1985 disclosed Banks on the 20th etc. european patent application 0133354, and the US4412934 of the Chung of promulgation on November 1 nineteen eighty-three etc. has disclosed this SYNTHETIC OPTICAL WHITNER.Preferred SYNTHETIC OPTICAL WHITNER also comprises 6-amino in the ninth of the ten Heavenly Stems-6-oxygen base peroxidation caproic acid, describes among the US4634551 of the Burns that this has issued on January 6th, 1987 etc.
Also can use peroxygen bleach.Suitable peroxy bleaching compound comprises peroxide hydrated sodium carbonate and corresponding " percarbonate " SYNTHETIC OPTICAL WHITNER, peroxide hydration trisodium phosphate, peroxide hydration urea and sodium peroxide.Also can use persulphate SYNTHETIC OPTICAL WHITNER (as the industrial OXONE that produces by DuPont).
Preferred percarbonate bleach comprises the dried particles of average particulate diameter in about 500 microns-Yue 1000 micrometer ranges, wherein no more than about by weight 10% described particle is less than about 200 microns, and no more than about by weight 10% described particle is greater than about 1250 microns.Optionally coat percarbonate with silicate, borate or water soluble surfactant active.Percarbonate can obtain as FMC, Solvay and Tokai Denka from various commercial sources.
Also can use the SYNTHETIC OPTICAL WHITNER mixture.
Peroxygen bleach, perborate, percarbonate etc. preferably mix with bleach activator, and wherein promoting agent can generate and the corresponding peroxy acid aqueous solution of bleach activator (promptly in washing process) on the spot.The various non-limitative examples that the US4915854 of the Mao of promulgation on April 10 nineteen ninety etc. and US4412934 have disclosed promoting agent.Nonanoyl phenolsulfonic acid ester (NOBS) and tetraacetyl ethylene diamine (TAED) promoting agent are typical, also can use its mixture.Be used for other typical SYNTHETIC OPTICAL WHITNER of the present invention and promoting agent referring to US4634551.
Amido deutero-bleach activator is more preferably those materials with following structural formula:
R 1N (R 5) C (O) R 2C (O) L or R 1C (O) N (R 5) R 2C (O) L is R wherein 1For containing the alkyl of about 12 carbon atoms of the 6-that has an appointment, R 2For containing the alkylidene group of about 6 carbon atoms of the 1-that has an appointment, R 5For H or contain alkyl, aryl or the alkaryl of about 10 carbon atoms of the 1-that has an appointment, and L is any suitable leavings group.Leavings group is by crossing the hydrolysis negatively charged ion bleach activator to be carried out any group of cementing out behind the nucleophilic attack from bleach activator, and preferred leavings group is a phenyl sulfonate.
Preferred example with bleach activator of following formula comprises (6-decoyl amino-caproyl) phenolsulfonic acid ester, (the amino caproyl of 6-nonanoyl) phenolsulfonic acid ester, (6-caprinoyl amino-caproyl) phenolsulfonic acid ester and composition thereof; this describes in US4634551, classifies this paper reference as.
The bleach activator of another kind comprises benzoxazine type promoting agent, and the US4966723 of the Hodge of promulgation on October 30 nineteen ninety etc. discloses this promoting agent, classifies this paper reference as.Preferred benzoxazine type promoting agent is:
Figure A9718035700491
Another preferred bleach activator comprises the acyl lactam promoting agent, particularly has the acyl caprolactam and the acyl group Valerolactim of following structural formula:
Figure A9718035700492
R wherein 6For H or contain alkyl, aryl, alkoxy aryl or the alkaryl of about 12 carbon atoms of 1-.Preferred lactan promoting agent comprises benzoyl caprolactam, capryloyl hexanolactam, 3; 5; 5-trimethyl acetyl base hexanolactam, nonanoyl hexanolactam, decanoyl hexanolactam, undecanoyl hexanolactam, benzoyl Valerolactim, capryloyl Valerolactim, decanoyl Valerolactim, undecanoyl Valerolactim, nonanoyl Valerolactim, 3; 5,5-trimethyl acetyl base Valerolactim and composition thereof.Referring to the US4545784 of the Sanderson that issued on October 8th, 1985, classify this paper reference as in addition, it has disclosed the acyl caprolactam that comprises benzoyl caprolactam that is adsorbed onto in the Sodium peroxoborate.
Other SYNTHETIC OPTICAL WHITNER except oxygen bleaching agent also is known in the art, and can be used for the present invention.A kind of non-oxygen bleaching agent with special value comprises photoactivation SYNTHETIC OPTICAL WHITNER such as sulfonated zinc and/or aluminium phthalocyanine.US4033718 referring to the Holcombe of on July 5th, 1977 promulgation etc.If you are using, detergent composition generally contains this SYNTHETIC OPTICAL WHITNER of about by weight 0.025%-about 1.25%, particularly sulfonated zinc phthalocyanine.
If desired, bleaching compounds can carry out catalysis with manganic compound.This compound is well known in the art, and comprise, for example, be disclosed in manganese-based catalyst among US5246621, US5244594, US5194416, US5114606 and european patent application № 549271A1,549272A1,544440A2 and the 544490A1.The preferred embodiment of this catalyzer comprises Mn IV 2(u-O) 3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(PF 6) 2, Mn III 2(u-O) 1(u-OAc) 2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(ClO 4) 2, Mn IV 4(u-O) 6(1,4, the 7-7-triazacyclononane) 4(ClO 4) 4, Mn IIIMn IV 4(u-O) 1(u-OAc) 2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2(ClO 4) 3, Mn IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) 2-(OCH 3) 3(PF 6) and composition thereof.Other metal matrix bleaching catalyst comprises those disclosed in US4430243 and the US5114611.Following US4728455,5284944,5246612,5256779,5280117,5274147,5153161 and 5227084 has reported that also use magnesium and various complex coordination body are to improve bleachability.
In fact, and not in order to limit, can adjust to provide the compositions and methods of the invention and contain at least one ten million/a active bleaching catalyst material in the wash water solution, and preferably in washings, contain the about 700ppm of the 0.1ppm-that has an appointment, the catalyst substance of the about 500ppm of more preferably about 1ppm-.
It is known being used for cobalt bleaching catalyst of the present invention, at for example M.L.Tobe, and " alkaline hydrolysis of transition metal complex " Adv.Inorg.Bioinorg.Mech., (1983), and 2, describe in the 1-94 page or leaf.Being used for most preferred cobalt catalyst of the present invention is formula [Co (NH 3) 5OAc] T yCobalt five amine acetates, " OAc " expression acetate part wherein, " T y" be negatively charged ion, five amine acetate cobalt chloride [Co (NH especially 3) 5OAc] Cl 2, [Co (NH 3) 5OAc] (OAc) 2, [Co (NH 3) 5OAc] (PF 6) 2, [Co (NH 3) 5OAc] (SO 4), [Co (NH 3) 5OAc] (BF 4) 2[Co (NH 3) 5OAc] (NO 3) 2(being called " PAC " herein).
These cobalt catalyst easily prepare by currently known methods, for example at Tobe paper and the document wherein quoted/at US4810410, the J.Chem.Ed. (1989) of the Diakun of promulgation on March 7th, 1989 etc., 66 (12), 1043-45, " the synthetic and sign of mineral compound ", W.L.Jolly (Prentice-hall; 1970), 461-3 page or leaf; Inorg.Chem., 18,1497-1502 (1979); Inorg.Chem., 21,2881-2885 (1982), Inorg.Chem., 18,2023-2025 (1979), Inorg.Synthesis.173-176 (1960) and Journalof Physical Chemistry, 56, discuss among the 22-25 (1952).
In fact, and not in order to limit, can adjust the active bleaching catalyst material that contains at least one hundred million/portion in the wash water solution to provide to automatic tableware cleaning composition of the present invention and washing methods, and preferably in washings, contain the about 25ppm of the 0.01ppm-that has an appointment, the about 10ppm of more preferably about 0.05ppm-, the bleaching catalyst material of the about 5ppm of most preferably from about about 0.1ppm-.For in the washing mother liquor of automatic tableware washing process, obtaining this content, the automatic tableware cleaning composition contains usually by the about 0.0005%-of detergent composition weight about 0.2%, more preferably from about bleaching catalyst, especially manganese or the cobalt catalyst of 0.004%-about 0.08%.
Remove clay soil/anti redeposition agent-composition of the present invention and can also optionally contain water-soluble ethoxylated amine with removal clay soil and antiredeposition performance.The granular detergent composition that contains these compounds generally contains the water-soluble ethoxylated amine of about by weight 0.01%-about 10.0%; Liquid detergent composition contains the 0.01%-that has an appointment about 5% usually.
Most preferred removal dirt and anti redeposition agent are the ethoxylation tetrens.The example of ethoxylated amine is described in the US4597898 of the Vander Meer of promulgation on July 1st, 1986.Another kind of preferred removal clay soil/anti redeposition agent be on June 27th, 1984 disclosed Oh and the european patent application 111965 of Gosselink in disclosed cation compound.Operable other are removed disclosed ethoxylated amine polymer in the european patent application 111984 that clay soil/anti redeposition agents comprise disclosed Gosselink on the 27th June in 1984; July in 1984 disclosed Gosselink on the 4th european patent application 112592 in disclosed amphoteric ion polymer; With disclosed amine oxide among the US4548744 of the Connor of on October 22nd, 1985 promulgation.As known in the art other are removed clay soil/anti redeposition agent and also can be used in the composition of the present invention.Referring to the US4891160 of the Vander Meer of July 1 nineteen ninety promulgation and November 30 nineteen ninety-five disclosed WO95/32272.Another kind of preferred anti redeposition agent comprises carboxymethyl cellulose (CMC) material.These materials are well known in the art.
Polymeric dispersant-polymeric dispersant can be advantageously be used for the present composition with the content of about 0.1%-about 7% by weight, especially when zeolite and/or layered silicate washing assistant exist.The polymeric dispersant that is fit to comprises polymeric polycarboxylate and polyoxyethylene glycol, though other known polymeric dispersants of this area also can use.Do not limited by theoretical although do not wish, but can be sure of when polymeric dispersant with other washing assistants (comprising low-molecular-weight polycarboxylate) when using, by the crystal growth restraining effect, especially free the peptization and the anti-redeposition of dirt, can improve the performance of all detergent builder compounds.
By making suitable unsaturated monomer, preferably the polymerization of unsaturated monomers of sour form or polymerization process can prepare polymer poly-carboxylate's material.Can comprise vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid through the suitable polymer poly-carboxylate's of polymerization preparation unsaturated monomer acid.In multi-carboxylate polymer of the present invention or monomer segment, contain and do not have carboxylate groups such as vinyl methyl ether, vinylbenzene, the monomer segment of ethene etc. is fit to, as long as it is no more than about by weight 40%.
Especially the multi-carboxylate polymer of Shi Heing can obtain from vinylformic acid.Such that uses among the present invention is the water-soluble salt of polymeric acrylic acid with vinylformic acid as the polymkeric substance of matrix.The molecular-weight average of this base polymer that exists with sour form is preferably about 2000-10000, and more preferably 4000-7000 most preferably is 4000-5000.The example of the water-soluble salt of such acrylate copolymer comprises an alkali metal salt, ammonium salt and substituted ammonium salt.Such polymer soluble is known.Such application of polypropylene hydrochlorate in detergent composition is disclosed among the US3308067 of the Diehl of promulgation on March 7th, 1967.
Vinylformic acid/maleic copolymer also can be as the preferred ingredient of dispersion/anti-deposition agent.This class material comprises the water-soluble salt of vinylformic acid and maleic acid.The molecular-weight average of this analog copolymer that exists with sour form is preferably about 2000-100000, and more preferably 5000-75000 most preferably is 7000-65000.The ratio of acrylate moiety and toxilic acid part was generally more preferably from about 10: 1 to 2: 1 about 30: 1 to about 1: 1 in this analog copolymer.The water-soluble salt of this class vinylformic acid/maleic acid can comprise, for example, and an alkali metal salt, ammonium salt and substituted ammonium salt.This class water-soluble acrylic/maleate copolymer is a known substances, it is disclosed in the disclosed european patent application 66915 on December 15 nineteen eighty-two, and on September 3rd, 1986 disclosed EP193360, it has also described this base polymer that contains the hydroxypropyl acrylate.Other useful dispersion agent comprises the trimer of toxilic acid/vinylformic acid/vinyl alcohol, and this material is also open in EP193360, and it comprises for example 45/45/10 trimer of toxilic acid/vinylformic acid/vinyl alcohol.
The another kind of polymkeric substance that can be comprised is polyoxyethylene glycol (PEG).PEG can demonstrate the performance and the conduct of dispersion agent and remove clay soil/anti redeposition agent.It is about 100000 to be generally about 500-as the molecular-weight average of the polyoxyethylene glycol of this purposes, and it is about 50000 to be preferably about 1000-, more preferably about 1500-about 10000.
Also can use polyaspartic acid salts and polyglutamic acid dipersant, especially be used in combination with zeolite builders.Dispersion agent, for example polyaspartic acid salts preferably has about 10000 molecular weight (on average).
Whitening agent-any white dyes well known in the art or other whitening agent generally can about by weight 0.01%-about 1.2% content mix in the detergent composition of the present invention.Can be used for commercially available white dyes of the present invention and can be divided into following group, it comprises, but needn't be so limited stilbene derivatives, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanines, dibenzothiophene-5, the 5-dioxide, the pyrroles, 5-and 6-unit heterocyclic derivative, and other variegated dose.The example of these whitening agent is disclosed in " preparation of white dyes and application ", and M.Zahradnik is by John Wiley﹠amp; Sons, New york (1982) publishes.
Disclosed identical among the US4790856 of the Wixon of the specific examples of the white dyes that in the present composition, uses and on December 13rd, 1988 promulgation.These whitening agent comprise the PHORWHITE whitening agent series of Verona.Disclosed other whitening agent comprise in this reference: the Tinopal UNPA of Ciba-Geigy, Tinopal CBS and Tinopal 5BM; Arctic White CC and ArticArtic White CWD; 2-(4-styryl phenyl)-2H-naphtho-[1,2-d] triazole; 4,4 '-two (1,2,3-triazoles-2-yl) stilbene; 4,4 '-bis-styrylbiphenyl and aminocoumarin.The specific examples of these whitening agent comprises: 4-methyl-7-diethyl amino coumarin; 1, the two (ethene of benzimidazolyl-2 radicals-yl) of 2-; 1, the 3-diphenylpyrazoline; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-styryl-naphtho-[1,2-d] oxazole and 2-(stilbene-4-yl)-2H-naphtho-[1,2-d] triazole.US3646015 referring to the Hamilton that issued on February 29th, 1972.
Dye transfer inhibitor-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 fabric material in washing process.Usually, such dye transfer inhibitor comprises multipolymer, manganese phthalocyanine, peroxidase and their mixture of polyvinylpyrrolidonepolymers polymers, polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.If use, these inhibitor account for composition weight about 0.01% to about 10%, preferred about 0.01% to about 5%, more preferably from about 0.05% to 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 be connected in 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, fragrant, the heterocycle of ethoxylation 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, pyrroline, 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 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, pi, polyacrylic ester 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: 1,000,000.Yet the number of the amine oxide group that exists in the polyamine oxide polymer can change by the N-oxidation of suitable copolymerization or appropriate level.The polyamine oxide compound almost can obtain by any extent of polymerization.Molecular-weight average is generally 500-1, and 000,000; More preferably 1,000-500,000; Most preferably be 5,000-100,000.The material of preferred class can be described as " PVNO ".
The 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 measured by the photoscanning method, and as Barth etc., at " chemical analysis ", volume 113 described in " modernism of polymer characterization ", is classified this paper reference as).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, and more preferably from about 3: 1 to about 10: 1.
Detergent composition of the present invention also optionally contains the hydrophilic white dyes of about by weight some type of 0.005% to 5%, and it also provides the dye transfer restraining effect.If use, composition of the present invention preferably contains this white dyes of about 0.01%-1% by weight.
The hydrophilic white dyes of Shi Yonging has following structural formula in the present invention: R wherein 1Be selected from anilino, the two hydroxyethyls of N-2-and NH-2-hydroxyethyl; R 2Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chlorine and amino; M is a salt-forming cation, for example sodium or potassium.
When in above-mentioned formula, R 1Be anilino, R 2Be N-2-two-hydroxyethyl and M are positively charged ions, for example during sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid and disodium salt.Concrete whitening agent material is sold with trade(brand)name Tinopal-UNPA-GX by Ciba-Geigy company commercial.Tinopal-UNPA-GX is the preferred hydrophilic white dyes that is used for detergent composition of the present invention.
When in above-mentioned formula, R 1Be anilino, R 2Be that N-2-hydroxyethyl-N-2-methylamino and M are positively charged ions, for example during sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid disodium salt.Concrete whitening agent material is sold with trade(brand)name Tinopal 5BM-GX by Ciba-Geigy company commercial.
When in above-mentioned formula, R 1Be anilino, R 2Be that morpholino and M are positively charged ions, for example during sodium, whitening agent is 4,4 '-two [(4-anilino-6-morpholino-s-triazine-2-yl) amino] 2,2 '-stilbene disulfonic acid disodium salt.Concrete whitening agent material is sold with trade(brand)name TinopalAMS-GX by Ciba-Geigy commercial.
Selection is used for concrete white dyes material of the present invention provides especially effectively that dye transfer suppresses effect when being used in combination with the above-mentioned polymeric dye transfer inhibitor of this paper that selects.Comparing when the polymkeric substance of this selection (for example PVNO and/or PVPVI) uses separately with two kinds of detergent composition components of combination and this of the white dyes of selecting (for example Tinopal-UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides obviously dyestuff inhibition preferably in the aqueous solution.Although do not plan to be limited to any theory, we believe that it is because they have high fabric avidity in washing soln that these whitening agent act on by this way, thereby is deposited on the fabric relatively soon.The degree that whitening agent is deposited on the fabric in washing soln can be by the parameter-definition that is called " exhaustion coefficient ".Exhaust coefficient and be generally whitening agent material and the b that a) is deposited on the fabric) at the ratio of the initial whitening agent concentration of washing mother liquor.In the present invention, there is the whitening agent of high relatively exhaustion coefficient to be suitable for suppressing dye transfer most.
Certainly, the compound of obvious conventional white dyes type optionally is used for composition of the present invention and " brightens " effect so that fabrics in general to be provided, rather than actual dye transfer suppresses effect.It is conventional that this class is used, and is that the detergent formulation teacher is known.
Sequestrant-detergent composition of the present invention also optionally comprises one or more iron and/or manganese sequestrant.This sequestrant can be selected from aminocarboxylate, amino phosphonates do, and aromatic chelator that polyfunctional group replaces and composition thereof hereinafter will define them.Although do not want to be subjected to the limitation of any theory, we think that the effect part of these materials is because they remove iron and mn ion by the formation of water soluble chelate compound from washings.
The aminocarboxylate of useful as selective sequestrant comprises edetate, the N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, DTPMP and ethanol Diglycocol, their basic metal, ammonium and substituted ammonium salt, and composition thereof.
When allowing to use the total phosphorus of low levels at least in detergent composition, amino phosphonates do also is adapted at being used as in the present composition sequestrant, and it comprises ethylenediamine tetraacetic (phosphonic acids methylene salt), as DEQUEST.These amino phosphonates do preferably do not comprise alkyl or the alkylidene group more than about 6 carbon atoms.
The aromatic chelator that polyfunctional group replaces also is suitable for the present composition.US3812044 referring to the Connor of on May 21st, 1974 promulgation etc.This compounds of preferred sour attitude is the dihydroxyl disulfobenzene, as 1, and 2-dihydroxyl-3,5-disulfobenzene.
Being used for biodegradable preferred sequestrant of the present invention is ethylenediamine disuccinate (" EDDS "), particularly as [S, S] isomer of describing among the US4704233 of the Hartman of on November 3rd, 1987 promulgation and Perkins.
Composition of the present invention can also contain water-soluble methylglycine oxalic acid (MGDA) salt (or acid) as sequestrant or with for example water-insoluble washing assistant, for example auxiliary washing assistant that uses together such as zeolite, layered silicate.
If use, these sequestrants are generally the about 0.1%-about 15% by detergent composition weight of the present invention.More preferably, if use, these sequestrants are about 0.1%-about 3% of said composition weight.
Suds suppressor-can in the present composition, mix the compound that is used to reduce or suppress foam formation.Foamy is suppressed at the what is called of describing in US4489455 and 4489574 " high density washing methods " and is particularly important when European plan front-loading washing machine situation.
Can use various materials as suds suppressor, suds suppressor is known in those skilled in the art.Referring to, for example, KirkOthmer " encyclopedia of chemical technology ", the 3rd edition, the 7th volume, 430-447 page or leaf (John Wiley ﹠amp; Sons, Inc., 1979).The suds suppressor of one class particularly important comprises monocarboxylic acid based lipid acid and its soluble salt, referring to the US2954347 of the Wayne St.John that issues September 27 nineteen sixty.Monocarboxylic acid based lipid acid and salt thereof as suds suppressor generally have about 24 carbon atoms of the 10-of containing, the hydrocarbyl chain of preferred 12-18 carbon atom.The salt that is fit to comprises an alkali metal salt, sodium for example, potassium and lithium salts; Ammonium and alkanol ammonium salts.
Detergent composition of the present invention can also contain the suds suppressor of nonsurfactant.The example of this class suds suppressor comprises: high-molecular-weight hydrocarbons, paraffin for example, fatty acid ester (as fatty acid triglyceride), the fatty acid ester of monovalent alcohol, aliphatic C 18-C 40Ketone (as stearone) etc.Other suds suppressors comprise the alkylating aminotriazine of N-, for example three-to six-alkyl melamine or two-to the tetraalkyl diammonium chloride for triazine, they are cyanuric chloride and 2 or 3 moles of uncle or secondary amine that contain 1-24 carbon atom, propylene oxide, with single stearic alkyl phosphate salt, product as single stearic alkanol phosphoric acid ester and single stearic alkylphosphonic acid carboxylic acid two basic metal (as K, Na, and Li) salt and phosphoric acid ester.Hydrocarbon such as paraffin and halo paraffin can use with liquid form.This liquid hydrocarbon should be liquid state under room temperature and normal atmosphere, and should have-40 ℃-Yue 50 ℃ pour point approximately, and minimum boiling point is not less than about 110 ℃ (normal atmosphere).It is known using waxy hydrocarbon, and preferably it has and is not less than about 100 ℃ fusing point.Such hydrocarbon is the preferred suds suppressor of a class of detergent composition.For example in the US4265779 of the Gandolfo of on May 5th, 1981 promulgation etc., the hydrocarbon suds suppressor has been described.Therefore, this hydrocarbon comprises and contain 12 aliphatic series to about 70 carbon atoms of having an appointment, and is alicyclic, the saturated or unsaturated hydrocarbons of aromatics and heterocycle.The term that uses in the discussion of relevant suds suppressor " paraffin " comprises the real paraffin and the mixture of cyclic hydrocarbon.
The suds suppressor of another kind of preferred nonsurfactant comprises the polysiloxane suds suppressor.Comprising using organopolysiloxane oil, polydimethylsiloxane for example, the dispersion agent of polysiloxane oil or resin or emulsifying agent, and the mixture of polysiloxane and silica dioxide granule, polysiloxane wherein is through chemisorption or be fused on the silicon-dioxide.The polysiloxane suds suppressor is known in the art, for example the US4265779 of the Gandolfo of on May 5th, 1981 promulgation etc. and February 7 nineteen ninety disclosed Starch, open in the european patent application 89307851.9 of M.S..
Other polysiloxane suds suppressor is disclosed among the US3455839, and this patent relates to by mixing a small amount of polydimethylsiloxane fluid to eliminate aqueous solution foamy composition and method in composition.
The mixture of polysiloxane and silanized silica is described in as German patent application DOS2124526.Polysiloxane defoamers in granular detergent composition and Foam Control are described in the US4652392 of the US3933672 of Bartolotta etc. and the Baginski of promulgation on March 24th, 1987 etc.
Be used for of the present invention with the polysiloxane be the example of the suds suppressor of matrix be foam inhibition amount basically by the following foam suds suppressor of forming:
(i) at 25 ℃ of polydimethylsiloxane fluids with the about 1500cs of the about 20cs-of viscosity;
The polyorganosiloxane resin of (ii) per by weight 100 parts (i) about 5-50 parts (weight), this resin is by (CH 3) 3SiO 1/2Unit and SiO 2The unit is by (CH 3) 3SiO 1/2Unit and SiO 2The ratio that unitary ratio about 0.6: 1-is about 1.2: 1 is formed; With
The about 20 parts of solid silicones of (iii) per by weight 100 parts of (i) about 1-;
In the preferred polysiloxane suds suppressor that uses among the present invention, the solvent that is used for external phase is by some polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers or its mixture (preferably), or polypropylene glycol is formed.Main polysiloxane suds suppressor is side chain/crosslinked, preferably is non-straight chain.
In order to further specify this point, general liquid laundry detergent with control foaming effect contains about by weight 0.001%-about 1% usually, preferred about 0.01%-about 0.7%, the described polysiloxane suds suppressor of 0.05%-about 0.5% most preferably from about, this suds suppressor contains the nonaqueous emulsion of (1) main suds suppressor, this suds suppressor is (a) polysiloxane, (b) arborescens polysiloxane or can produce the polysiloxane compound of polyorganosiloxane resin, (c) filler in small, broken bits and (d) impel component of mixture (a), (b) and (c) reaction is to generate the mixture of silanol salt catalyst; (2) at least a nonionic silicones tensio-active agent; (3) solubleness in water surpasses the polyoxyethylene glycol of 2% (weight) or the multipolymer of polyethylene glycol-propylene glycol under the room temperature; Wherein there is not polypropylene glycol.Similarly amount can be used for particulate composition, in the gel etc.In addition referring to the US4978471 of the Starch of December 18 nineteen ninety promulgation, US4983316 with the Starch that issued on January 8th, 1991, US4639489 and 4749740, the 1 hurdles the 46th of authorizing 5288431 and the Aizawa etc. of Huber etc. on February 22nd, 1994 walk to the 4th hurdle the 35th row.
Preferred polysiloxane suds suppressor comprises among the present invention: the multipolymer of polyoxyethylene glycol and polyethylene/polypropylene glycol, their molecular-weight average are lower than about 1000, are preferably about 100-800.Solubleness under the multipolymer room temperature of polyoxyethylene glycol of the present invention and polyethylene/polypropylene glycol in water surpasses 2% (weight), preferably surpasses about 5% (weight).
It is about 1000 that the preferred solvent of the present invention is that molecular-weight average is lower than, and more preferably about 100-800 most preferably is the polyoxyethylene glycol of 200-400 and the multipolymer of polyethylene/polypropylene glycol, preferred PPG200/PEG300.Polyoxyethylene glycol: the weight ratio of polyethylene glycol-propylene glycol copolymers preferably about 1: 1-1: 10, most preferably be 1: 3-1: 6.
The polysiloxane suds suppressor that the present invention preferably uses does not contain polypropylene glycol, does not especially contain molecular weight and be 4000 polypropylene glycol.The segmented copolymer of its also preferred oxygen-free ethene and propylene oxide is as PLURONIC L101.
Other suds suppressors that the present invention uses comprise the mixture of secondary alcohol (as the 2-alkyl chain triacontanol) and these alcohol and polysiloxane oil, as are disclosed in the polysiloxane in United States Patent (USP) 4798679,4075118 and the European patent 150872. secondary alcohol comprises having C 1-C 16The C of chain 6-C 16Alkyl alcohol.Preferred alcohol is 2-butyl octanol, and this alcohol can obtain from Condea by the trade mark of ISOFOL 12.The secondary alcohol mixture can obtain from Enichem with the trade mark of ISALCHEM 123.It is 1 that the mixing suds suppressor generally contains weight ratio: 5-5: the mixture of 1 pure and mild polysiloxane.
For any detergent composition that is used for automatic washing machine, the foam of formation should not overflow washing machine.When using suds suppressor, preferably it exists with " foam inhibition amount ".The implication of " foam inhibition amount " is the prescription Shi Xuanding of composition, this amount fully control foam to obtain being used for the low foam cloth-washing detergent of automatic washing machine.
Composition of the present invention contains the suds suppressor of 0%-about 10% usually.When using monocarboxylic acid based lipid acid and its salt as suds suppressor, its consumption is the highest 5% of the detergent composition weight that is about usually.The preferred fatty monocarboxylate suds suppressor that uses about 0.5%-3%.Although also can adopt higher consumption, the consumption of polysiloxane suds suppressor the highest general about 2.0% of the detergent composition weight that is about.Because at first will consider to make cost to keep efficient minimum and the low effective control foam of consumption, this upper limit is effective.The preferred polysiloxane suds suppressor that uses about 0.01%-1%, more preferably about 0.25%-0.5%.Among the present invention, comprise whole silicon-dioxide that can use with polysiloxane and any auxiliary substance that may use in these weight percent numerical value.The consumption of single stearic alkylphosphonic suds suppressor is generally about 0.1%-about 2% of composition weight.Although can use the hydrocarbon suds suppressor of higher consumption, its consumption is generally about 0.01%-about 5.0%.The consumption of alcohol suds suppressor is generally the 0.2%-3% of final composition weight.
Alkoxylate polycarboxylate-alkoxylate polycarboxylate, for example the material by the polyacrylic ester preparation is applicable to that the present invention is to provide additional degrease performance.These materials WO91/08281 and PCT90/01815 page 4 and following in describe, classify this paper reference as.Chemically, these materials comprise the polyacrylic ester of an oxyethyl group side chain of every 7-8 acrylic ester unit, and side chain is formula-(CH 2CH 2O) m(CH 2) nCH 3, wherein m is 2-3, n is 6-12.Side chain is connected in polyacrylic ester " skeleton " so that " comb shape " polymer type structure to be provided with ester bond.Molecular weight can change, but common scope at about 2000-about 50000.Composition of the present invention can contain this alkoxylate polycarboxylate of about by weight 0.05%-about 10%.
The fabric softener of fabric softener-various experience washing whole processes, disclosed particulate montmorillonitic clay among the US4062647 of the Storm of on December 13rd, 1977 promulgation and Nirschl particularly, and other clay known in the prior art optionally is used for composition of the present invention with the content of about 0.5%-about 10% by weight, thereby makes the effect that obtains soft fabric in clean textile.The clay softening agent can be used with amine and cationic softener, as disclosed among the US4291071 of the US4375416 of the Crisp of March 1 nineteen eighty-three promulgation etc. and the Harris of promulgation on September 22nd, 1981 etc.
The spices of spices-be used for the compositions and methods of the invention and perfume composition comprise various natural and synthetic chemical compositions, and it comprises, but is not restricted to aldehyde, ketone, ester etc.Also comprise various natural extracts and essence, they can contain the complex mixture of component, for example orange oil, lemon oil, rose extract, lavandula angustifolia, Moschus, Wrinkled Gianthyssop Herb, face cream essence, santal wood oil, pine tar, cdear etc.Final spices can contain the extremely complicated mixture of these components, and detergent composition of the present invention contains the final spices of about by weight 0.01%-about 2% usually, and independent perfume composition can account for about 0.0001%-about 90% of final flavor compositions.
The limiting examples that is used for perfume composition of the present invention comprises: 7-ethanoyl-1; 2; 3; 4; 5; 6; 7; 8-octahydro-1; 1; 6; 7-durene naphthalene; irone; γ-irone; the methyl deodarone; 7-ethanoyl-1; 1; 3; 4; 4; 6-hexamethyl naphthane; 4-ethanoyl-6-the tertiary butyl-1; 1-dimethyl indane; right-the hydroxy phenyl butanone; benzophenone; methyl betanaphthyl ketone; 6-ethanoyl-1; 1; 2; 3; 3; 5-hexamethyl indane; 5-ethanoyl-3-sec.-propyl-1; 1; 2; 6-tetramethyl-indane; the 1-lauric aldehyde; 4-(4-hydroxy-4-methyl phenyl)-3-tetrahydrobenzene-1-aldehyde; 7-hydroxyl-3; 7-dimethyl octanal; 10-hendecene-1-aldehyde; dissident's thiazolinyl hexahydrobenzaldehyde; the formyl radical tristane; the condensation product of laurine and methyl ammonia fennel ester; the condensation product of laurine and indoles; the condensation product of phenyl acetaldehyde and indoles; 2-methyl-3-(right-tert-butyl-phenyl) propionic aldehyde; vanirone; heliotropine; hexyl cinnamic aldehyde; amyl cinnamic aldehyde; 2-methyl-2-(right-isopropyl phenyl) propionic aldehyde; tonka bean camphor; γ-decalone; the normuscol acid anhydride; 16-hydroxyl-palmitoleic acid lactone; 1; 3; 4; 6; 7,8-six hydrogen-4,6; 6; 7,8,8-pregnancy basic ring penta-γ-2-chromene; β-naphthalene alcohol methyl ether; ambrox alkane; ten dihydros-3a; 6; 6,9a-tetramethyl-naphtho-[2,1b] furans; cypress camphor; 5-(2; 2; 3-front three basic ring penta-3-thiazolinyl)-3-methylpent-2-alcohol; 2-ethyl-4-(2,2,3-trimethylammonium-3-cyclopentenes-1-yl)-2-butylene-1-alcohol; caryophyllenol; the tricyclic decenyl propionic ester; the tricyclo decene yl acetate; the benzyl salicylate; cdear acetic ester and right-(tertiary butyl) cyclohexyl acetic acid ester.
Especially preferred fragrance material is the material that provides maximum smell to improve at the final product composition that contains cellulase.These spices comprise, but are not restricted to hexyl cinnamic aldehyde; 2-methyl-3-(right-isopropyl phenyl) propionic aldehyde; 7-ethanoyl-1; 2,3,4; 5,6,7; 8-octahydro-1,1,6; 7-tetramethyl-naphthalene; the benzyl salicylate; 7-ethanoyl-1,1,3; 4,4,6-hexamethyl naphthane; right-the tert-butylcyclohexyl acetic ester; methyl dihydro jasmine acid esters; β-naphthalene alcohol methyl ether; methyl betanaphthyl ketone; 2-methyl-2-(right-isopropyl phenyl) propionic aldehyde; 1; 3,4,6; 7,8-six hydrogen-4,6; 6; 7,8,8-pregnancy basic ring penta-γ-2-chromene; ten dihydros-3a; 6; 6,9a-tetramethyl-naphtho-[2,1-b] furans; aubepine; tonka bean camphor; cypress camphor; vanillin food grade,1000.000000ine mesh; the normuscol acid anhydride; tricyclo decene yl acetate and tricyclic decenyl propionic ester.
Other fragrance material comprises volatile oil, resinoid and the resin that is obtained by various sources, and it comprises, but is not restricted to Surinam balsam, olibanoresin, Styrax, ladanum resin, Semen Myristicae, Oleum Cinnamomi, styrax resinoid, Fructus Coriandri oil and lavandula angustifolia element.Other flavor compounds comprises phenylethyl alcohol, terpene alcohol, linalool, linalyl acetic ester, Geraniol, vernol, 2-(1, the 1-dimethyl ethyl) adnoral acetate, benzylacetic acid ester and oxymethoxyallylbenzene.Carrier, for example diethyl phthalate can be used in the final flavor compositions.
Other components-can also include other useful in various detergent composition components in the present composition, it comprises other active ingredients, carrier, solubilizing agent, processing aid, dyestuff or pigment, the solvent of liquid formulations, the solid packing of bar composition.High if desired foam then can add as C in said 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, sultaine use together.If desired, also usually the content of 0.1%-2% add as the water soluble magnesium and/or the calcium salt of magnesium chloride, sal epsom, calcium chloride, calcium sulfate etc. add foam and improve the degrease performance to provide.
The various detergent components that use in the present composition can also be optionally by these components are adsorbed on the porous hydrophobic matrix, and then with hydrophobicity apply agent with this matrix coated with further making its stabilization.Preferably before adsorbing, this detergent component is mixed with tensio-active agent with porous matrix.In use, this detergent component is discharged into the wash water solution from matrix, finishes the washing functions of its expection.
In order to illustrate in greater detail this technology, with porous hydrophobic silicon-dioxide (trade mark SIPERNATD10, DeGussa) with contain 3%-5%C 13-15The proteolysis enzyme solution of the nonionogenic tenside of ethoxylated alcohol (EO7) mixes.The amount of this enzyme/surfactant soln generally is 2.5 times of silica weight.The gained powder (can use the various polysiloxane oils of viscosity as 500-12500) through dispersed with stirring in polysiloxane oil.Add in the final washing composition matrix with the polysiloxane oil dispersion liquid emulsification of gained or with it.By this method, above-mentioned enzyme, SYNTHETIC OPTICAL WHITNER; bleach activator, bleaching catalyst, optical active matter, dyestuff; white dyes, fabric regulator and hydrolyzable tensio-active agent can be used for washing composition with " protected form ", comprise in the liquid laundry detergent compositions.
Liquid detergent composition can contain as the water of carrier and other solvent.Lower molecular weight uncle or secondary alcohol, for example methyl alcohol, ethanol, propyl alcohol and Virahol are suitable.Be solubilizing surfactant, single hydroxyl alcohol is preferred, but also can use polyvalent alcohol, for example contains 2 to about 6 carbon atoms and 2 polyvalent alcohols to about 6 hydroxyls (for example, 1, ammediol, ethylene glycol, glycerine and 1,2-propylene glycol).Composition can contain 5% to 90%, is generally such carrier of 10% to 50%.
Composition of the present invention preferably be mixed with when its when water washing is operated, the pH6.5 of washing water is preferably about 7.5 to 10.5 to about 11.Liquid dishwashing washing formula optimization has about 6.8 to about 9.0 pH.The laundry product is generally pH9-11.Being used to control the technology of pH in needed use range and comprising use damping fluid, alkali, acid etc., is well known by persons skilled in the art.
Granules preparation
In stirring mixer, add alkoxylate cats product of the present invention,, help to remove any remnants, potential short chain amine pollutent odorous then by conventional spraying drying.The makers-up wish to prepare be used for high density granular detergent for example contain the blendable particle of alkoxylate cats product the time, particulate composition preferably is not overbasic.Preparation high-density (surpassing 540g/l) particulate method is described in US5366652.This particle can be mixed with in use has 9 or lower pH, to avoid the smell of impurity amine.This can be by adding a spot of acid source in particle, for example boric acid, citric acid etc. or suitable pH buffer reagent are realized.In other method, but the spices of the problem the application of the invention discussion relevant with the amine smell is covered.
Liquid washing agent
The heavy duty liquid laundry detergent composition can be according to US4753570,4767558,4772413,4889652,4892673 in particular for the preparation that contains the nonaqueous carrier medium of fabric washing; This paper reference is classified in GB-A-2158838, GB-A-2195125, GB-A-2195649, US4988462, US5266233, EP-A-225654 (6/16/87), EP-A-510762 (10/28/92), EP-A-540089 (5/5/93), EP-A-540090 (5/5/93), US4615820, EP-A-565017 (10/13/93), the preparation of EP-A-030096 (6/10/81) disclosed method as.Said composition can contain and stably is suspended in wherein each kind of granular detergent component (SYNTHETIC OPTICAL WHITNER for example described herein).Therefore this non-aqueous composition contains liquid phase and optionally, but solid phase preferably, all are described in detail hereinafter and in the reference of quoting.The AQD dispersion agent adds in the composition to prepare other laundry detergent composition in content and the mode of above describing.
Composition of the present invention can be used for being formed for doing washing and the aqueous cleaning solution of bleached woven fabric, and the said composition with significant quantity adds in the entry usually, preferably in the fabrics in general automatic washing machine, to form this moisture laundry/liquid lime chloride.Formed laundry/liquid lime chloride and preferred under agitation contacts with the fabric of need washing and bleaching subsequently.
The significant quantity that adds in the entry with the liquid detergent composition that forms moisture laundry/liquid lime chloride can comprise the quantity that is enough to form about 500-7000ppm in aqueous solution.More preferably in aqueous cleaning/liquid lime chloride, provide about 800-3000ppm detergent composition of the present invention.
Following embodiment is used to illustrate the present invention, but is not restriction or the scope that additionally defines it.All umbers, percentage ratio and the ratio that are used for this paper represent with weight percentage, except as otherwise noted.
In following embodiment, all content use the % by composition weight meter to represent.
Example I
Be prepared as follows liquid detergent composition:
Component Embodiment a Embodiment b Embodiment c
Weight % Weight % Weight %
C12-15 alkyl polyethoxylated (1.8) vitriol ?21.4 ?20.2 ?-
C12-15 alkyl polyethoxylated (2.5) vitriol ?- ?- ?19.0
Ethanol ?3.7 ?3.6 ?3.4
Monoethanolamine ?1.0 ?1.0 ?1.0
C10 amido propyl-dimethyl amine ?0.5 ?0.5 -
Propylene glycol ?6.8 ?6.4 ?6.2
C12-13 alkyl polyethoxylated (9) ?0.7 ?0.6 ?2.0
The C12-14 alkyl glucose amide ?2.7 ?2.5 ?3.5
C12-14 lipid acid ?2.0 ?2.0 ?2.0
Toluenesulfonic acid sodium salt ?2.3 ?2.5 ?2.5
Citric acid ?3.5 ?3.0 ?3.0
Borax ?2.5 ?2.5 ?2.5
Sodium hydroxide (to pH8.0) ?2.5 ?2.5 ?3.0
Lipolytic enzyme (100KLU/g) ?0.1 ?0.08 ?0.04
Amylase (300KNU/g) ?0.2 ?0.2 ?0.1
Carezyme(5000cevu/g) ?0.05 ?0.5 ?0.3
Proteolytic enzyme (32g/L) ?0.9 ?0.8 ?1.0
Soil release polymer * ?0.2 ?0.5 ?0.3
AQD** ?1.0 ?2.0 ?1.2
Polymine, MW600 ethoxylation (20mol EO/ nitrogen) ?1.0 ?- ?-
Water, spices, enzyme, suds suppressor, other optional ingredient of whitening agent ﹠ To 100% To 100% To 100%
* 2-[2-(2-hydroxyl-oxethyl) oxyethyl group] oligopolymer or the quaternized hexamethylene-diamine of the described mixture * of US5415807 * 24-ethoxylation of ethylsulfonic acid sodium, dimethyl terephthalate (DMT), 2-(2,3-dihydroxyl propoxy-) ethylsulfonic acid sodium, ethylene glycol and propylene glycol.
Example II
Be prepared as follows liquid detergent composition:
Component Embodiment a Embodiment b Embodiment c
Weight % Weight % Weight %
C12-15 alkyl polyethoxylated (3) vitriol ?12.5 ?21.9 ?20.0
The C12-15 alkyl-sulphate ?7.7 ?- ??-
Ethanol ?5.5 ?5.5 ?5.5
Monoethanolamine To pH7.8 To pH7.8 To pH7.8
C10 amido propyl-dimethyl amine ?1.2 ?1.2 ?1.5
Propylene glycol ?8.4 ?8.5 ?8.5
C12-13 alkyl polyethoxylated (6.5) ?2.5 ?2.8 ?2.7
The C12-14 alkyl glucose amide ?3.8 ?4.2 ?4.1
C12-16 lipid acid ?4.5 ?4.5 ?4.5
Sodium xylene sulfonate ?1.9 ?1.9 ?1.9
Citric acid ?3.0 ?3.0 ?3.0
Sodium hydroxide ?0.7 ?0.4 ?0.9
Proteolytic enzyme (32g/L) ?1.5 ?1.5 ?1.5
Amylase (300KNU/g) ?0.1 ?0.4 ?0.14
Carezyme(5000cevu/g) ?0.8 ?0.1 ?0.5
Lipolase?Ultra(100KLU/g) ?0.1 ?0.2 ?0.15
AQD* ?3.0 ?3.0 ?2.0
Polymine, MW1200 ethoxylation (7mol EO/ nitrogen) ?- ?- ?1.00
Soil release polymer * * ?0.3 0.3 ?0.3
Water, spices, enzyme, white dyes, stablizer, other optional ingredient of suds suppressor ﹠ To 100% To 100% To 100%
* the quaternized hexamethylene-diamine * of 24-ethoxylation * 2-[2-(2-hydroxyl-oxethyl) oxyethyl group] oligopolymer of ethylsulfonic acid sodium, dimethyl terephthalate (DMT), 2-(2,3-dihydroxyl propoxy-) ethylsulfonic acid sodium, ethylene glycol and propylene glycol.
EXAMPLE III
Be prepared as follows liquid detergent composition:
Component Embodiment a
Weight %
C12-15 alkyl polyethoxylated (3) vitriol ?4.0
The C12-15 alkyl-sulphate, side chain ?14.0
Ethanol ?2.2
Monoethanolamine ?4.5
C8-10 amido propyl-dimethyl amine ?1.3
Propylene glycol ?9.0
C13-15 alkyl polyethoxylated (4.0) ?4.5
The C12-14 alkyl glucose amide ?4.0
C12-16 lipid acid ?7.5
Coleseed lipid acid ?3.2
Citric acid ?1.0
Sodium hydroxide ?2.4
Proteolytic enzyme (34g/L) ?0.6
Duramyl ?0.1
Termamyl(300KNU/g) ?0.1
Carezyme(5000Cevu/g) ?0.03
Lipolase?Ultra(100KLU/g) ?0.1
Endolase(3000cevu/g) ?0.2
AQD* ?1.3
PEI?600-E20** ?1.3
Soil release polymer * * * ?0.2
Water, spices, enzyme, white dyes, stablizer, other optional ingredient of suds suppressor ﹠ To 100%
* ethoxylation polymine E20***2-[2-(2-hydroxyl-oxethyl) oxyethyl group of the quaternized hexamethylene-diamine * of 24-ethoxylation * average MW about 600] oligopolymer of ethylsulfonic acid sodium, dimethyl terephthalate (DMT), 2-(2,3-dihydroxyl propoxy-) ethylsulfonic acid sodium, ethylene glycol and propylene glycol.

Claims (10)

1. a detergent composition is characterized in that, or the preparation method is to mix the quaternized polyamine dispersion agent of one or more following formulas of significant quantity:
Figure A9718035700021
Wherein R is selected from straight or branched C 2-C 12Alkylidene group, C 3-C 12Hydroxy alkylidene, C 4-C 12Alkyl sub-dihydroxy, C 8-C 12Dialkyl group arylidene, [(CH 2CH 2O) qCH 2CH 2]-and-CH 2CH (OH) CH 2O-(CH 2CH 2O) qCH 2CH (OH) CH 2]-, wherein q is 1-100; Each R 1Be selected from C respectively 1-C 4Alkyl, C 7-C 12Alkylaryl or A; A has following formula: R wherein 3Be selected from H or C 1-C 3Alkyl, n are 5-100, and B is selected from H, C 1-C 4Alkyl, acetyl or benzoyl base; X is a water soluble anion; Described composition also contains the washing composition or the fabric nursing auxiliary component of significant quantity, and it is selected from tensio-active agent, stain remover, lipase or amylase; MW is less than 1000 polyethoxylated polyvinylamine polymers or ethoxylation polymine and their mixture.
2. the composition of claim 1, wherein R is selected from C 4-C 8Alkylidene group, R 1Be selected from C 1-C 2Alkyl or C 2-C 3Hydroxyalkyl; A is:
Figure A9718035700023
R wherein 3Be selected from H or methyl; N is that 10-50 and m are 1.
3. the composition of above-mentioned arbitrary claim, wherein R is straight or branched C 6R 1It is methyl; R 3Be that H and n are 20-50.
4. the composition that arbitrary aforesaid right requires, it is the form of particle, piece, liquid, aqueous or on-aqueous liquid or sheet.
5. the composition that arbitrary aforesaid right requires, for the on-aqueous liquid form, and wherein said tensio-active agent is a linear alkylbenzene sulfonate.
6. the composition that arbitrary aforesaid right requires, for liquid, aqueous form, and wherein said tensio-active agent does not have linear alkylbenzene sulfonate and contains alkyl-sulphate and the alkyl alkoxy sulfate tensio-active agent.
7. the composition that arbitrary aforesaid right requires, it also contains the amido propyl-dimethyl amine.
8. the composition that arbitrary aforesaid right requires, for particle form, and it also contains the polycarboxylate washing assistant.
9. the composition that arbitrary aforesaid right requires, it contains stain remover, and described stain remover contains at least 0.01% non-cotton stain remover by weight, and it is selected from the terephthalic acid salt copolymer, it contains: i) skeleton, and it contains: a) at least one has the group of following formula:
Figure A9718035700031
B) at least one has the group of following formula: R wherein 9Be C 2-C 6Straight-chain alkyl-sub-, C 3-C 6Branched alkylidene, C 5-C 7Ring alkylidene group and their mixture; R 10Be selected from respectively H or-LSO 3-M +, wherein L is the pendant moiety that is selected from alkylidene group, oxyalkylene, alkyleneoxyalkylene group, arylidene, oxygen arylidene, alkylene oxide group arylidene, poly-(oxyalkylene group), oxygen alkylene oxide group arylidene, poly-(oxyalkylene group) oxygen arylidene, alkylidene group poly-(oxyalkylene group) and their mixture; M is H or salt-forming cation; I is 0 or 1; C) at least one trifunctional forms a chain portion of ester; D) at least one 1,2-oxygen alkylene oxide group; Ii) one or more end-blockings unit, it contains: a) formula (MO 3S) (CH 2) m(R 11O) n-ethoxylation or propoxylation hydroxyethyl sulfonate or ethoxylation or propoxylation hydroxypropyl sulfonate unit, wherein M is a salt-forming cation, R 11Be ethylidene, propylidene and their mixture, m be 0 or 1 and n be 1-20; B) C (C of formula-(O) 6H 4) (SO 3 -M +) sulfo group aroyl unit, wherein M is a salt-forming cation; C) formula R 12O (CH 2CH 2O) k-modification poly-(oxyethane) oxygen monoalky lether unit, wherein R 12Contain 1-4 carbon atom, k is 3-100; And d) formula MO 3S (C 6H 4) (OR 13) nThe ethoxylation of O-or propoxylation phenolsulfonate end-blocking unit, wherein n is 1-20; M is a salt-forming cation; And R 13Be ethylidene, propylidene and their mixture; Sulfonation oligomer ester mixture, it contains the sulfonated products of the preformed oligopolymer of linear ester basically, every mole of described linear ester oligopolymer contains: i) 2 moles of end group unit, wherein the described end group of 1-2 mole unit is obtained by the unsaturated component of the alkene that is selected from allyl alcohol and methallyl alcohol, other unit that the unitary any rest part of described end group is described linear ester oligopolymer; The ii) nonionic hydrophilic unit of 1-4 mole, described hydrophilic unit is obtained by olefinic oxide, and described olefinic oxide contains the oxyethane of 50%-100%; The iii) repeating unit that obtains by aryl dicarbapentaborane component of 1.1-20 mole, wherein said aryl dicarbapentaborane component contains the dimethyl terephthalate (DMT) of 50%-100%, thereby the repeating unit that is obtained by described dimethyl terephthalate (DMT) is a terephthaloyl; The iv) 0.1-19 mole by being selected from C 2-C 4The repeating unit that the diol component of glycol obtains; The sulfonation degree of wherein said sulfonation oligomer ester mixture makes described end group unit by following group chemical modification: the v) formula-SO of 1-4 mole xThe end group unit substituting group of M, wherein x is 2 or 3, described end group unit substituting group is by being selected from HSO 3The hydrosulphite component of M obtains, and wherein M is conventional water-soluble cationic; The end-blocking terephthalic acid ester copolymer of following formula: X[(OCH 2CH 2) n(OR 5) m] [(A-R 1-A-R 2) n(A-R 3-A-R 2) v]-A-R 4-A[(R 5O) m(CH 2CH 2O) n] X wherein each A be the group that is selected from following formula:
Figure A9718035700041
With their mixture, each R 1Be selected from 1,4-phenylene and they and 1,3-phenylene, 1,2-phenylene, 1,8-naphthylidene, 1,4-naphthylidene, 2,2 '-biphenylene, 4,4 '-biphenylene, C 1-C 8Alkylidene group, C 1-C 8The combination of alkenylene and their mixture, each R 2Part is selected from ethylidene and contains C 1-C 4The ethylidene part and their mixture of the replacement of alkyl, alkoxy substituent; R 3The part be contain at least one-CO 2M ,-O[(R 5O) m(CH 2CH 2O) n] X or-A[(R 2-A-R 4-A)] w[(R 5O) m(CH 2CH 2O) n] the substituent C of X 2-C 18Alkylene; R 4Be R 1Or R 3Or their mixture; Each R 5Be C 1-C 4Alkylidene group or-R 2-A-R 6-group, wherein R 6Be C 1-C 12Alkylidene group, alkenylene, arylidene or alkarylene part, each M is H or water-soluble cationic; Each X is C 1-C 4Alkyl; Coefficient m and n make part-CH 2CH 2O-accounts for part-[(R 5O) m(CH 2CH 2O) n] by weight at least 50%, its prerequisite is to work as R 5Be-R 2-A-R 6In-time, m is 1; Each n is 10 at least, and coefficient u and v make u+v's and for 3-25; Coefficient w is 0 or at least 1; When w was at least 1, coefficient u, v and w made that the summation of u+v+w is the numerical value of 3-25 and their mixture.
10. remove the method for dirt and spot, the aqueous medium that comprises the detergent composition that makes dirt and spot and aforementioned claim or contain described detergent composition contacts.
CN97180357A 1996-10-07 1997-09-24 Alkoxylated quaternized diamine detergent ingredients Pending CN1239984A (en)

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CN116529285A (en) * 2020-12-23 2023-08-01 巴斯夫股份公司 Amphiphilic alkoxylated polyamines and uses thereof

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JP3910530B2 (en) 2002-12-16 2007-04-25 花王株式会社 Dirt release agent
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US20140308162A1 (en) 2013-04-15 2014-10-16 Ecolab Usa Inc. Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing
US9994799B2 (en) 2012-09-13 2018-06-12 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US9023784B2 (en) 2012-09-13 2015-05-05 Ecolab Usa Inc. Method of reducing soil redeposition on a hard surface using phosphinosuccinic acid adducts
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WO2015172284A1 (en) * 2014-05-12 2015-11-19 The Procter & Gamble Company Anti-microbial cleaning composition
CN106232793A (en) * 2014-05-12 2016-12-14 宝洁公司 antimicrobial cleansing compositions
CN107208361A (en) * 2015-02-06 2017-09-26 巴斯夫欧洲公司 Alkoxylate polyethyleneimine hydrophilic modifying fiber
CN107208361B (en) * 2015-02-06 2021-07-09 巴斯夫欧洲公司 Alkoxylated polyethyleneimine hydrophilic modified fiber
CN116529285A (en) * 2020-12-23 2023-08-01 巴斯夫股份公司 Amphiphilic alkoxylated polyamines and uses thereof

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TR199900753T2 (en) 1999-07-21
BR9712498A (en) 2001-12-04
WO1998015607A2 (en) 1998-04-16
AU4653397A (en) 1998-05-05
EP0929628A2 (en) 1999-07-21
HUP9904548A3 (en) 2001-11-28
CA2267294A1 (en) 1998-04-16
MA24368A1 (en) 1998-07-01
ZA978603B (en) 1998-03-18
HUP9904548A2 (en) 2000-05-28

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