CN1220694A - Fabric softener composition - Google Patents

Fabric softener composition Download PDF

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Publication number
CN1220694A
CN1220694A CN97195086A CN97195086A CN1220694A CN 1220694 A CN1220694 A CN 1220694A CN 97195086 A CN97195086 A CN 97195086A CN 97195086 A CN97195086 A CN 97195086A CN 1220694 A CN1220694 A CN 1220694A
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China
Prior art keywords
acid
fabric softener
component
mixture
softener composition
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CN97195086A
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Chinese (zh)
Inventor
R·A·A·瑟勒曼斯
F·J·M·德布罗克
B·A·J·胡贝施
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Procter and Gamble Co
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Procter and Gamble Co
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Publication of CN1220694A publication Critical patent/CN1220694A/en
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening compositions
    • C11D3/0015—Softening compositions liquid
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2082—Polycarboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • 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
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/3726—Polyurethanes

Abstract

There is provided a liquid fabric softening composition exhibiting excellent viscosity and phase stability as well as softness performance and comprising: a) from 0.01 % to 10 % by weight of a fabric softener component; b) at least 0.001 % of a thickening agent selected from the group consisting of: i) associative polymers having a hydrophilic backbone and at least two hydrophobic groups per molecule attached to the hydrophilic backbone; ii) cross-linked cationic polymers that are derivable from a water-soluble cationic ethylenically unsaturated monomer or blend of monomers which is cross-linked by 5 to 45 ppm of a cross-linking agent comprising polyethylenic functions; and iii) mixtures thereof; c) a component capable of sequestering metal ions and selected from the group consisting of: i) chelating components selected from the group consisting of amino carboxylic acid, organo aminophosphonic acid components, and mixtures thereof; ii) polycarboxylic building components, other than those defined under i) as chelating components, comprising at least two carboxylic radicals separated from each other by not more than two carbon atoms; and iii) mixtures thereof.

Description

Fabric softener composition
Invention field
The present invention relates to have the fabric softener composition of good storage stability.More particularly, the present invention relates to the liquid fabric softener composition.
Background of invention
Fabric softener composition, the particularly fabric softener composition that adopts in the rinsing operation of laundry washing are known concerning the user to make it to have softness and comfort feel.This based composition can be two kinds of forms: contain concentrate composition and the diluted composition that contains the fabric softener that is less than 10% weight greater than the fabric softener of 10% weight.
But the character that the acceptable form of the user of this based composition not only depends on these products and had also depends on relevant with it outward appearance.Therefore the viscosity of this product is the importance of the successful prescription of this class commercially available prod, the stable of the first-selected medium-high viscosity of user.So-called medium-high viscosity is meant when fabric softener composition is diluted state to be the viscosity of 50cps to 150cps, is the viscosity of 30cps 90cps when fabric softener composition is enrichment stage.
But the problem that adopts rare composition to run into is opposite with concentrate composition, and enriched material is owing to their high-content activeconstituents has " autosynergism viscosity (self-building) ", and there is the problem of unstable mutually and viscosity in diluted composition.Also there is this class problem for diluted product that has prepared or the concentrated composition when diluted.
For this reason, thickening material, for example polyacrylamide, polysaccharide or polyurethane class thickening material all have been widely used in this based composition.This compounds is disclosed in EP0422179 and EP0309052.But the problem that adopts this class thickening material to run into is must exist just with high-content for their part effective thickening effectiveness can be provided.When adopting high-content when addressing this problem, can improve the cost of said preparation.
Even the compound of association polymer class or crosslinked cation polymer class when lower concentration, also is effective thickening material.This compounds is disclosed in EP0385789 and EP0422179.But, find to use this compounds to be unfavorable for the phase stability and the viscosity performance of this product storage now, and therefore be unfavorable for the fabric-softening character of product.
Be not limited to theory, can think that this compounds can discharge negatively charged ion, they can make the balance of preparation lose stable.
This class problem more likely appears when softening compositio contains ionogen.
The applicant has now found that the component that adds a kind of component, especially specified quantitative that can chelated metal ions can address this problem.
Thickening material is meant the component with thickening properties, that is can not generate more a kind of compound of high viscosity composition under the polymkeric substance situation than not existing existing under the polymkeric substance situation in joining fabric softener composition the time.Said scope does not comprise the component with detersive power, is for example put down in writing among the US4702857.
Therefore an advantage of the invention is the composition with good phase stability and viscosity is provided.
Another advantage of the present invention provides the softening compositio with effective softening performance.
The present invention also has an advantage to provide softening compositio, and its allow to use ionogen and does not destroy the balance of preparation.
Summary of the invention
The present invention relates to a kind of liquid fabric softener composition, comprising:
A) the fabric softener component of 0.01% to 10% weight,
B) at least 0.001% thickening material, it is selected from:
ⅰ) association polymer has hydrophilic backbone and each molecule of being connected on the hydrophilic backbone has two hydrophobic groupings at least,
ⅱ) crosslinked cation polymer, they are by the preparation of water-soluble cationic ethylenically unsaturated monomer or monomeric mixture, these monomers undertaken crosslinked by 5 to 45ppm the linking agent that contains polyethylene functional group and
ⅲ) their mixture,
C) a kind of component that can chelated metal ions, it is selected from:
ⅰ) chelating component is selected from aminocarboxylic acid, organic aminophosphonic acid component and composition thereof,
ⅱ) poly carboxylic acid helps and washes component rather than ⅰ) in the component that limits as the chelating component, comprise at least two quilts be no more than carboxyl that two carbon atoms are separated from each other and
ⅲ) their mixture.
Detailed description of the invention
Fabric softener
A basal component of the present invention is the fabric softener component.That this fabric softener material can be selected from is cationic, the fabric-softening material of non-ionic type, both sexes or anionic.
The fabric softener components contents here is 0.01% to 10% weight, and the preferred fabric emollient component is 1% to 5% weight of said composition.
In general, this based composition contains the softening activeconstituents of water-soluble quaternary ammonium fabric, and the most frequently used is to have double long-chain alkyl ammonium chloride.
In recent years, more and more need to be more conducive to the material of environmental protection, and the quaternary ammonium compound of existing fast degraded biologically replaces the conventional two long-chain ammonium chlorides that use.This class quaternary ammonium compound contains long-chain alkane (alkene) base that is for example interrupted by the functional group of carboxyl.These materials are disclosed on a large amount of publications with the fabric softener composition that contains them, for example EPA040562 and EPA239910.
Quaternary ammonium compound and its amine precursor have following logical formula I or (II):
Figure A9719508600071
Or
Q is selected from-O-C (O)-,-C (O)-O-,-O-C (O)-O-,-NR 4-C (O)-,-C (O)-NR 4-;
R 1Be (CH 2) n-Q-T 2Perhaps T 3
R 2Be (CH 2) m-Q-T 4Perhaps T 5Perhaps R 3
R 3Be C 1-C 4Alkyl or C 1-C 4Hydroxyalkyl or H;
R 4Be H or C 1-C 4Alkyl or C 1-C 4Hydroxyalkyl;
T 1, T 2, T 3, T 4, T 5Be respectively C 11-C 22Alkyl or alkenyl;
N and m are from 1 to 4 integers; And X -It is the negatively charged ion that is fit to tenderizer.
The anionic non-limiting example that is fit to tenderizer comprises chlorine root or methylsulfate.
Alkyl or alkenyl, chain T 1, T 2, T 3, T 4, T 5Must contain at least 11 carbon atoms, preferably at least 16 carbon atoms.This chain can be a straight or branched.
Tallow is that use always and the cheap chain alkyl and the raw material of alkenyl material.Wherein particularly preferred compound is T 1, T 2, T 3, T 4, T 5Representative is generally the mixture of the long-chain material of tallow.
The particular instance that is applicable to the quaternary ammonium compound of aquosity fabric softener composition comprises:
1) N, N-two (tallow base-oxygen-ethyl)-N, N-alkyl dimethyl ammonium chloride;
2) N, N-two (tallow base-oxygen-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium chloride;
3) N, N-two (2-tallow base-oxygen-2-oxo-ethyl)-N, N-alkyl dimethyl ammonium chloride;
4) N, N-two (2-tallow base-oxygen-ethyl ketonic oxygen ethyl)-N, N-alkyl dimethyl ammonium chloride;
5) N-(2-tallow base-oxygen-2-ethyl)-N-(2-tallow base oxygen-2-oxo-ethyl)-N, the N-alkyl dimethyl ammonium chloride;
6) N, N, N-three (tallow base-oxygen-ethyl)-N-ammonio methacrylate;
7) N-(2-tallow base-oxygen-2-oxoethyl)-N-(tallow base-N, N-dimethyl-ammonium chloride); With
8) 1,2-two tallow base-oxygen-3-trimethylammonium aminopropane muriate; Mixture with above-mentioned any material.
Wherein compound 1-7 is logical formula I examples for compounds; Compound 8 is logical formula II examples for compounds.
Particularly preferably be N, N-two (tallow base-oxygen-ethyl)-N, the N-alkyl dimethyl ammonium chloride, wherein the tallow chain is undersaturated to small part.
The degree of unsaturation of tallow chain can be measured by the iodine number (IV) of corresponding lipid acid, and should be preferably in 5 to 100 scope under the present situation, IV be lower than or be higher than 25 for the different compound of two classes.
For being 5 to 25 by IV, the compound of the logical formula I of preferred 15 to 20 tallow fatty acid preparation, find really: weight ratio is greater than 30/70, is preferably greater than 50/50 and have the ideal condensability more preferably greater than suitable/trans isomer of 70/30.
For by the compound of IV, need very high concentration unless find the cis and the ratio of trans-isomer(ide), otherwise do not have strict the restriction greater than the logical formula I of 25 tallow fatty acid preparation.
Other example of the quaternary ammonium salt that logical formula I and (II) are suitable is by following step preparation, as:
-adopt for example coco group, palmityl, lauryl, oil base, castor-oil plant base, stearic acid-base, palmityl etc., replace in " tallow base " in the above-claimed cpd said fatty acyl chain or all saturated or preferably undersaturated to small part;
-employing ethyl, oxyethyl group, propyl group, propoxy-, sec.-propyl, butyl, isobutyl-or the tertiary butyl replace " methyl " in the above-claimed cpd;
-adopt bromide, sulfuric acid formate, formate, vitriol, nitrate to wait " muriate " that replaces in the above-claimed cpd.
In fact, negatively charged ion exists as just the counter ion of the quaternary ammonium compound of positively charged.The character of counter ion does not have strict restriction to enforcement of the present invention.Scope of the present invention is unqualified to be any specific negatively charged ion.
" precursor of its amine " is meant and corresponding secondary amine of above-mentioned quaternary ammonium compound or tertiary amine, said amine in said composition because desired pH value and basically by protonated.
For above-mentioned biodegradable fabric softener, the pH of said composition is a significant parameter of the present invention.It influences quaternary ammonium salt or amine precursor compound really, particularly the stability under long-time condition of storage.
PH is clean composition as defined herein 20 ℃ of mensuration.For the optimum hydrolysis stability of these compositions, the clean pH of Ce Dinging must be in 2.0 to 4.5 scopes under these conditions.When liquid fabric softener composition of the present invention was the dilution body, the pH of clean composition was preferably in 2.0 to 3.0 scope.The pH of these compositions can regulate by adding protonic acid.
The example of appropriate acid comprises mineral acid, carboxylic acid, particularly low-molecular-weight (C 1-C 5) carboxylic acid and alkylsulphonic acid.Suitable mineral acid comprises HCl, H 2SO 4, HNO 3And H 3PO 4Appropriate organic comprises formic acid, acetate, citric acid, methylsulphonic acid and ethylsulfonic acid.Preferred acid is citric acid, spirit of salt, phosphoric acid, formic acid, methylsulphonic acid and phenylformic acid.
Except biodegradable fabric softener, can add or add alternatively other fabric-softening material again.They can be selected from the softening material of cationic fabric, as the fabric-softening material of double long-chain alkyl ammonium chloride, non-ionic type, amphoteric or anionic.These materials are disclosed among the US4327133,4421792,4426299,4460485,3644203 and 4661269.
In general, the HLB of this class non-ionic type fabric-softening material is about 2 to 9, more preferably is about 3 to 7.This class non-ionic type fabric-softening material itself or when and other material, for example below with the single-long-chain alkyl cats product described in detail in conjunction with the time can be easy to dispersion.Dispersed can by adopt more single-long-chain alkyl cats product, with the mixture of other material that the following describes, adopt that the water and/or more stirring of heat are improved.Selected material should have reasonable crystallization, high melt point (as＞40 ℃) and suitable water-insoluble usually.
Preferred non-ionic type tenderizer is the part polyol ester of lipid acid, perhaps its acid anhydrides, and wherein alcohol or acid anhydrides contain 2 to 18, preferred 2 to 8 carbon atoms, each fatty acid part contains 12 to 30, preferred 16 to 20 carbon atoms.In general, this each molecule of class tenderizer contains 1 to 3, preferred 2 fatty acid groups.
The polyhydroxy-alcohol part of ester can be ethylene glycol, glycerine, poly-(as: two, three, four, five and/or six) glycerine, Xylitol, sucrose, tetrahydroxybutane, tetramethylolmethane, sorbyl alcohol or anhydro sorbitol.Isosorbide Dinitrate and Polyglycerine monostearate are particularly preferred.
The fatty acid part of ester generally is by containing 12 to 30, the lipid acid preparation of preferred 16 to 20 carbon atoms, the general example of said lipid acid is lauric acid, tetradecanoic acid, palmitinic acid, stearic acid and mountain Yu acid.
Be used for most preferably Isosorbide Dinitrate of optional non-ionic type tenderizer of the present invention, it is the esterification dewatered product of sorbyl alcohol, and glyceryl ester.
Commercially available Arlacel-60 is a proper raw material.The weight ratio of stearate/cetylate is about 10: 1 to about 1: 10 sorbitan monostearate and the mixture of Span 40, and 1, the 5-Isosorbide Dinitrate also is effective.
Glyceryl ester and polyglycerol ester, the monoesters of concrete preferably glycerine, two glycerine, triglycerin and Polyglycerine and/or diester are preferred, at this more preferably monoesters (for example Polyglycerine monostearate of commodity Radiasurf7248 by name).
Useful glyceryl ester and polyglycerol ester comprise and stearic acid, oleic acid, palmitinic acid, lauric acid, Unimac 5680, tetradecanoic acid and/or the monoesters of mountain Yu acid and the diester of stearic acid, oleic acid, palmitinic acid, lauric acid, Unimac 5680, mountain Yu acid and/or tetradecanoic acid.General monoesters be should understand and some diester or three esters etc. contained.
" glyceryl ester " also comprises polyglycerol ester, as two glyceryl ester to eight glyceryl ester.The many alcohol of Polyglycerine connect glycerine by ehter bond together and partly prepare by glycerine or Epicholorohydrin are condensed to.The monoesters and/or the diester of the many alcohol of preferred Polyglycerine, fatty acyl group generally is those that mention when narrating anhydro sorbitol and glyceryl ester in the above.
Thickening material
Second kind of main component of the present invention is thickening material.The general concentration of this class thickening material is at least 0.001% of composition, is preferably 0.001～3%, is 0.01-1% more preferably, most preferably is 0.1-0.5% weight.
Suitable thickening be selected from contain hydrophilic backbone and have two association polymers that are connected the hydrophobic grouping on this hydrophilic backbone at least at each molecule, by the crosslinked cation polymer of water-soluble cationic ethylenically unsaturated monomer or the preparation of monomeric mixture, said monomer is crosslinked by 5 to 45ppm the linking agent that contains polyethylene functional group, and their mixture.
Contain hydrophilic backbone and at least two association polymers that are connected the hydrophobic grouping on this hydrophilic backbone are being arranged on each molecule
Can think that for association polymer the polymerizable molecular with at least two hydrophobic parts helps thickening effectiveness.But, for the ease of actually operating, generally adopt the reaction mixture of polymerizable molecular, in this case, molecule needn't on average contain two hydrophobic groupings in this mixture; When mean value is less than two,, also can obtain satisfied result as long as the major portion of molecule contains two or more hydrophobic groupings.But preferably adopt each molecule on average to contain the polymerization reaction mixture of two or more hydrophobic groupings.
The polymeric viscosifier that uses in fabric softener composition of the present invention preferably contains non-ionic type or cationic hydrophilic backbone.The preferred polymeric thickening material is the non-ionic polyalcohol of hydrophobically modified.
The non-ionic polyalcohol of preferred hydrophobically modified is based on the material of polyoxy alkylidene or polyvinyl alcohol hydrophilic backbone, is connecting the minority alkyl on it.The example of these materials is:
(ⅰ) oxyethane and/or propylene oxide has a small amount of C 8-C 24The multipolymer of side chain for example has following basic general formula:
[R 4](4-X)-C-[CH 2O-(CH(R 5)-CH 2O) y-CH(R 6)-CH(R 7)OH]X
Each R wherein 4Be separately C 1-C 4Alkyl, preferred C 2Alkyl;
Each R wherein 5Be separately hydrogen or methyl;
Each R wherein 6, R 7Be selected from H, C respectively 8-C 24Alkyl and contain C 8-C 24The group of alkyl, preferred C 16Perhaps contain C 16The group of alkyl; Condition to each chain is R 6Or R 7In one be H, and another R 6Or R 7Be C 8-C 24Alkyl and contain C 8-C 24The group of alkyl, preferred C 16Alkyl or contain C 16The group of alkyl.
Wherein y is 20 to 1000, and is preferred 50 to 500, more preferably 200 to 400 integer;
Wherein x is 2 to 4 integer, is preferably 3.
Preferably above-mentioned associative thickener contains 10% weight that is less than that accounts for polymeric material, preferably is less than the hydrophobic grouping of 6% weight.
General formula ⅱ) associative thickener can be by the preparation of following method: at first with oxyethane or propylene oxide with generally be a kind of rudimentary olefin oxide and at least a active hydrogen-contg compound reaction that contains an active hydrogen, follow or simultaneously itself and at least a long chain aliphatic alpha-olefin oxide compound or glycidyl ether are reacted.The carbon chain lengths of said long-chain oxide compound or glycidyl ether is 8 to 24 aliphatic carbon atoms, preferred 12 to 18 carbon atoms.The said alpha-olefin oxide compound that exists in the polyethers thickening material or the amount of glycidyl ether are 1 to 20% weight based on the gross weight of thickening material.
The suitable active hydrogen-contg compound that contains at least one active hydrogen comprises MHA and polyhydroxy-alcohol initiator.Effectively the polyhydroxy-alcohol initiator is selected from alkane polyol, how pure alkene is, how pure alkynes is, how pure and mild fragrance oxyalkylene be how pure.Effective MHA initiator comprises aliphatic MHA and contain the alkylphenol of 12 to 18 carbon atoms on aliphatic series or alkyl.In addition, the aliphatic mercaptan that contains 12 to 18 carbon atoms is effective initiator.
The preferred embodiment of thickening material is general formula ⅰ) association polymer, wherein said thickening material is the polymkeric substance (80% oxyethane and 15% propylene oxide) that has the middle portion of being made by the polyolefin epoxide chain, wherein 5% hydrophobic chain is side chain (1,2-epoxy n-Hexadecane).
General formula ⅰ more preferably) thickening material mixes with the tensio-active agent of ethoxyquin.In this case, the alcohol of ethoxyquin can change aspect the degree of chain length and ethoxyquin or their any mixture to some extent.The preferred embodiment of the tensio-active agent of ethoxyquin is Lutensol T08 TM, average ethoxyquin degree is 8 C 13Ethoxylated alcohol is provided by BASF.General formula ⅰ) the thickening material and the tensio-active agent of ethoxyquin are preferably with polymkeric substance and Lutensol T08 TMRatio be that 25: 75 amount exists.
The preferred embodiment for preparing said thickening material is as follows:
According to the following steps preparation contain 80% weight ring oxidative ethane residue, 15% weight 1, the residue of 2-propylene oxide and 5% weight contain the liquid copolymer of residue of alpha-olefin oxide compound that length is the aliphatic carbochain of 15 to 18 carbon atoms.By prepared in reaction is by oxyethane and 1 in stainless steel autoclave in two steps with TriMethylolPropane(TMP), the 2-propylene oxide is with 1 of 75% oxyethane and 25%, the polyethers that the weight ratio of 2-propylene oxide is made.First intermediate product is by trimethylammonium alcohol, potassium hydroxide, 1, and the mixture of 2-propylene oxide and oxyethane was made 120 ℃ of reactions in 18 hours.Final product be by in second step with the intermediate product and 1 for preparing previously, the mixture of 2-propylene oxide and oxyethane under nitrogen atmosphere 115 ℃ the reaction 22 hours the preparation.The molecular weight of this product is 23000.
The final polyether products of the above-mentioned preparation of 1410 grams is put into a glass flask and is heated to 105 ℃, keep nitrogen atmosphere simultaneously.Then under stirring state, add 10.2 gram sodium and made mixture reaction 24 hours.With the intermediate product cool to room temperature before using that obtains.Afterwards, together with 3.3 grams 1,2-propylene oxide and 19 gram oxyethane join in one 250 milliliters the centrifugal bottle with 100 these intermediate products of gram.The content of this bottle is at room temperature mixed, and after clogging this bottle, bottle was placed in the vapor bath 24 hours with rubber plug.Before further using with this product cool to room temperature.In the centrifugal bottle that contains this product, add alhpa olefin oxide compound and 3.3 grams 1 that 2.5 length that restrain aliphatic carbochain are 15 to 18 carbon atoms, 2-propylene oxide and 19 gram oxyethane.Content in the hybrid bottle is lived bottle stopper once more, is placed in the vapor bath 21 hours, obtains the thickness product afterwards.
(ⅱ) oxyethane and/or propylene oxide and a spot of C 8-C 24The multipolymer of side chain for example has following basic general formula:
Figure A9719508600131
Group-(CH wherein 2CH 2O) n(C pH 2PCH 2O) m-by at least two R 1Group replaces, can be at any CH along main polymer chain 2Be substituted on the group;
(ⅲ) hydrophobically modified poly-(oxyethane and/or propylene oxide/urethane) for example has following general formula:
Figure A9719508600132
Group-(CH wherein 2CH 2O) n(C pH 2PCH 2O) m-by at least two R 1Group replaces, can be at any CH along main polymer chain 2Be substituted on the group; With
(ⅳ) poly-(vinyl) alcohol of alkyl replacement for example has following general formula:
Figure A9719508600133
Group-(CH wherein 2CHOH) n-by at least two R 1Group replaces, can be at any CH along main polymer chain 2Be substituted on the group; With
Wherein arrive (ⅵ) for general formula (ⅱ):
N=is greater than 10
P=1 to 4, preferred 1 or 2
N+m=is greater than 10
If m=p is greater than 1, m makes related group constitute 50 moles of polymkeric substance below the %, preferred 25 moles below the %.
R 1=C 8-C 24Wire or branched-chain alkyl or alkenyl
R 2=hydrogen or C 8-C 24Wire or branched-chain alkyl or alkenyl
R 3=at least two R 1Group can be at any CH along main polymer chain 2The group place is substituted.
The hydrophobically modified of general formula (ⅲ) poly-(oxyethane and/or propylene oxide/urethane) is to be sold with UCAR SCT trade mark by UNION CARBIDE, is used for the thickening latex system, and molecular weight is about 40000 usually.
The number that preferably is connected the hydrophobic grouping on the hydrophilic backbone for the compound of general formula (ⅱ) to (ⅳ) is fewer.Hydrophobic grouping preferably constitutes below 5% weight of polymkeric substance, more preferably between 0.5～2% weight.Preferred hydrophobic grouping is alkyl wire or side chain or alkenyl, and the length of preference chain is less than 40, more preferably between 8 and 24 carbon atoms.
Other is the acrylic acid polymer of hydrophobically modified based on the hydrophobically modified non-ionic polyalcohol (wherein being connected with a spot of alkyl) of polyoxy alkylidene hydrophilic backbone preferably, for example poly-alkyl acrylic, be Viscalex, Rheovis CRX, RheovisCR, the Rheovis CR2 that provides by Allied Colloid, by Rohm ﹠amp; The Acusol 810 that Haas provides, Acusol 820, Acusol 823, Acusol 830, Acusol 842.
The preferred molecular weight of adoptable above-mentioned thickening material material is preferably greater than 10000, and more preferably from 10000 to 1000000, more preferably from 15000 to 100000, especially preferably from 20000 to 70000.
By the crosslinked cation polymer of water-soluble cationic ethylene linkage unsaturated monomer or monomeric mixture preparation, these monomers are crosslinked with 5 to 45ppm the linking agent that contains polyethylene functional group
Crosslinked cation type polymer (claiming " CP " later on) is to be made by the unsaturated monomer of monoethenoid, this monomer is water miscible cationic monomer, or the monomeric cationic mixture that only is made of cationic monomer or by cationic mixture cationic and that nonionic monomers constitutes at the mixture that exists under the situation of linking agent.If adopt monomeric mixture so the part of mixture can be low water solubility, as long as this mixture is water miscible.This monomer can be the propenyl monomer, generally is vinyl, preferably vinylformic acid.
Cationic polymers can be by containing one or more (a) dialkyl aminoalkyl-acrylate or methacrylic ester, (b) dialkyl aminoalkyl-acrylamide or Methacrylamide and (c) the cationic monomer preparation of (a) or quaternary salt (b) or acid salt, for example Methacrylamide oxypropyl trimethyl ammonium chloride and Manny phase product, for example quaternized dialkyl amido Methacrylamide.Alkyl generally is C 1-C 4Alkyl.
Suitable nonionic monomers is acrylamide, Methacrylamide, N-vinyl pyrrolidone and low alkyl group water-insoluble vinylformic acid (perhaps other ethylene linkages are unsaturated) monomer, for example methyl methacrylate, vinylbenzene or vinyl cyanide, they can be very a spot of, so that this mixture is soluble.
5～90%, the acrylamide of preferred 5-50% and dialkyl aminoalkyl acrylate, perhaps preferably with acid-adducting salt or season the adduct form-methacrylic ester, perhaps the mixture of cationic homopolymer (not containing the acrylamide group) is preferred.
This monomer can contain hydrophobic grouping, puts down in writing as EP-A-0172723, for example the 10th page of specification sheets.If this monomer is in order to make this polymkeric substance increase solvability, if there is oxyethyl chain, can to shorten, perhaps not having, i.e. n=0.Allyl ether monomers is particularly preferred.
Cationic polymers must be with granularity less than 10 microns, preferably add less than 2 microns particulate form.This can prepare by pulverizing crosslinked polymer sol, but preferred particulates is made with cross-linked state at first.The form of these particles with decomposable aggregation or sheet can be joined in the aqueous solution, but preferably add with the liquid dispersion form, generally be non-aqueous liquid, as hydrocarbon.This dispersion can still preferably exist the reverse polymerization under the situation to prepare by monomer or monomer mixture at linking agent by ready-made particles dispersed is prepared in liquid.
The unsaturated raw material of monoethenoid can be doped with a spot of linking agent, and can select to add a certain amount of additive-crosslinking agent in view of the above.The preferred unsaturated raw material of monoene key does not have linking agent as industrial conforming to possible, and for example the amount of the contained linking agent branching that will make crosslinked or chain is less than contain the amount that linking agent produced that is useful on polyethylene of the present invention functional group as 1ppm.Here the used term " polyethylene functional group " with in the specification sheets is meant that each molecule of linking agent has the linking agent of two or more ethylenically unsaturated groups.Therefore, the example of this class linking agent is methylene-bisacrylamide (Wen Zhongwei " MBA ").Contain polyethylene functional group, as the add-on of the linking agent of MBA be at least 5ppm to 45ppm (based on monomer), generally be 10 to 40ppm.Accurate amount will depend on polyreaction and other processing condition.Replace adopting MBA, obtain crosslinked other two ethylene linkages unsaturated compounds that can pass through empoly effective amount, as glycol diacrylate, diacrylamine, cyano methyl acrylate, vinyl oxygen ethyl propylene acid esters or methacrylic ester and other crosslinking methods, as adding formaldehyde or oxalic dialdehyde or metal-salt.Water-soluble cross-linked dose of preferred employing.
Nonlinear degree can also be controlled by add chain-transfer agent in polymerization reaction mixture.They are used in combination the branching that can impel chain with linking agent, rather than crosslinked.This amount can change in wide region.For example 1000 to the medium chain-transfer agent of 5000ppm (based on monomer), is suitable as Virahol, and more a small amount of, generally is 100 to 500ppm more effective chain branching agent, is effective as mercaptoethanol.But, adopt the MBA of commercially pure monoethylenically unsaturated monomer and specified quantitative or other linking agents by under normal condition, carrying out polyreaction usually, and need not deliberately to add chain-transfer agent, also can obtain goodish result.
Preferred CP normally adopts dialkyl amido ethyl-methyl vinylformic acid quaternary salt (20% acrylamide for example of the acrylamide that is up to 40%w/w and 100 to 60%w/w, 80% dimethyl aminoethyl methacrylic acid quaternary salt) with 10 to 40ppm, the MBA of preferred 10～30ppm or other linking agents are cross-linked to form.All shares and percentage are weight.Can determine by observing the character of said composition when adopting the CP thickening of selected amount for the optimum quantity of any particular composition, CP by 5 in the 45ppm scope amount of change MBA and differing from each other.
The condition optimization of polyreaction is a polymkeric substance wherein, if uncrosslinked, has high molecular in theory, is 500 ten thousand to 3,000 ten thousand, and intrinsic viscosity (this paper is IV) is higher than 4, preferably is higher than 6, as up to 10 or 15dl/g.If this polymkeric substance is crosslinked (CP), preferred polymeric is not for there to be linking agent to have the such molecular weight that forms under the situation.But crosslinked meeting reduces IV, but as following illustrated, then shearing can make IV improve.
In the emulsion of reverse polymerization reaction mixture, granularity can be by being used for monomeric shear rate and by existing emulsifying agent to control.When polymerization water-soluble monomer not for example, as acrylate or water insoluble but be dissolved in acid monomer, during as amine (CP of generation is dispersed in the acidic aqueous compositions), can adopt emulsion polymerization, but, when monomer or monomer mixture are water-soluble, generally adopt inverse emulsion polymerization reaction or suspension polymerization.Water-containing monomer is emulsified into suitable on-aqueous liquid, generally has oil-water emulsifiers to exist, its amount subcritical micellar concentration.The particular content of emulsifying agent, stablizer, non-aqueous liquid and other reverse phase polymerisation reaction raw materials and method for example is documented among the EP-A-0126528.The CP particle can dewater, and for example dispersion is carried out component distillation.
From the general direct use of product liquid of reverse phase polymerisation reaction or emulsion polymerization, and separation of polymeric composition granule therefrom not, but if desired, can from dispersion, separate dried polymer pellets with currently known methods.Because these dried particles are finely powdered, they preferably are made into to add the resolvent tablet of entry.
Can with the emulsion of the oily packet aggregation thing that generates by reverse phase polymerisation reaction have oil-water emulsifiers to exist under the situation to join with ordinary method will be by the composition of thickening in.
When polymer raw is crosslinked with cationic, and particularly working as it is acrylamide and at least 5%, during the multipolymer of the propenoic acid dialkyl aminoalkyl ester (generally as acid-adducting salt or quaternary amine) of preferred at least 10% weight, the ion that nonlinear degree is preferably CP reclaims (IR) and is at least 15%.IR calculates with (x-y/x) 100, and wherein x is the ionization degree of measuring after the employing standard is sheared, and y is the ionization degree of polymkeric substance before the employing standard is sheared.
These values preferably by make 1% the composition of CP in deionized water, are placed them 2 hours, and redilution becomes to contain 0.1% active CP to be measured.The ionization degree of CP, y is by measuring in the Colloid Titration method that its disclosed 4/77 KLCD-1 is put down in writing as Koch-Light Laboratories Limited.
(optional approach of putting down in writing among the GB-A-1579007 can be used for measuring y).Ionization degree x after shearing can determine by adopting the ionization degree of this solution of same technical measurement after carrying out the standard shearing.
It is 200 ml solns in the container cylindraceous basically that this shearing is preferably used in, and the diameter of this container is about 8 centimetres, and have rotatable diameter in its bottom be 6 centimetres blade, and an arm of blade upwards is about 45 degree, and another is 45 degree downwards.About 1 mm thick of this blade, and in the bottom of container with 16500rpm rotation 10 minutes.These conditions are preferably by adopting the Moulinex homogenizer to provide, and other gratifying conditions can be by adopting kitchen mixer, provide as Kenwood, Hamilton Beach, Iona or the Osterizer of Waring Blender.
In fact, the accurate condition of shearing is inessential comparatively speaking, this is because as long as degree and the determined size sheared are the same order of magnitude, will find the very big influence of the big variation that IR can the amount of being subjected to, time length of Jian Qieing for example, and when shearing displacement is low (for example at 16500rpml minute), IR can be subjected to shearing the influence of a small amount of variation to a great extent.Therefore in general, x value is to make the ionization degree change little or definite when further not changing when adopting the high speed blade, further shearing.It generally needs to shear 10 minutes, but needs the long time sometimes, as the time that may need to be thirty minutes long under the cooling conditions.
Be used for the preferred IR of CP of the present invention and be higher than 30%, generally 35～45%.IR is zero peak value or the flat-top of bringing up at for example linking agent about 10-25ppm of linking agent never, and preferred IR or near this peak value or flat-top, generally be low-level when degree of crosslinking and high IR value are consistent.
The preferred embodiment of crosslinked polymkeric substance is as follows:
Prepare reverse dispersion by being distributed in the conventional anti-phase non-aqueous liquid that contains emulsifying agent and amphipathic stablizer by the water-containing monomer mixture that the dimethyl amino ethyl methacrylate Methochloride quaternary salt of 80% weight and 20% acrylamide and 15ppm methylene diacrylamine constitute.With the degassing of this mixture and cause in a usual manner and polyreaction is carried out fully.Then mixture is carried out component distillation, with polymer beads the substantially anhydrous dispersion in mineral oil (50%w/w) of generation granularity less than 2 microns, this mineral oil is Shell oil 60Solvent Pale.
Preferred industrial representational crosslinked cation polymer is the BP 7050 from BP Chemicals TM
Component that can chelated metal ions
The third main component of the present invention is the component with chelating character, and it can play the effect of chelated metal ions.This class component can be selected from chelating component, poly carboxylic acid synergy component and their mixture.
A. chelating component
The amount of chelating component is at least 0.001% (10ppm) of composition, and preferred 0.001% (10ppm) be to 0.5%, more preferably 0.005% to 0.25%, and 0.01% to 0.1% weight most preferably.
Be used for suitable chelating component of the present invention and be selected from aminocarboxylic acid, organic aminophosphonic acid compound and their mixtures.
Chelating component with acid state of phosphonic acids for example or carboxylic acid functional, can exist with its sour form, perhaps with suitable counter cation mutually, exist as the form of the title complex/salt of the ammonium ion of basic metal or alkaline-earth metal ions, ammonium or replacement or their any mixture.Preferred all salt/title complexs are water-soluble.The molar ratio of said phase counter cation and chelating component preferably at least 1: 1.
Here used suitable chelating component comprises aminocarboxylic acid, as ethylene diamine-N, N '-two Succinic Acid (EDDS), ethylene diaminetetraacetic acid (EDTA), N-hydroxy ethylene ethylenediamine triacetic acid, nitrilotriacetic acid(NTA) (NTA), ethylene diamine four propionic acid, ethylene diamine-N, N '-two L-glutamic acid, 2-hydroxy propylidene diamines-N, N '-two Succinic Acid, triethylenetetraaminehexaacetic acid, diethylene triaminepentaacetic acid(DTPA) (DETPA), anti-1,2-diamino-cyclohexane-N, N, N ', N '-tetraacethyl or ethanol Diglycocol.
Here the chelating component that other of Cai Yonging are suitable comprises organic aminophosphonic acid, as ethylene diamine four (methylene phosphonic acid), diethylenetriamine-N, N, N '; N "; N "-five (methylene phosphonic acids) (DETMP), 1-hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid (HEDP) or hydroxyl ethane dimethylene phosphonic acids.
Also can adopt any mixture of above-mentioned chelating component.
Particularly preferably be ethylene diamine-N, N '-two Succinic Acid (EDDS), most preferably with S, the form of S isomer exists, and it is preferred to its biodegradable form.
B poly carboxylic acid synergy component
The amount that poly carboxylic acid synergy component exists is at least 0.01% (10ppm) of composition, is generally at least 0.045% (450ppm), is preferably 0.045% to 0.5%, more preferably 0.09% to 0.25%, most preferably be 0.1% to 0.2% weight.
Here the suitable poly carboxylic acid synergy component that is adopted can be monomer or oligopolymer, although monomeric polycarboxylates is usually owing to the reason of price and performance is preferred.
The poly carboxylic acid that contains two carboxyls comprises Succinic Acid, propanedioic acid, (ethylidene dioxy) oxalic acid, toxilic acid, Glycerol dimer acid, tartrate, tartronic acid and fumaric acid, and ether carboxylic acid and sulfinyl carboxylic acid.The poly carboxylic acid that contains three carboxyls can be particularly including citric acid, equisetic acid and citraconic acid and butanedioic acid derivative, carboxyl methyl oxygen Succinic Acid described in English Patent 1379241, the newborn oxygen Succinic Acid (lactoxysuccinic) described in the English Patent 1389732, the oxypolymerization carboxylic acid material of record in the amino-succinic acid of record and the English Patent 1387447 in Holland's application 7205873, as 2-oxa--1,1, the 3-tricarballylic acid.
The poly carboxylic acid that contains four carboxyls comprises the oxygen di-Succinic Acid, 1,1,2 that is disclosed in the English Patent 1261829,2-ethane tetracarboxylic acid, 1,1,3,3-propane tetracarboxylic acid and 1,1,2,3-propane tetracarboxylic acid.Contain the substituent poly carboxylic acid of sulfo group comprise be disclosed in English Patent 1398421 and 1398422 and United States Patent (USP) 3936448 in sulfosuccinate derivant, and in the English Patent 1439000 record sulfonated pyrolysis citric acid.
Alicyclic ring comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid, cyclopentadiene pentacarboxylic acid, 2,3,4 with the heterocycle poly carboxylic acid, 5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetracarboxylic acid, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylic acid, 2,2,5,5-tetrahydrofuran (THF)-tetracarboxylic acid, 1,2,3,4,5,6-hexane-hexacarboxylic acid, and polyvalent alcohol, for example the carboxyl methyl-derivatives of sorbyl alcohol, mannitol and Xylitol.The fragrance poly carboxylic acid comprises benzene hexacarboxylic acid, 1,2,4,5-pyromellitic acid and the phthalic acid derivative of record in the English Patent 1425343.Although citric acid can use, not preferred for purpose of the present invention.
In the above-mentioned acid, preferred poly carboxylic acid is that each molecule contains the carboxylic acid that is up to three carboxyls, particularly toxilic acid.
Another component of the present invention is a liquid vehicle.Be applicable to that liquid vehicle of the present invention is selected from water, organic solvent and their mixture.The liquid vehicle that is used for instant compositions preferably at least at first is a water, this be because its low cost, relatively easily obtain, safe and environmentally acceptable.The content of water in liquid vehicle preferably accounts at least 50%, most preferably the carrier of at least 60% weight.Water and lower molecular weight, the organic solvent as＜200 as lower alcohol, can be used as carrier liq as the mixture of ethanol, propyl alcohol, Virahol or butanols.Low-molecular-weight alcohol comprises MHA, dihydroxy alcohol (1 etc.), trihydroxy-alcohol (glycerine etc.) and senior poly-hydroxy (polyvalent alcohol) alcohol.
Optional component
The tensio-active agent concentrated assistant
Also can randomly adopt the surfactant concentrate auxiliary agent.The surfactant adjuvant enriched material generally is selected from single-long-chain alkyl cats product, nonionogenic tenside, amine oxide, lipid acid and their mixture, and general concentration is 0 to 15% of composition.
The single-long-chain alkyl cats product
This class can be effective to single-long-chain alkyl cats product of the present invention preferably general formula be: [R 2N +R 3] X -Quaternary ammonium salt, R wherein 2Group is C 10-C 22Alkyl, preferred corresponding ester chain is by the short alkylidene group (C between ester chain and N 1-C 4) C that interrupts 12-C 18Alkyl, and have similar alkyl, as the fatty acid ester of choline, preferably have the C of 0.1% to 20% weight of softening active ingredient 12-C 14(coconut) cholinesterase and/or C 16-C 18The butter cholinesterase.Each R is C 1-C 4Alkyl or replacement (as hydroxyl) alkyl or hydrogen, preferable methyl and gegenion X -Be the compatible negatively charged ion of tenderizer, for example chlorion, bromide anion, methyl sulfate etc.
Also can adopt other cationic substance that has ring structure, as have C 12-C 30The alkyl imidazoline of alkyl strand, tetrahydroglyoxaline, pyridine and pyridinium salt.The low-down pH of needs stablizes the ring texture such as tetrahydroglyoxaline.
Some can be used for alkyl imidazoline salt of the present invention and their tetrahydroglyoxaline precursor has following general formula:
Figure A9719508600201
Y wherein 2Be-C (O)-O-,-O-(O) C-,-C (O)-N (R 5)-or-N (R 5)-C (O)-, R wherein 5Be hydrogen or C 1-C 4Alkyl; R 6Be C 1-C 4Alkyl or hydrogen (for the tetrahydroglyoxaline precursor); R 7And R 8Be selected from respectively as above for described R of single long chain cation tensio-active agent and R2, but have only one to be R 2
Some can be used for Fixanol of the present invention and have following general formula:
Figure A9719508600211
R wherein 2And X -As mentioned above.Typical this class material is a pyrisept.
Nonionic surface active agent (alkoxylate material)
Here can be used for suitable nonionic surface active agent of the present invention and comprise oxyethane and the adduction product of propylene oxide and Fatty Alcohol(C12-C14 and C12-C18), lipid acid, aliphatic amide etc. randomly.
Suitable compound is water-soluble basically tensio-active agent, and general formula is:
R 2-Y-(C 2H 4O) z-C 2H 4OH
R wherein 2Be selected from primary, secondary and branched alkyl and/or acyl group alkyl; The primary, the second month in a season and branched alkenyl alkyl; And primary, secondary and branched alkyl-and the phenol alkyl that replaces of alkenyl; The alkyl chain length of said alkyl is 8 to 20, preferred 10 to 18 carbon atoms.
Y generally is-O-,-C (O) O-,-C (O) N (R)-or-C (O) N (R) R-, wherein there is R 2During with R, they have the implication that the front is given, and/or R can be hydrogen, and z is 8 at least, preferably 10-11 at least.
Nonionogenic tenside is characterised in that HLB (hydrophile-lyophile balance) is 7 to 20, preferably from 8 to 15.
The example of specially suitable nonionic surface active agent comprises
-straight chain, primary alconol alcoxylates are as tallow alcohol-EO (11), tallow alcohol-EO (18) and tallow alcohol-EO (25);
-straight chain, secondary alcohol alkoxylates are as 2-C 16EO (11), 2-C 20EO (11) and 2-C 16EO (14);
-alkylphenol alkoxylates, as to three decyl phenol EO (11) with to five decyl phenol EO (18), and
-olefinic alkoxide and branched alkane oxide compound, as branched primary alconol and secondary alcohol, they are provided by known " OXO " method.
Amine oxide
Suitable amine oxide comprises that having one has 8 to 28 carbon atoms, and the alkyl of preferred 8 to 16 carbon atoms or hydroxyalkyl and two are selected from the alkyl that has 1 to 3 carbon atom and the alkyl of hydroxyalkyl.
Example comprises dimethyl octyl group amine oxide, diethyl decyl amine oxide compound, two-(2-hydroxyethyl) dodecyl amine oxide, dimethyl dodecyl amine oxide, dipropyl tetradecyl amine oxide, methylethyl hexadecyl amine oxide, dimethyl-2-hydroxyl octadecyl amine oxide and coconut fat alkyl dimethyl amine oxide.
Lipid acid
Suitable fatty acids comprises that total carbon atom number is 12 to 25, preferred 16 to 20 lipid acid, and wherein Zhi Fang part contains 10 to 22, preferred 15 to 17 carbon atoms (the middle cut-out).
The ionogen concentrated assistant
Composition of the present invention also optionally contains one or more ionogen.Have been found that when the ionogen concentrated assistant being joined containing thickening material but when not having in the softening compositio of chelating component, can increasing when storing mutually and the viscosity problem of unstable of dilution.Be that composition of the present invention allows to adopt the ionogen concentrated assistant unexpectedly, and phase and viscosity stability when still having good storage.
The ionogen concentrated assistant, as inorganic viscosity control agent, it also can play and be similar to or the effect of enhanced tensio-active agent concentrated assistant, comprises water miscible ionogenic salt.These inorganic viscosity control agents also can randomly be attached in the composition of the present invention.These components are joined in the said composition and must carry out with speed very slowly.Can adopt ionizable widely salt.The example of suitable salt is the I A of the periodic table of elements and the halogenide of II A family metal, as Repone K, calcium chloride, magnesium chloride, sodium-chlor, Potassium Bromide and lithium chloride.Prepare that to adopt ionogenic salt in the process of said composition be useful especially mixing these components, and can obtain required viscosity.The amount of used ionizable salt depends on the amount of the active constituent that is used for said composition, and can adjust according to preparation teacher's wish.The general concentration that is used for the salt of control combination thing viscosity is 20 to 20000 parts (ppm) of each 1,000,000 parts of composition weight, preferred 20 to 11000ppm.
The poly-ammonium salt of alkylidene group can be joined in the said composition with control viscosity, can be to add or replace above-mentioned water miscible ionizable salt in addition.In addition, these reagent can be used as scavenging agent, and by forming ion pair at the main anionic detergent of washing in the process, in rinsing and on fabric of bringing into, and can improve softness.These reagent compare with inorganic electrolyte can be in wide temperature range stable viscosity, particularly at low temperatures.
The object lesson of the poly-ammonium salt of alkylidene group comprises 1-Methionin monohydrochloride and 1,5-two ammonium 2-methylpentane dihydrochlorides.
Still having other optional components is stablizer, antioxidant and reductive agent as is well known, soil release polymer, emulsifying agent, sterilant, tinting material, spices, protective material, white dyes, anti-ionic agent, foam reducing composition and enzyme.
Randomly be responsive component, can come in the porous hydrophobic material to separating its hostile environment by said compound is reversibly absorbed as spices or enzyme.By this way with " cage " of porous hydrophobic material as coated responsive component.As a result, the hole of the porous hydrophobic material of filling seals by this porous material is distributed in the hydrophobic liquid.
By the hole of sealing hydrophobic material, hydrophobic liquid plays the effect of " shell ", therefore; protect responsive component not to be subjected to the influence of its environment; reduced active loss, this being lost in the hostile environment can run into, and can not reduce responsive component and bring into play its normal function.Should be disclosed in to " shell and cage " system illustrative EPA0583512.
The present invention illustrates with following indefiniteness embodiment, and wherein all percentage are based on weight, unless stated otherwise.
Embodiment 1
The fabric softener composition 1 and 2 of prior art below the preparation
Composition 1 Composition 2
DEQA(1) 20 ?18
Spirit of salt 0.02 ?0.02
Lipid acid (2) - ?1.0
Spices 1.0 ?-
Ionogen (3) 0.20 ?0.06
The silicon antifoams 0.01 ?0.01
Dyestuff 0.005 ??-
Macrogol 4000 ?1.0 ?0.60
Water and minor component constitute 100
(1) two-(tallow oxygen ethyl) alkyl dimethyl ammonium chloride
(2) stearic acid IV=O
(3) calcium chloride
Currently known methods according to the preparation fabric softener composition prepares these compositions, for example by fusion DEQA being injected into the hot water bath (60-70 ℃) that contains minor component, then add ionogen lentamente, add spices then, again product is cooled off until required viscosity.
Then, with 4 times of the product of composition 1 dilutions and add as thickening materials that following (5) limit, and 2 times of the product of composition 2 dilutions add the BP7050 that BP Chemicals provides again TMThough the fabric softener composition of the dilution that generates be freshly prepd or stored all have good viscosity and a phase stability.
The prescription of dilution is as follows:
Composition 3 Composition 4
Composition 1 25 50
Spirit of salt - ?-
Toxilic acid 1200ppm ?-
DETMP(4) - 750ppm
Thickening material (5) 0.25 -
BP7050TM(6) - 0.3
Dyestuff - 7.5ppm
Spices - 2.0
Water To 100 To 100
(4) diethylenetriamine-N, N, N ', N ", N " and-five (methylene phosphonic acids)
(5) multipolymer of oxyethane and/or propylene oxide, it has above-mentioned a small amount of C 8-C 24Side chain, it is branched that 5% hydrophobic chain (1,2-epoxy n-Hexadecane) is arranged on the centre portions that is formed by polyalkylene oxides chain (80% oxyethane and 15% propylene oxide) wherein, said multipolymer and Lutensol T08 TMWith multipolymer and Lutensol T08 TMIt is 25: 75 mixed.
(6) BP7050 that provides by BP Chemicals TM

Claims (14)

1. liquid fabric softener composition, contain:
A) the fabric softener component of 0.01% to 10% weight,
B) at least 0.001% thickening material, it is selected from:
ⅰ) association polymer has hydrophilic backbone and has at least two hydrophobic groupings with each molecule that is connected on the hydrophilic backbone,
ⅱ) crosslinked cation polymer, they are by the preparation of water-soluble cationic ethylene linkage unsaturated monomer or monomeric mixture, these monomers by 5 to 45ppm the linking agent that contains polyethylene functional group crosslinked and
ⅲ) their mixture,
C) a kind of component that can chelated metal ions, it is selected from:
ⅰ) chelating component is selected from aminocarboxylic acid, organic aminophosphonic acid component and their mixture,
ⅱ) poly carboxylic acid helps and washes component rather than ⅰ) in the component that limits as the chelating component, contain at least two quilts be no more than hydroxy-acid group that two carbon atoms are separated from each other and
ⅲ) their mixture.
2. the fabric softener composition of a claim 1, wherein said component that can chelated metal ions is the sequestrant that is selected from aminocarboxylic acid, organic aminophosphonic acid compound and their mixture.
3. the fabric softener composition of a claim 2, wherein said chelating component is an aminocarboxylic acid, be selected from ethylene diamine-N, N '-two Succinic Acid, ethylene diaminetetraacetic acid, N-hydroxy ethylene ethylenediamine triacetic acid, nitrilotriacetic acid(NTA), ethylene diamine four propionic acid, ethylene diamine-N, N '-two L-glutamic acid, 2-hydroxy propylidene diamines-N, N '-two Succinic Acid, triethylenetetraaminehexaacetic acid, diethylene triaminepentaacetic acid(DTPA), anti-1,2-diamino-cyclohexane-N, N, N ', N '-tetraacethyl, ethanol Diglycocol and their mixture, preferred ethylene diamine-N, N '-two Succinic Acid.
4. the fabric softener composition of a claim 2, wherein said chelating component is organic aminophosphonic acid, be selected from ethylene diamine four (methylene phosphonic acid), diethylenetriamine-N, N, N ', N "; N "-five (methylene phosphonic acids), 1-hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid, hydroxyl ethane dimethylene phosphonic acids and their mixture, preferred 1-hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid.
5.-the fabric softener composition of any one in the kind claim 1～4, the amount that wherein said chelating component exists is at least 10ppm.
6. the fabric softener composition of a claim 1, wherein the component of said chelated metal ions is that poly carboxylic acid helps and washes component, be selected from poly carboxylic acid, the poly carboxylic acid that contains three carboxyls that contains two carboxyls, the poly carboxylic acid that contains four carboxyls, alicyclic ring and heterocycle poly carboxylic acid, fragrant poly carboxylic acid and their mixture.
7. the fabric softener composition of a claim 6; wherein said poly carboxylic acid helps to be washed component and is selected from: Succinic Acid; propanedioic acid; (ethylidene dioxy) oxalic acid; toxilic acid; bi oxyacetate (diglycolic acid); tartrate; tartronic acid; fumaric acid; the ether carboxylic acid; the sulfinyl carboxylic acid; citric acid; equisetic acid (aconitric acid) and citraconic acid; butanedioic acid derivative; oxidation poly carboxylic acid material; oxygen two Succinic Acid; 1; 1; 2; the 2-ethane tetracarboxylic acid; 1; 1; 3; 3-propane tetracarboxylic acid; 1; 1; 2; 3-propane tetracarboxylic acid; sulfosuccinate derivant; pentamethylene-suitable; suitable; suitable-tetracarboxylic acid; cyclopentadiene (cyclopentadienide) pentacarboxylic acid; 2; 3,4,5-tetrahydrofuran (THF)-suitable; suitable; suitable-tetracarboxylic; 2,5-tetrahydrofuran (THF)-suitable-dicarboxylic acid; 2,2; 5; 5-tetrahydrofuran (THF)-tetracarboxylic acid; 1,2,3; 4; 5, the carboxyl methyl-derivatives of 6-hexane-hexacarboxylic acid and polyhydroxy-alcohol; benzene hexacarboxylic acid; 1; 2; 4,5-pyromellitic acid and phthalic acid derivative and their mixture, preferred toxilic acid.
Claim 6 or 7 the record fabric softener compositions, wherein said poly carboxylic acid helps the amount of washing component to be at least 100ppm.
9. the fabric softener composition of claim 8 record wherein contains said poly carboxylic acid and help and wash component, and its amount is at least 450ppm.
10. the fabric softener composition of any one record in the claim 1～9, wherein said associative thickener is selected from the multipolymer of oxyethane and/or propylene oxide, and it has a spot of C 8-C 24Poly-(vinyl) alcohol that poly-(oxyethane and/or the propylene oxide/urethane) of side chain, hydrophobically modified, alkyl replace, the acrylic acid polymer of hydrophobically modified and their mixture.
11. the fabric softener composition of any one record in the claim 1～9, wherein said crosslinked thickening material are to be prepared by the monomer that contains Acrylic Acid Monomer.
12. that the fabric softener composition of any one record among the claim 1-11, wherein said fabric softener are selected from is cationic, the fabric-softening material of non-ionic type, both sexes or anionic.
13. the fabric softener composition of claim 12 record, wherein said fabric softener is cationic biodegradable fabric-softening material.
14. the fabric softener composition of any one record in the claim 1～13, wherein said composition further contains one or more electrolyte components.
CN97195086A 1996-04-01 1997-03-27 Fabric softener composition Pending CN1220694A (en)

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EP96870041A EP0799887B1 (en) 1996-04-01 1996-04-01 Fabric softener compositions

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CN107868710A (en) * 2017-11-07 2018-04-03 邵莹 Stud filter filter element cleaning liquid
CN111117812A (en) * 2020-01-08 2020-05-08 上海江笙生物科技有限公司 Environment-friendly sterilization composition and preparation method thereof
CN115216968A (en) * 2021-04-20 2022-10-21 高尔斯顿科技公司 Textile softener, aqueous solution of textile softener, method for producing aqueous solution of textile softener, textile, and method for producing textile

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CN107868710A (en) * 2017-11-07 2018-04-03 邵莹 Stud filter filter element cleaning liquid
CN111117812A (en) * 2020-01-08 2020-05-08 上海江笙生物科技有限公司 Environment-friendly sterilization composition and preparation method thereof
CN111117812B (en) * 2020-01-08 2021-04-13 上海江笙生物科技有限公司 Environment-friendly sterilization composition and preparation method thereof
CN115216968A (en) * 2021-04-20 2022-10-21 高尔斯顿科技公司 Textile softener, aqueous solution of textile softener, method for producing aqueous solution of textile softener, textile, and method for producing textile

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AR006473A1 (en) 1999-08-25
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CA2250909C (en) 2002-10-01
ZA972774B (en) 1997-10-24
MX9808114A (en) 1999-02-28
AU2595197A (en) 1997-10-22
EP0799887B1 (en) 2003-06-11
CA2250909A1 (en) 1997-10-09
WO1997036981A1 (en) 1997-10-09
BR9710451A (en) 1999-08-17
EP0799887A1 (en) 1997-10-08

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