CN104093752A - Thickener containing at least one polymer based on associative monomers - Google Patents

Thickener containing at least one polymer based on associative monomers Download PDF

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Publication number
CN104093752A
CN104093752A CN201280054845.8A CN201280054845A CN104093752A CN 104093752 A CN104093752 A CN 104093752A CN 201280054845 A CN201280054845 A CN 201280054845A CN 104093752 A CN104093752 A CN 104093752A
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thickening material
monomer
polymkeric substance
acid
alkyl
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R·J·莱雷尔
C·阿里桑迪
O·本拉玛
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BASF SE
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BASF SE
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8105—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • A61K8/8111—Homopolymers or copolymers of aliphatic olefines, e.g. polyethylene, polyisobutene; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/817—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions or derivatives of such polymers, e.g. vinylimidazol, vinylcaprolactame, allylamines (Polyquaternium 6)
    • A61K8/8182—Copolymers of vinyl-pyrrolidones. Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/02—Preparations for cleaning the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/16—Purification
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions 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
    • C11D3/16—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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/48—Thickener, Thickening system

Abstract

The invention relates to a thickener containing i) at least one polymer which can be obtained by the polymerisation of a) at least one water-soluble ethylenically unsaturated monomer comprising at least one anionic monomer and/or at least one non-ionic monomer, b) at least one ethylenically unsaturated associative monomer, c) optionally at least one cross-linking agent, d) optionally at least one chain transfer agent, ii) at least one activator, the ratio between the activator and the polymer being > 10 wt.% to 100 wt.%.

Description

The thickening material that comprises at least one polymkeric substance based on associativity monomer
The present invention relates to a kind of thickening material that comprises at least one polymkeric substance and at least one activator, wherein the ratio of activator and polymkeric substance is >10:100[% by weight/% by weight].This polymkeric substance can be by polymerization at least one water-soluble olefinic unsaturated monomer that comprises at least one anionic monomer and/or at least one non-ionic monomer and the unsaturated associativity monomer of at least one olefinic prepare.In addition, the present invention relates to a kind of produce the method for thickening material of the present invention and comprise in addition at least one thickening material containing the preparaton of tensio-active agent.The present invention further provides this purposes containing the preparaton of tensio-active agent, for example, as the purposes of tenderizer or liquid washing agent, and also had the purposes of this thickening material, for example, as the purposes of viscosity modifier.
WO03/102043 relates to and comprising by (i) water-soluble olefinic unsaturated monomer or the monomer mixture that comprises at least one cationic monomer, (ii) is greater than at least one linking agent of 50ppm and (iii) aqueous formulation of cationic polymers prepared by least one chain-transfer agent based on component (i).This aqueous formulation can be used as thickening material in family expenses preparaton.
WO2009/019225 relates to a kind of water dispersion of alkali-soluble copolymer, and it is suitable as associative thickeners.The polymerized unit that this multipolymer comprises following monomer: a) at least one ethylenically unsaturated carboxylic acids, b) the unsaturated surfactant monomer of at least one nonionic olefinic, c) at least one methacrylic acid C 1-C 2alkyl ester and d) at least one vinylformic acid C 2-C 4alkyl ester, wherein on the alkyl number of alkyl acrylate, average alkyl chain length is 2.1-4.0.This associative thickeners can be prepared by letex polymerization.This associative thickeners is suitable in washing composition and sanitising agent.
Liquid dispersion polymer (LDP) composition is disclosed in WO2005/097834.These LDP compositions comprise the wetting ability that degree of neutralization is about 25-100%, water-soluble or swelling polymer, nonaqueous carrier phase and oil-in-water tensio-active agent.This wetting ability, water-soluble or swelling polymer preferably obtain by for example acrylic or methacrylic acid of polymerization.This LDP dispersion is applicable to producing microgranular thickening material, for example, for aqueous composition or organic composite, is particularly useful in personal care or pharmaceutical formulation.
WO2010/078959 relates to the cationic polymer thickeners being made up of the crosslinked water-swellable cationic polymers that comprises at least one cationic monomer and optional nonionic or anionic monomer, and wherein this polymer-based carbon comprises the water-soluble polymers chain that is less than 25% in the gross weight of this polymkeric substance.In addition, this polymer phase comprises linking agent for this polymkeric substance with the concentration of 500-5000ppm.This cationic polymers is prepared by inverse emulsion polymerization.
WO2010/079100 discloses the fabric softening agent composition comprising according to the polymkeric substance of WO2010/078959.
US2008/0312343 relates to inverse latex composition and the purposes as thickening material and/or emulsifying agent thereof, for example, for the production of makeup or pharmaceutical formulation.This inverse latex composition comprises at least at least one linearity of 50-80 % by weight, branching or crosslinked organic polymer (P), the emulsifier system of at least 5 % by weight to 10 % by weight water-in-oil types, at least one oil of 5-45 % by weight and at the most 5% water.This polymer P comprises neutral monomer and optional positively charged ion or anionic monomer.This inverse latex composition can optionally comprise the emulsifier system of 5 % by weight oil-in-water types at the most.This inverse latex composition can be prepared by inverse emulsion polymerization.
EP-A172025 relates to the dispersion of polymkeric substance in Continuous Liquid Phase, this polymkeric substance contain by aggregate packet at least 8 carbon atoms hydrophobic group ethylenically unsaturated monomer and can form with the ethylenically unsaturated monomer of its copolymerization.This dispersion is stable, substantially anhydrous and comprise at least 40 % by weight polymkeric substance.In polymerization process, for example can be by anionic monomer as copolymerizable ethylenically unsaturated monomer.Polymerization can be used as inverse emulsion polymerization and carries out.
EP-A172724 relates to the ethylenically unsaturated monomer that a) comprises the hydrophobic group with at least 8 carbon atoms by copolymerization and the polymkeric substance that b) prepared by water-soluble olefinic unsaturated monomer.It is soluble in water that all monomers can be used as mixture, and this polymkeric substance is prepared by inverse emulsion polymerization.The dry size <4 μ m that polymer beads has.As monomer component b), can use anionic monomer as free acid form or as the vinylformic acid of water-soluble salt, and also have non-ionic monomer as acrylamide.
EP-A172723 relates to the method for water-soluble, the substantially linear polymkeric substance flocculated suspension liquid of a kind of " single-point limiting viscosity " >3 of use.This polymkeric substance is the multipolymer of two or more ethylenically unsaturated monomers, and it comprises the monomer that at least 0.5 % by weight comprises hydrophobic group.This polymkeric substance can also be cationic polymers.
The problem that the present invention faces is to provide New stablization.This object is realized by the thickening material of the present invention that comprises following component:
I) at least one polymkeric substance that can obtain by the following material of polymerization:
A) at least one water-soluble olefinic unsaturated monomer that comprises at least one anionic monomer and/or at least one non-ionic monomer,
B) the unsaturated associativity monomer of at least one olefinic,
C) optional at least one linking agent,
D) optional at least one chain-transfer agent,
Ii) at least one activator,
Wherein the ratio of activator and polymkeric substance is >10 to 100[% by weight/% by weight].
Thickening material of the present invention is characterised in that they have advantageous property aspect deposition, shear thinning, stabilization and/or viscosity (thickening).Deposition is interpreted as referring to the activeconstituents of for example fabric softening agent deposition on fiber in washing operation.Be applied to the present invention, this refers to that the thickening material of the present invention that for example comprises at least one polymkeric substance (activeconstituents) is present in fabric softening agent and this fabric softening agent uses in washing operation or after washing operation.Thickening material of the present invention promotes this deposition of this activeconstituents in washing operation or after washing operation with significance degree.When use based on being mainly neutral monomer polymkeric substance time can realize in the special superperformance aspect deposition, this polymer-based carbon at least one associativity monomer, non-ionic monomer as acrylamide and optional anionic monomer.
In the time evaluating shear thinning, importantly this thickening material or respective fabric softener are thickness and dense under its base state, and thin in the time stirring.This improved shear thinning life-span on pump and performance in the production process of fabric softening agent have positive impact, promote human consumer's convenient batching and promote the noresidue of fabric softening agent to use, especially in the washing machine with automatic recipe maker.Thickening material of the present invention improves the stability of thickening material itself and corresponding preparaton.Effectively prevent sedimentation or the creaming of particle, whether irrelevant in nanometer, micron or mm-scale with them.The contribution factor is here the favourable yield-point of thickening material of the present invention.In addition the advantage that, they have is to realize very rapidly any desired redispersion and thickening.
Wherein exist the thickening material of the present invention of mixture of at least two kinds of activators to have additional advantage, wherein at least one activator has high HLB value and at least one activator has low HLB value.Such activating mixtures causes the spontaneous phase reversion (within the several seconds) in the time of dilute with water thickening material with the combination of the polymkeric substance that comprises the unsaturated associativity monomer of at least one olefinic block unit, and do not require input additional energy, for example, with whipped form.
In addition,, the in the situation that of thickening material of the present invention, advantageously associativity monomer is relative low with the ratio of total polymer.When using this thickening material in the preparaton of tensio-active agent, the effect of this associativity monomer is even best under the amount of approximately 0.5 % by weight (based on this polymkeric substance).
If thickening material of the present invention keeps constant inverse emulsion polymerization preparation by temperature wherein at least 40 DEG C, can observe the excellent homogeneity of this distribution of associativity monomer block unit in this polymkeric substance.Particularly in the little consumption situation of for example 0.1-1 % by weight associativity monomer, this at whole above-mentioned rheological property as thickening, shear thinning, stabilization and to also have on washing and wash effect be favourable.
The polymkeric substance being wherein present in this thickening material uses little linking agent or does not use the present embodiment prepared by linking agent to have equally advantage.Due to relatively high (water) soluble component of this polymkeric substance, reduce the resoiling in washing operation.Therefore, treat that Cleaning preparations even has the clean fiber of effectively having removed dirty particle after repetitive scrubbing process, this means and can't detect graying.Do not observe or only observe the very slight adhesion and/or distribute again on Cleaning preparations of dirty particle/polymkeric substance.
Within the scope of the present invention, for example, below to the radicals R in formula (I) 9defined definition is as C 1-C 30alkyl refers to that this substituting group (group) is for having the alkyl of 1-30 carbon atom.This alkyl can be linearity or branching and also have optional ring-type.Having the two alkyl of ring-type and linear component falls in this definition equally.This is equally also applicable to other alkyl, as C 1-C 4alkyl or C 16-C 22alkyl.Alkyl can also be optionally by functional group as amino, quaternary ammonium, hydroxyl, halogen, aryl or heteroaryl list-or polysubstituted.Unless otherwise, alkyl does not preferably have any functional group as substituting group.The example of alkyl is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, 2-ethylhexyl, the tertiary butyl (tert-Bu/t-Bu), cyclohexyl, octyl group, stearyl or docosyl.
The present invention is below with term description more accurately.
Thickening material of the present invention comprises at least one polymkeric substance as component i).This polymkeric substance can be by the following component of polymerization a) and b) and also have optional c) and d) preparing.
As component a), use at least one water-soluble olefinic unsaturated monomer, it comprises at least one anionic monomer and/or at least one non-ionic monomer.Negatively charged ion and non-ionic monomer are known by those of ordinary skill in the art itself.
If at least one anionic monomer be present in component a) in, it is preferably selected from vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid or its salt, especially this anionic monomer is sodium acrylate.
If at least one non-ionic monomer be present in component a) in,, except following nitrogen containing monomer is suc as formula (I) compound, the ester of above-mentioned anionic monomer is also suitable as non-ionic monomer.Such non-ionic monomer is preferably the methyl of acrylic or methacrylic acid or ethyl ester as ethyl propenoate or methyl acrylate.The ester that also preferably corresponding dimethylamino replaces, as (methyl) dimethylaminoethyl acrylate.
Preferably this non-ionic monomer is selected from NVP, N-vinyl imidazole or formula (I) compound:
Wherein
R 7for H or C 1-C 4alkyl,
R 8for H or methyl, and
R 9and R 10be H or C independently of each other 1-C 30alkyl.
This non-ionic monomer is particularly preferably acrylamide, Methacrylamide or dialkyl amido acrylamide.
In a preferred embodiment of the invention, in this polymkeric substance, component a) comprises at least one anionic monomer of 30-99.5 % by weight and at least one non-ionic monomer of 0.5-70 % by weight.
In another preferred embodiment of the present invention, component a) comprises at least one non-ionic monomer of 100 % by weight.
In another preferred embodiment of the present invention, component a) comprises at least one anionic monomer of 100 % by weight.
In addition, within the scope of the present invention, preferred ingredient a) does not comprise cationic monomer.
As components b), in the polymerization by unsaturated at least one olefinic associativity monomer for the production of this polymkeric substance.Associativity monomer is known by those of ordinary skill in the art itself.Suitable associativity monomer is for example described in WO2009/019225.Associativity monomer is also referred to as surfactant monomer.
Preferably in this polymkeric substance this according to components b) the unsaturated associativity monomer of olefinic be selected from formula (II) compound:
R-O-(CH 2-CHR’-O) n-CO-CR”＝CH 2(II)
Wherein
R is C 6-C 50alkyl, preferably C 8-C 30alkyl, especially C 16-C 22alkyl,
R' is H or C 1-C 4alkyl, preferably H,
R'' is H or methyl,
N is integer 0-100, preferably 3-50, especially 25.
As components b), particularly preferably use the compound as shown in the formula (II), wherein
R is C 16-C 22alkyl,
R' is H,
R'' is H or methyl, and
N is 25.
Formula (II) compound is can solution commercial, for example with title Plex6954O by gmbH is commercial.These are the methacrylic ester of fatty alcohol ethoxylate, as commercial aT25 (BASF SE, German Ludwigshafen).
Radicals R in formula (II) compound also can be used as has different chain length, as C 16and C 18group mixture exist.An one example is C 16-C 18fatty alcohol (ethylene glycol) 25-ether metacrylic acid ester, wherein C 16and C 18the two all exists fatty alcohol group (using the amount of can not ignore) as mixture.In contrast, for example, in compound (formula (II)) docosyl-25 methacrylic ester and hexadecyl-25 methacrylic ester, corresponding radicals R is not to exist as mixture, but as C 22or C 16chain exists.Other chain lengths only occur with impurity form.Numeral " 25 " in these formulas (II) compound represents the size of variable n.
Preparing by polymerization in this polymkeric substance, at least one linking agent can be optionally as amount of component b) exist.Suitable linking agent is known to those skilled in the art.Preferably in this polymkeric substance according to amount of component b) linking agent be selected from Vinylstyrene, tetra allyl ammonium chloride, vinylformic acid allyl ester, allyl methacrylate, the diacrylate of glycols or poly-glycol and dimethacrylate, divinyl, 1,7-octadiene, allyl group acrylamide or allyl methyl acrylamide, bisacrylamide guanidine-acetic acid, N, N'-methylene-bisacrylamide or polyvalent alcohol polyenoid propyl ether are as poly-allyl sucrose or pentaerythritol triallyl ether.What be also suitable as preferred linking agent is dialkyl dimethyl ammonium chloride.
In addition,, preparing by polymerization in this polymer process, at least one chain-transfer agent can be used as to component d).Suitable chain-transfer agent is known to those skilled in the art.Be selected from mercaptan, lactic acid, formic acid, Virahol or phosphinate according to component preference chain transfer agent d).
Be applicable to the polymerization process of this polymkeric substance of preparation or the thickening material of the present invention that comprises at least one polymkeric substance and be also useful on this polymerization or this thickening material production method in any additive or auxiliary agent in specific definition more below.
Preferably in thickening material of the present invention, the polymkeric substance that exists at least one to prepare by the following material of polymerization:
A) 20-99.99 % by weight, preferably at least one water-soluble olefinic unsaturated monomer that comprises at least one anionic monomer and/or at least one non-ionic monomer of 95-99.95 % by weight (based on this polymkeric substance),
B) 0.01-80 % by weight, preferably 0.05-5 % by weight, the particularly preferably unsaturated associativity monomer of at least one olefinic of 0.1-1 % by weight (based on this polymkeric substance),
C) 0-0.3 % by weight, preferably optional at least one linking agent of 0.01-0.1 % by weight (based on this polymkeric substance),
D) 0-0.3 % by weight, preferably at least one optional chain-transfer agent of 0.01-0.1 % by weight (based on this polymkeric substance).
In another embodiment of the present invention, the water-soluble fraction of this polymkeric substance is greater than 25 % by weight (based on the gross weight of this polymkeric substance), particularly in the time seldom using except this associativity monomer or do not use linking agent.Be preferably greater than 40 % by weight, especially in this polymkeric substance water soluble of 70-100 % by weight.The solvability of this polymkeric substance is measured by the procedure known to those skilled in the art, wherein this polymkeric substance being present in thickening material of the present invention is mixed with the water of limited amount (for example, referring to EP-A343840 or preferably according to P.Schuck, " Size-distribution analysis of macromolecules bysedimentation velocity ultracentrifugation and Lamm equation modeling, Biophysical Journal78, (3) (2000), the measuring method of the settling ratio in Svedberg (sved) unit of 1606-1619).
Preferably in this embodiment, linking agent used (amount of component b) in the polymerization of this polymkeric substance) ratio <10 % by weight (based on component a)-total amount d)).Particularly preferably in not using any linking agent in the polymerization of this polymkeric substance.
In addition, thickening material of the present invention comprises at least one activator as component ii).Activator itself is known in principle to those skilled in the art.
Suitable activator is preferably tensio-active agent, for example negatively charged ion, nonionic, positively charged ion and/or amphoterics, and they are for example disclosed in WO2009/019225.Preferably use negatively charged ion and/or nonionogenic tenside.
Nonionogenic tenside used is preferably fatty alcohol alkoxy compound.Fatty alcohol alkoxy compound is also referred to as polyalkylene glycol ethers.Preferred fatty alcohol alkoxy compound is oxyalkylated, advantageously ethoxylation, especially preferably there is the primary alconol that 8-18 carbon atom and average every mol of alcohol have 1-12mol ethylene oxide (EO), wherein alcohol radical can be linearity or branching, preferred 2-methyl-branched, or can comprise linear and methyl-branched group with mixture, as being conventionally present in oxo process alcohol groups.But, especially the preferred alcohol with 12-18 carbon atom from natural or industrial source, for example, from coconut alcohol, palmityl alcohol, tallow fatty alcohol or oleyl alcohol-or mixture, as for example can being derived by Viscotrol C-the alcohol ethoxylate that there is linear group and average every mol of alcohol and have 2-8 EO.Preferred ethoxylated alcohol for example comprises the C with 3 EO, 4 EO or 7 EO 12-C 14alcohol, has the C of 7 EO 9-C 11alcohol, has the C of 3 EO, 5 EO, 7 EO or 8 EO 13-C 15alcohol, has the C of 3 EO, 5 EO or 7 EO 12-C 18the mixture of alcohol and these, as there is the C of 3 EO 12-C 14alcohol and the C with 7 EO 12-C 18the mixture of alcohol.Described degree of ethoxylation is can be the statistical average value of integer or mark to specific product.Preferred alcohol ethoxylate has narrow homologue distribution (ethoxylate of close limit, NRE).Except these nonionogenic tensides, can also use and there is the fatty alcohol that is greater than 12 EO.The example is the tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.Can also use the nonionogenic tenside that comprises together EO and PO group in this molecule.Here can use the segmented copolymer with EO-PO block unit or PO-EO block unit, also have EO-PO-EO multipolymer or PO-EO-PO multipolymer.Certainly can also use wherein EO and PO unit not to be block distributed, but be the mixed oxyalkyl nonionogenic tenside of random distribution.Such product can be acted on fatty alcohol and obtain simultaneously by ethylene oxide and propylene oxide.
In addition, alkyl glycoside or alkyl poly glucoside also can be used as other nonionogenic tensides.Alkyl glycoside and alkyl poly glucoside are interpreted as by those skilled in the art the compound that finger comprises at least one alkyl segment and at least one sugar or glycan segment conventionally.Alkyl segment is preferably derived from the fatty alcohol that carbonatoms is 12-22, and sugar chain section is preferably derived from glucose, sucrose or sorbitan.
For example, can use the alkyl glycoside of general formula (1):
R 1O(G) x(1)
Wherein R 1for straight chain or methyl-branched, especially 2-methyl-branched has 8-22, and preferably uncle's aliphatic group of 12-18 carbon atom, and G is the glycoside units with 5 or 6 carbon atoms, preferred glucose.The oligomeric degree x of the distribution of regulation monoglycosides and oligoglycosides is any number between 1-10, and preferably x is 1.2-1.4.
The nonionogenic tenside of the another kind of preferred use that uses or use with other nonionic surfactant combinations as unique nonionogenic tenside is oxyalkylated, preferably ethoxylation or ethoxylation and propenoxylated fatty acid alkyl ester, preferably in alkyl chain, there is 1-4 carbon atom, especially fatty acid methyl ester, for example, described in Japanese patent application JP58/217598, or preferably by the method preparation described in International Patent Application WO-A-90/13533.
The nonionogenic tenside of amine oxide type, for example N-cocounut oil alkyl-N, N-dimethyl oxidation amine and N-tallow alkyl-N, N-dihydroxy ethyl amine oxide, and the nonionogenic tenside of Marlamid type may be also suitable.The amount of these nonionogenic tensides is preferably no more than the amount of ethoxylized fatty alcohol, is especially no more than the half of its amount.
Other suitable tensio-active agents are polyhydroxy fatty acid amides of formula (2):
Wherein R 2c (=O) is for having the aliphatic acyl of 6-22 carbon atom, R 3for hydrogen, the alkyl with 1-4 carbon atom or hydroxyalkyl and [Z] are for having linearity or the branching polyhydroxy alkyl of 3-10 carbon atom and 3-10 hydroxyl.Polyhydroxy fatty acid amide is conventionally can be by the known substance also obtaining by lipid acid, fatty acid alkyl ester or fatty acid chloride acidylate subsequently with ammonia, alkylamine or alkanolamine reductive amination reducing sugar.
This group polyhydroxy fatty acid amide also comprises formula (3) compound:
Wherein R 4for thering is linearity or branched-alkyl or the alkenyl of 7-12 carbon atom, R 5for thering is linearity, branching or the cyclic alkylidene of 2-8 carbon atom or thering is arylidene and the R of 6-8 carbon atom 6for thering is linearity, branching or cyclic alkyl or aryl or the oxyalkyl of 1-8 carbon atom, wherein preferred C 1-C 4alkyl or phenyl, and [Z] 1for its alkyl chain is by the linear polyhydroxy alkyl of at least two hydroxyls replacements, or the alkoxylate of this group, preferably ethoxylation or propoxylated derivative.[Z] 1preferably by reductive amination carbohydrate, for example glucose, fructose, maltose, lactose, semi-lactosi, seminose or wood sugar and obtain.N-alkoxyl group-or N-aryloxy replace compound can change into subsequently required polyhydroxy fatty acid amide, for example according to WO-A-95/07331 by with fatty acid methyl ester alcoxylates as catalyzer exist under react.
Anion surfactant used is for example those of sulfonate and vitriol type.Suitable sulfonate type tensio-active agent is here alkylbenzene sulfonate, preferably C 9-C 13alkylbenzene sulfonate, alkene sulfonate, i.e. alkene-and the mixture of hydroxyl alkane sulfonate, also have stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, for example, by the C with terminal double bond or internal double bond 12-C 18monoolefine is by also obtaining sulfonated products alkalescence or acidic hydrolysis subsequently with gaseous sulfur trioxide sulfonation.Also suitable is sulfonated alkane, preferred secondary alkansulfonic acid ester, and it is for example by C 12-C 18paraffinic hydrocarbons is by chlorosulphonation or sulfoxidation is also hydrolyzed subsequently or neutralization obtains.The ester (sulfonated ester) of alpha-sulfo-fatty acid, α-sulfonation methyl ester of for example hydrogenation fatty acid distribution of coconut oil, palm kernel fatty acid or tallow fatty acid is equally also suitable.
Other suitable anion surfactants are sulfation glycerin fatty acid esters.That glycerin fatty acid ester is interpreted as referring to is single-, two-and three esters, and composition thereof, this in preparation process by obtaining with 1-3mol fatty acid esterification list glycerine or in the transesterify of triglyceride level and 0.3-2mol glycerine.Preferred sulfation glycerin fatty acid ester is here the saturated fatty acid with 6-22 carbon atom, for example the sulfonated products of caproic acid, sad, capric acid, tetradecanoic acid, lauric acid, palmitinic acid, stearic acid or docosoic acid.
Other suitable anion surfactants are aliphatic alcohol sulfates, for example alkane (alkene) base vitriol.Preferred alkane (alkene) base vitriol is C 12-C 18fatty alcohol, for example coconut oil fat alcohol, tallow fatty alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol or stearyl alcohol, or C 10-C 20the sulfuric acid monoester of oxo alcohol and there is an alkali metal salt, the especially sodium salt of those monoesters of the secondary alcohol of these chain lengths.The further preferably alkane of described chain length (alkene) base vitriol, it comprises taking petrochemical industry as the synthetic straight chained alkyl that basis produces, and has the degradation behavior that is similar to the isovalent compounds based on chemistry of fats raw material.For washing technology, preferably C 12-C 16alkyl-sulphate and C 12-C 15alkyl-sulphate, and also have C 14-C 15alkyl-sulphate.For example, according to US Patent specification 3,234,258 or 5,075,041 preparation and can be used as commercially available prod by Shell Oil Company with title obtain 2,3-alkyl-sulphate is also suitable anion surfactant.
With straight chain or the branching C of 1-6moL ethoxylated 7-C 21alcohol, as on average having the 2-methyl-branched C of 3.5mol ethylene oxide (EO) 9-C 11alcohol or there is the C of 1-4 EO 12-C 18the sulfuric acid monoester of fatty alcohol is also suitable.
Other suitable anion surfactants also have the salt of alkyl sulfo-succinic acid, and it is also referred to as sulfosuccinic ester and be sulfo-succinic acid and alcohol, the monoesters of preferred fat alcohol, especially ethoxylized fatty alcohol and/or diester.Preferred sulfosuccinic ester comprises C 8-C 18fatty alcohol group or these mixture.Particularly preferred sulfosuccinic ester comprises the fatty alcohol group that is derived from ethoxylized fatty alcohol.Thus, particularly preferably its fatty alcohol group is derived from the sulfosuccinic ester with the ethoxylized fatty alcohol that narrower homologue distributes again.Can also use equally alkane (alkene) base succsinic acid or its salt preferably with 8-18 carbon atom in alkane (alkene) base chain.
Other suitable anion surfactants are alkyl carboxylates, the sodium salt of for example saturated or unsaturated fatty acids, and wherein this alkyl carboxylate's alkyl is preferably linear.
Within the scope of the present invention, this activator is preferably selected from fatty alcohol alkoxy compound, alkyl glycoside, and alkyl carboxylic acid ester, benzene sulfonamide acid esters, secondary bond alkyl sulfonic acid ester and fatty alcohol sulfate, be particularly preferably selected from fatty alcohol alkoxy compound.An example of preferred fat alcohol alkoxylate is C 6-C 17(second month in a season)-poly-(3-6) ethoxylate.
In addition, preferably use within the scope of the present invention the activator with (relatively) high HLB value (hydrophile-lipophile balance value).Preferably the HLB of this activator is 7-18, more preferably 8-15, particularly preferably 9-13.
The activator with high HLB value is preferably i) by secondary alcohol or has the mixture of alcohol of 12-18 carbon atom and fatty alcohol alkoxy compound that ethylene oxide or propylene oxide form, and ii) by sucrose and C 8-C 22the alkyl glycoside that fatty alcohol forms.The example of such activator is by Croda GmbH, Herrenpfad-S ü d33,41334Nettetal, the Synperonic87K that Germany is commercial; Croduret40 or other ethoxylated hydrogenated castor oils are as Etocas40 or Crodesta F110, all from Croda.
In another embodiment of the present invention, preferably use the mixture of at least two kinds of activators, wherein at least one activator has high HLB value and at least one activator has low HLB value.Having the HLB value that the HLB value >12-20 that the activator of high HLB value preferably has and the activator with low HLB value preferably have is 1-12.In this embodiment, the activator that has the activator of high HLB value and have a low HLB value can exist mutually with the known any required ratio of those skilled in the art.Preferably in this mixture, use 20-50 % by weight to there is the activator of high HLB value and 50-80 % by weight to have the activator of low HLB value.Further preferably regulate the activator with high HLB value with have low HLB value activator this ratio so that totally HLB value be 7-18, more preferably 8-15, particularly preferably 9-13.
In these mixtures of at least two kinds of activators, the activator with high HLB value used is preferably based on sucrose or sorbitan and C 8-C 22the low polyoxyethylene glucosides of the alkyl glycoside of fatty alcohol or poly-alkyl glycoside or poly-alkyl, as polyoxyethylene glycol sorbitan monostearate or polyoxyethylene sorbitan monostearate.The example of such activator is commercially available Crillet1, Crillet3 or Crodesta F160, all from Croda.As the activator with low HLB value, preferably use by sucrose or sorbitan and C 8-C 22the alkyl glycoside that fatty alcohol or lipid acid form, as sorbitan laurate esters or sorbitan stearate.The example of such activator is from commercially available Crill1, the Crill3 of Croda or Crodesta F10.
According to the present invention, the ratio >10:100[% by weight/% by weight of activator and polymkeric substance], preferably 10.5-50:100[% by weight/% by weight] and, particularly preferably 11.5-20:100[% by weight/% by weight].
In thickening material of the present invention, except this polymkeric substance and this activator, can also there are other components.Other suitable components specific definition more hereinafter with regard to the preparation of this thickening material and this polymkeric substance.Other suitable components can be for example oil and solvent.
In thickening material of the present invention, this polymkeric substance can be with discrete form, and the anhydrous polymer being preferably dispersed in oil as reverse phase dispersion, water-in-oil dispersion or conduct is present in this oil phase.
The present invention further provides a kind of method of preparing thickening material of the present invention.Thickening material preparation method itself is known with the method for preparing polymkeric substance to those skilled in the art.Preferably this polymkeric substance is by letex polymerization, and especially prepared by inverse emulsion polymerization.Preferably first prepare this polymkeric substance and after polymerization, preferably add activator to obtain this thickening material by after inverse emulsion polymerization.
This polymkeric substance can be prepared in every way, preferably by letex polymerization, and especially inverse emulsion polymerization preparation.Inverse emulsion polymerization is conventionally interpreted as and refers to basis as undefined polymerization process by those skilled in the art: hydrophilic monomer is scattered in hydrophobicity oil phase.Directly in these hydrophilic monomer particles, carry out polymerization by adding initiator.
In addition, preferably after this inverse emulsion polymerization and before adding this activator, from this oil phase, steam except at least some water and at least some low boiling point components, especially steam and remove by LDP (liquid dispersion polymer) technology.LDP technology itself is known to those skilled in the art; For example it is described in WO2005/097834.
Unless otherwise, details are below applicable to all types of letex polymerizations, as the letex polymerization in the water that also forms subsequently external phase, are especially also applicable to inverse emulsion polymerization, and wherein hydrophobicity oil phase forms external phase.Suitable polymerization starter is used for to polymerization.Preferential oxidation reduction initiator and/or heat-activatable radical polymerization initiator.
The right oxidisability component of suitable heat-activatable radical initiator or redox initiator is mainly those of peroxide and azo-type.These especially comprise hydrogen peroxide, peracetic acid, t-butyl hydroperoxide, di-t-butyl peroxide, dibenzoyl peroxide base, hydroperoxidation benzoyl, peroxidation 2, 4-dichloro-benzoyl base, 2, 5-dimethyl-2, 5-bis-(hydroperoxy) hexane, peroxybenzoic acid, t-butylperoxy pivarate, t-butyl peroxy-acetate, dilauroyl peroxide base, peroxidation two caproyls, peroxidation distearyl acyl group, dibenzoyl peroxide base, peroxide two carbonic acid diisopropyl esters, peroxide two carbonic acid didecyl esters, peroxide two carbonic acid two-eicosyl esters, peroxybenzoic acid di tert butyl carbonate, Diisopropyl azodicarboxylate, 2, 2'-azo two-2, 4-methyl pentane nitrile, ammonium persulphate, Potassium Persulphate, Sodium Persulfate and peroxophosphoric acid sodium.
Most preferably persulphate (peracetic dithionite), especially Sodium Persulfate.
In the time carrying out letex polymerization, this initiator uses with the amount that is enough to initiated polymerization.This initiator conventionally gross weight based on monomer used uses with the amount of about 0.01-3 % by weight.The gross weight of the amount of initiator based on monomer used is preferably about 0.05-2 % by weight, especially 0.1-1 % by weight.
Letex polymerization is carried out conventionally at 35-100 DEG C.It can be used as batch processes or carries out with feed process form.In charging program, polymerization temperature is introduced and be heated to at least some polymerization starters and more optional monomers as just expecting, in maintaining polymerization, introduce continuously or progressively subsequently the polyblend of remainder, conventionally via multiple chargings that separate, wherein one or more comprise monomer pure or emulsification form.Preferred monomers charging is carried out with monomer emulsion form.Be parallel to monomer feed, can be metered into further polymerization starter.
In preferred embodiments, all the initiator of amount, as the introducing of just expecting, is not parallel to the further initiator metering feeding of monomer feed.
In preferred embodiments, therefore using heat-activatable radical polymerization initiator all as the introducing of just expecting, and add monomer mixture, preferably with monomer emulsion form.Starting before monomer mixture charge, make this first expect reach activation temperature or the higher temperature of heat-activatable radical polymerization initiator.This activation temperature is considered to after 1 hour at least temperature of half decomposition of initiator.
According to another preferred preparation method, this polymkeric substance obtains by polymeric monomer intermixture under existing in redox initiator system.Redox initiator system comprises at least one oxidant constituents and at least one reductive agent component, and now heavy metal ion is preferably additionally present in this reaction medium as catalyzer, for example cerium salt, manganese salt or iron (II) salt.
Suitable oxidant constituents is for example superoxide and/or hydroperoxide, as hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, pinane hydroperoxide, hydroperoxidation diisopropyl phenyl, percarbonic acid dicyclohexyl ester, dibenzoyl peroxide base, dilauroyl peroxide base and diacetyl peroxide base.Preferably hydrogen peroxide and t-butyl hydroperoxide.
Suitable reductive agent component is alkali metal sulfite, basic metal hyposulfite, basic metal sulfoxylate, sodium bisulfite, Rongalit C (sodium formaldehyde sulphoxylate), single-and otan, carbohydrate (for example glucose or dextrose), xitix and salt thereof, the basic metal of acetone/bisulfite adduct and/or hydroxyl methane-sulfinic acid, preferably sodium bisulfite or Sodium Pyrosulfite.
What be also suitable as reductive agent component or catalyzer is iron (II) salt, and as ferric sulfate (II), tin (II) salt is as tin chloride (II), and titanium (III) salt is as titanium sulfate (III).
The gross weight of the consumption of oxygenant based on monomer used is 0.001-5.0 % by weight, preferably 0.005-1.0 % by weight, particularly preferably 0.01-0.5 % by weight.The gross weight of reductive agent based on monomer used be with 0.001-2.0 % by weight, preferably 0.005-1.0 % by weight, and particularly preferably the amount of 0.01-0.5 % by weight is used.
Particularly preferred redox initiator system is sodium peroxydisulfate/sodium hydrogen sulfite system, for example 0.001-5.0 % by weight sodium peroxydisulfate and 0.001-2.0 % by weight sodium bisulfite, especially 0.005-1.0 % by weight sodium peroxydisulfate and 0.005-1.0 % by weight sodium bisulfite, particularly preferably 0.01-0.5 % by weight sodium peroxydisulfate and 0.01-0.5 % by weight sodium bisulfite.
Further particularly preferred redox initiator system is t-butyl hydroperoxide/hydrogen peroxide/ascorbic acid system, for example 0.001-5.0 % by weight t-butyl hydroperoxide, 0.001-5.0 % by weight hydrogen peroxide and 0.001-2.0 % by weight xitix, especially 0.005-1.0 % by weight t-butyl hydroperoxide, 0.005-1.0 % by weight hydrogen peroxide and 0.005-1.0 % by weight xitix, particularly preferably 0.01-0.5 % by weight t-butyl hydroperoxide, 0.01-0.5 % by weight hydrogen peroxide and 0.01-0.5 % by weight xitix.
Preferably this polymkeric substance is prepared by inverse emulsion polymerization, wherein first prepares water and the oil phase of water soluble ingredient with being separated from each other.Then two-phase is obtained by mixing to water-in-oil dispersion mutually.The polymerization by adding redox initiator system of this mixture; Can be by its thermal activation if now optionally also can add thermal initiator or exist.
In water, preferably there is chain-transfer agent, linking agent, anionic monomer and/or neutral monomer and also have optional associativity monomer, and also have other optional components.Other suitable components are for example for salt uses coordination agent as diethylene triaminepentaacetic acid(DTPA) five sodium.
In oil phase, preferably there is emulsifying agent, stablizer, high boiling point oil, lower boiling oil and/or optional associativity monomer.In addition, in this oil phase, can optionally there is non-ionic monomer.
Emulsifying agent, stablizer, lower boiling oil and high boiling point oil itself are known to those skilled in the art.These compounds can use separately or with form of mixtures.
Typical emulsifying agent is anionic emulsifier, as the sodium salt of Sodium Lauryl Sulphate BP/USP, tridecyl ether sodium sulfate, sodium dioctyl sulfosuccinate and alkyl aryl polyether sulfonic acid; And nonionic emulsifying agent, as alkyl aryl polyether alcohol and ethylene oxide/propylene oxide multipolymer.Sorbitan trioleate is suitable as emulsifying agent equally.
Preferred emulsifying agent has following general formula:
R-O-(CH 2-CHR′-O) n-X，
Wherein R is C 6-C 30alkyl,
R ' is hydrogen or methyl,
X is hydrogen or SO 3m,
M is hydrogen or basic metal, and
N is the integer of 2-100.
Suitable stablizer is for example described in EP-A172025 or EP-A172724.Preferred stablizer is the multipolymer of methacrylic acid stearyl and methacrylic acid.
Suitable high boiling point oil is for example stearic acid 2-(ethyl hexyl) ester and (hydroheated) heavy naphtha that also has hydro-thermal, and suitable lower boiling oil is for example de-aromatization aliphatic hydrocrbon or low viscous mineral oil.
In a preferred embodiment of the invention, in inverse emulsion polymerization process by components b) (the unsaturated associativity monomer of at least one olefinic) add in this oil phase.
In inverse emulsion polymerization process, temperature can be kept to constant or also can improve temperature.The raising of temperature can be carried out continuously or progressively.Therefore, for example the temperature in polymerization process can improve 0.2-10 DEG C/min, preferably 1-3 DEG C/min.Temperature improves by the rate-controlling that adds of initiator.Temperature initial value can be 0-30 DEG C, preferably 10-20 DEG C.
In another embodiment of the present invention, the temperature in inverse emulsion polymerization process is kept to constant (cold program), this temperature is 0-30 DEG C, preferably 10-20 DEG C.In another embodiment of the present invention, temperature is kept to constant (warm program) in higher temperature scope.Temperature in polymerization process is 40-150 DEG C, preferably 70-120 DEG C.
In particularly preferred embodiment of the present invention, in this inverse emulsion polymerization process, temperature is kept to constant, this temperature is at least 40 DEG C, preferably 50-90 DEG C.
If within the scope of the present invention by temperature in polymerization process, especially in inverse emulsion polymerization process, keep constant, this means that this temperature starts to remain steady state value from polymerization.5 DEG C of +/-in polymerization process process, the fluctuation of preferably 2 DEG C of +/-, especially 1 DEG C of +/-is considered to steady temperature (based on required steady temperature value).It is constant until polymerization is complete that this temperature keeps; This preferably remains to transformation efficiency and is greater than 90% monomer used, after 95 % by weight, particularly preferably in transforming (100 % by weight) afterwards completely.This temperature can keep constant by the reaction heat being occurred by cooling dissipation.The beginning of polymerization normally adds polymerization starter, preferably adds redox initiator system.First this system is conventionally heated to temperature required and waits for steady temperature in stirring.Then add polymerization starter, result starts polymerization process.In one embodiment of the invention, this temperature is held constant to the value higher than the fusing point of associativity monomer used.
The present invention further provides the acid preparaton containing tensio-active agent, it comprises at least one thickening material of the present invention as defined above.The pH of this preparaton is 1 to <7.
The present invention further provides the alkaline preparaton containing tensio-active agent, it comprises at least one thickening material of the present invention as defined above.The pH of this preparaton is 7-13.
The present invention can comprise the known composition of other those skilled in the art containing the acid or alkaline preparaton of tensio-active agent.Suitable composition comprises that one or more are selected from following material: washing assistant, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, enzyme, ionogen, non-aqueous solvent, pH properties-correcting agent, spices, fragrance carrier, fluorescent agent, dyestuff, hydrotropic agent, froth suppressor, silicone oil, anti redeposition agent, white dyes, graying inhibitor, sanforzing agent, anti-creasing agent, dye transfer inhibitor, Antibacterial Constituents, sterilant, mycocide, antioxidant, corrosion inhibitor, static inhibitor, flatiron auxiliary agent, thinization and soaker, swelling and slipproofing agent and UV absorption agent.
The present invention further provides the present invention containing the acid preparaton of tensio-active agent in hair cosmetic, the Hairsetting, as shampoo, as tenderizer, as care composition, as amendment, as skin ointment, as shower gels, as doing washing with fabric softening agent or as acidic cleaning agent, be preferred for the purposes of the acidic cleaning agent of lavatory or bathtub.
The present invention further provides the present invention containing the alkaline preparaton of tensio-active agent as care composition, liquid washing agent or machine washing or the purposes of washing dish sanitising agent for hand washing.
Having the present invention further provides thickening material of the present invention as viscosity modifier, for optimizing shear thinning, as thickening material, is that nanometer is to the suspension composition of millimeter scope and/or in the acidity containing tensio-active agent or the purposes of alkaline preparaton for stable dimensions.
In the explanation that comprises all embodiment, use following abbreviation:
Monomer
ACM acrylamide
AA vinylformic acid
MAA methacrylic acid
NaAc sodium acrylate
BEM docosyl-25 methacrylic ester
MBA methylene-bisacrylamide (linking agent)
TAAC tetra allyl ammonium chloride (linking agent)
NaHP sodium hypophosphite (chain-transfer agent)
C16EO25MAc C 16-C 18-fatty alcohol-(ethylene glycol) 25ether metacrylic acid ester
Other
The umber of every hundred parts of monomers of pphm (based on component a) and b))
Demin. softening
Below with reference to embodiment, the present invention is described.
Embodiment
Comparative example C1
Start there is no synthetic thickening agent/polymkeric substance under associativity monomer by anionic monomer, but use linking agent and chain-transfer agent and also improve polymerization temperature.
Prepare the water of water soluble ingredient by mixing following component:
250.24g (139.02pphm) water,
0.89g (0.49pphm) diethylene triaminepentaacetic acid(DTPA) five sodium,
11.05g (0.06pphm) methylene-bisacrylamide (1%, in water),
180g (100pphm) vinylformic acid, and
146.8g (40.78pphm) NaOH (50%, in water)
Use NaOH (50%, in water) to regulate water to pH5.5.
Prepare oil phase by mixing following component:
20.62g (8.59pphm) dehydrated sorbitol mono-fatty acid ester (75%, in the heavy naphtha (oil) [Isopar G] of hydro-thermal)
93.19g (12.27pphm) polymer stabilizer: methacrylic acid stearyl-Sipacril 2739OF (23.7%, in the heavy naphtha [Isopar G] of hydro-thermal),
120.24g (66.8pphm) low viscosity mineral oil (Kristol M14) and
The heavy naphtha [Isopar G] of 236.28g (131.27pphm) hydro-thermal.
Use high-shear that this two-phase is mixed the ratio of 44.4 parts of oil phases with 55.6 parts of waters and produce water-in-oil emulsion.Gained water-in-oil emulsion is introduced and is equipped with in the reactor of nitrogen sparge tube, agitator and thermometer.By this emulsion nitrogen purging, result is removed oxygen, and is cooled to 20 DEG C.
Polymerization is by adding by 13g (0.014pphm) Sodium Pyrosulfite (0.2%, in the heavy naphtha (oil) [Isopar G] of hydro-thermal) and 13g (0.014pphm) t-butyl hydroperoxide (0.2%, in the heavy naphtha (oil) [Isopar G] of hydro-thermal) form redox couple realize.Progressively add this redox couple so that temperature rises to 2 DEG C/min.Once reach isothermal, divide 2 steps (second step is after 45 minutes) to add radical initiator (2,2'-azo two (2-methylbutyronitrile), CAS:13472-08-7) and this emulsion is remained at 85 DEG C to 75 minutes.
Use vacuum distilling except anhydrating and the low boiling point component (Isopar G) of this oil phase.
Low viscosity mineral oil (Kristol M14) is added in this product to realize 54% solids content.In this product, add 8% (the total mass mark based on this product) fatty alcohol alkoxylate (C12/15 alcohol alkoxylate [Synperonic87K tM]) to produce the thickening material (dispersion) of polymer solids mark as 50%.Therefore the ratio of activator and polymkeric substance is 16.0:100[% by weight/% by weight].
Embodiment 1
Started the thickening material/polymkeric substance under associativity monomer and constant polymerization temperature by anionic monomer:
Embodiment 1.1
Prepare the water of water soluble ingredient by mixing following component:
246.13g (140.65pphm) water,
0.86g (0.49pphm) diethylene triaminepentaacetic acid(DTPA) five sodium,
174.13g (99.5pphm) vinylformic acid, and
154.26g (44.07pphm) NaOH (50%, in water)
Use NaOH (50%, in water) to regulate water to pH5.5.
Prepare oil phase by mixing following component:
20.05g (8.59pphm) dehydrated sorbitol mono-fatty acid ester (75%, in the heavy naphtha (oil) [Isopar G] of hydro-thermal)
90.6g (12.27pphm) polymer stabilizer: methacrylic acid stearyl-Sipacril 2739OF (23.7%, in the heavy naphtha [Isopar G] of hydro-thermal),
119.03g (68.02pphm) low viscosity mineral oil (Kristol M14) and
The heavy naphtha [Isopar G] of 229.72g (131.27pphm) hydro-thermal
1.09g (0.5pphm) associativity monomer: 60 % by weight C16EO25Mac: be included in commercially available prod Plex6954-O (containing 20 % by weight methacrylic acids, 20 % by weight water).
Use high-shear that this two-phase is mixed the ratio of 44.4 parts of oil phases with 55.6 parts of waters and produce water-in-oil emulsion.Gained water-in-oil emulsion is introduced and is equipped with in the reactor of nitrogen sparge tube, agitator and thermometer.This emulsion is used in being heated to 50 DEG C to nitrogen purging, result is removed oxygen.
Polymerization is by adding the redox couple being made up of 13.6g (0.016pphm) Sodium Pyrosulfite (0.2%, in water) and 13.6g (0.016pphm) t-butyl hydroperoxide (0.2%, in water) to realize.At 50 DEG C, in 2 hours, add redox couple.Then this mixture is heated to 85 DEG C, then divide 2 steps (second step is after 45 minutes) to add radical initiator (2,2'-azo two (2-methylbutyronitrile), CAS:13472-08-7) and this emulsion is remained at 85 DEG C to 75 minutes.
Use vacuum distilling except anhydrating and the low boiling point component (Isopar G) of this oil phase.
Low viscosity mineral oil (Kristol M14) is added in this product to realize 54% solids content.In this product, add 8% (the total mass mark based on this product) fatty alcohol alkoxylate (C12/15 alcohol alkoxylate [Synperonic87K tM]) to produce the thickening material (dispersion) of polymer solids mark as 50%.Therefore the ratio of activator and polymkeric substance is 16.0:100[% by weight/% by weight].
Prepare according to embodiment 1.1 according to the following example of table 1, consider the described variation of monomer composition.Associativity monomer C16EO25Mac is added in oil phase.Use commercially available prod Plex6954O; This ratio using about 1:1 comprises 60 % by weight associativity monomers and water and MAA as solvent.Weight data in table 1 relates to does not have the associativity of solvent amount of monomer.Being 16.0:100[% by weight/% by weight in each case according to the ratio of activator and polymkeric substance in all embodiment of table 1]; Unless otherwise, the polymer solids mark of corresponding thickening material (dispersion) is 50%.
table 1
Embodiment C16EO25MAc(pphm) Sodium acrylate Acrylamide MBA(pphm) Explanation
1.1 0.38 99.5 -
1.2 0.38 99.5 0.06
1.3(comp.) - 100 -
1.4 0.38 99.5 -
Embodiment 2
Started by anionic monomer, at associativity monomer and also improve the thickening material/polymkeric substance under polymerization temperature:
According to comparative example C1 preparation, consider the described variation of monomer composition according to the following example of table 2.Associativity monomer C16EO25Mac is added in oil phase.Use commercially available prod Plex6954O; This ratio using about 1:1 comprises 60 % by weight associativity monomers and water and MAA as solvent.Weight data in table 2 relates to does not have the associativity of solvent amount of monomer.Being 16.0:100[% by weight/% by weight in each case according to the ratio of activator and polymkeric substance in all embodiment of table 2]; Unless otherwise, the polymer solids mark of corresponding thickening material (dispersion) is 50%.
table 2
Embodiment C16EO25Mac Propylene Propylene MBA Explanation
(pphm) Acid sodium Acid amides (pphm)
2.1 1.5 98 0.06
2.2 0.38 99.5 0.06
2.3 1.5 98 0.06 Starting temperature is 14 DEG C
2.4 1.5 98 --
2.6 0.38 99.5 -
2.5(comp.) - 100 0.2
C1 - 100 0.06
2.7(comp.) - - 100 -
2.8 0.38 - 99.5 -
universal measurement method:
Unless otherwise, in the following example, use following universal measurement method:
Viscosimetric analysis:
Consider according to DIN51550, DIN53018, the program of DIN53019, is used Brookfield DV II type viscometer, unless separately indicated in following table, under the speed of 20 revs/min, measures described viscosity mPa*s with No. 6 spindles.
Measure shear thinning
Measure and carry out in the ASC from Antonpaar (automatic sample-changer) rotational rheometer, this instrument has CC27 right cylinder geometry, and the radius of measuring body is that the radius of 13.33mm and measuring cup is 14.46mm.Measuring temperature is 23 DEG C.Sample starts to bring up to high-shear (0.01s under steady state shearing under low shearing -1-1000s -1) and (1000s that again returns -1-0.01s -1) and measure.
Embodiment 3
In water, use thickening material/polymkeric substance
At room temperature thickening material slowly added in distilled water and stir until this preparaton homogenizing according to table 3.The aqueous formulation that result obtains according to table 3 comprise 1.0 % by weight polymkeric substance to 99.0 % by weight water or 0.5 % by weight polymkeric substance to 99.5 % by weight water.The results are summarized in table 3.
table 3
The rheologic behavio(u)r of the thickening material/polymkeric substance being started by anionic monomer in water, measures for 5 minutes after this preparaton of preparation
If the associativity monomer of increasing amount is mixed in this polymkeric substance, more significantly improve thickening effectiveness compared with there is no the C1 of associativity monomer.Lower according to starting temperature in the polymerization process of embodiment 2, thickening effectiveness is larger.Program under the constant polymerization temperature of 50 DEG C produces the thickening effectiveness improving to monomer composition identical aspect other.Last 4 embodiment of table 3 relate to the polymkeric substance containing acrylamide.
Embodiment 4.1
In the standard preparaton of care composition, use thickening material/polymkeric substance
Care composition preparaton (P1) comprises the composition in table 4.1.P1 is prepared by each case phase A and B being heated to 80 DEG C.Then this two-phase is merged and homogenizing.Then under agitation this mixture is cooled to approximately 40 DEG C, then adds this mixture of phase C homogenizing.
the composition of table 4.1.1:P1
this thickening material is added in care composition preparaton P1:
At room temperature slowly add in care composition preparaton P1 and stir until this preparaton homogenizing by the table listed thickening material of the present invention of 4.1.2 or according to the thickening material of comparative example.The thickening material of the care composition preparaton obtaining in this way to comprise described concentration with respect to the % by weight of 100 % by weight gained care composition preparatons.
Within latter 1 day, measure Brookfield viscosity in preparation.The results are summarized in table 4.1.2.
table 4.1.2: thickening material performance and shear thinning in care composition
The rheological property of the fabric softening agent that comprises the thickening material/polymkeric substance being started by anionic monomer:
If the associativity monomer of increasing amount is mixed in this polymkeric substance, more significantly improve thickening properties compared with there is no the V1 of associativity monomer.
Embodiment 4.2
In the standard preparaton W3 of fabric softening agent, use thickening material/polymkeric substance
W3: prepare methyl three (hydroxyethyl) ammonium two tallow fatty acid METH vitriol, partially hydrogenated fabric softening agent (5.5% actives mark):
The pH of this fabric softening agent is 2.7 and comprises 5.5 % by weight methyl three (hydroxyethyl) ammonium two tallow fatty acid METH vitriol (partial hydrogenation) and 94.5 % by weight deionized waters.
This thickening material is added in fabric softening agent preparaton W3:
At room temperature by according to embodiment 1 and 2 and the thickening material (in table 4.2) of comparative example slowly add in respective fabric softener preparaton and stir until this preparaton homogenizing.
Within latter 1 day, measure Brookfield viscosity in preparation.The results are summarized in table 4.2.
the thickening material performance of table 4.2. in fabric softening agent W3
The rheological property of the fabric softening agent that comprises the thickening material/polymkeric substance being started by neutral monomer:
If associativity monomer is mixed in this polymkeric substance, more significantly improve thickening properties compared with there is no the comparative example of associativity monomer.
Embodiment 5
In following table 5, study the stability in storage of thickening material of the present invention.Find that thickening material of the present invention is obviously more stable.
table 5:
The stability in storage of the thickening material/polymkeric substance being started by anionic monomer:
Embodiment Thickening material number Instant throw out Throw out at 40 DEG C after 4 days
5.1(comp.) V1 Nothing Significantly, not redispersible
5.2 2.1 Nothing Nothing
Bring remarkable improvement by thickening material of the present invention, i.e. sedimentation reduces.
Embodiment 6
Stability in storage according to the care composition preparaton (P1) of the thickening material/polymkeric substance being started by anionic monomer comprising of embodiment 4:
Bring remarkable improvement by thickening material of the present invention, i.e. sedimentation reduces.Almost after 3 months, to using the visible significantly sedimentation of preparaton of thickening material V1, and to use the only visible minimum sedimentation (storing) of preparaton of thickening material 2.1 under RT.
Embodiment 7
Thickening material/the polymkeric substance containing associativity monomer being started by anionic monomer and the impact on thickening efficiency in aqueous formulation of activation dosage:
The listed embodiment 7.1-7.5 of table 6 is prepared according to embodiment 2.1, change after the distillation activation dosage that adds in corresponding in table 11 to the activator concentration in thickening material (A%) (all data are with the % by weight of the amount of anionic polymer in based on this thickening material).The polymer solids mark that all thickening materials (dispersion) of preparation have is in this way 50%.Then under agitation thickening material is added to the water.The aqueous formulation obtaining in this way comprises 1 % by weight thickening material to 99 % by weight water, and 0.5 % by weight anionic polymer is to 99.5 % by weight water.Comp. refer to comparative example.
table 6
Use associativity monomer, requirement exceedes 10% activation dosage to realize fast thickening performance (the final thickening based in 1 minute exceedes 40%).

Claims (20)

1. a thickening material, comprises
I) at least one polymkeric substance that can obtain by the following material of polymerization:
A) at least one water-soluble olefinic unsaturated monomer that comprises at least one anionic monomer and/or at least one non-ionic monomer,
B) the unsaturated associativity monomer of at least one olefinic,
C) optional at least one linking agent,
D) optional at least one chain-transfer agent,
Ii) at least one activator,
Wherein the ratio of activator and polymkeric substance is >10 to 100[% by weight/% by weight].
2. according to the thickening material of claim 1, wherein in described polymkeric substance, component a) comprises at least one anionic monomer, wherein said anionic monomer is selected from vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid or its salt, and especially described anionic monomer is sodium acrylate.
3. according to the thickening material of claim 1 or 2, the described water-soluble fraction of wherein said polymkeric substance is greater than 25 % by weight (based on the gross weight of described polymkeric substance).
4. according to the thickening material of any one in claim 1-3, wherein in described polymkeric substance, component a) comprises at least one non-ionic monomer, and wherein said non-ionic monomer is selected from NVP, N-vinyl imidazole or formula (I) compound:
Wherein
R 7for H or C 1-C 4alkyl,
R 8for H or methyl, and
R 9and R 10be H or C independently of each other 1-C 30alkyl.
5. according to the thickening material of any one in claim 1-4, be wherein selected from formula (II) compound at the unsaturated associativity monomer of olefinic described in described polymkeric substance (components b):
R-O-(CH 2-CHR’-O) n-CO-CR”＝CH 2(II)
Wherein
R is C 6-C 50alkyl, preferably C 8-C 30alkyl, especially C 16-C 22alkyl,
R' is H or C 1-C 4alkyl, preferably H,
R'' is H or methyl,
N is integer 0-100, preferably 3-50, especially 25.
6. according to the thickening material of any one in claim 1-5, wherein be selected from Vinylstyrene at linking agent described in described polymkeric substance (amount of component b), tetra allyl ammonium chloride, vinylformic acid allyl ester, allyl methacrylate, the diacrylate of glycols or poly-glycol and dimethacrylate, divinyl, 1,7-octadiene, allyl group acrylamide or allyl methyl acrylamide, bisacrylamide guanidine-acetic acid, N, N'-methylene-bisacrylamide or polyvalent alcohol polyenoid propyl ether are as poly-allyl sucrose or pentaerythritol triallyl ether.
7. according to the thickening material of any one in claim 1-6, wherein at chain-transfer agent described in described polymkeric substance, (component d) is selected from mercaptan, lactic acid, formic acid, Virahol or phosphinate.
8. according to the thickening material of any one in claim 1-7, wherein said activator is selected from fatty alcohol alkoxy compound, alkyl glycoside, alkyl carboxylic acid ester, benzene sulfonamide acid esters, secondary bond alkyl sulfonic acid ester and fatty alcohol sulfate, is preferably selected from fatty alcohol alkoxy compound.
9. according to the thickening material of any one in claim 1-8, the mixture that wherein uses at least two kinds of activators, wherein the HLB value (hydrophile-lipophile balance value) of at least one activator is that the HLB value of >12 to 20 and at least one activator is 1-12.
10. according to the thickening material of any one in claim 1-9, wherein said polymkeric substance is present in described oil phase with discrete form, preferably as reverse phase dispersion, water-in-oil dispersion or be dispersed in the anhydrous polymer in oil.
Prepare according to the method for the thickening material of any one in claim 1-10 for 11. 1 kinds, wherein said polymkeric substance, by letex polymerization, especially obtains by inverse emulsion polymerization.
12. according to the method for claim 11, wherein after described inverse emulsion polymerization and before adding activator, from described oil phase, steam except at least some water and at least some low boiling point components, especially by LDP (liquid dispersion polymer) technology.
13. according to the method for claim 11 or 12, wherein in described inverse emulsion polymerization process by components b) add in described oil phase.
14. according to the method for any one in claim 11-13, and wherein the temperature in described inverse emulsion polymerization process keeps constant or improves.
15. according to the method for any one in claim 11-14, and wherein the temperature in described inverse emulsion polymerization process keeps constant and is at least 40 DEG C, preferably 50-90 DEG C.
16. 1 kinds comprise at least one according to the thickening material of any one in claim 1-10 containing the acid preparaton of tensio-active agent, the pH of wherein said preparaton is 1 to <7.
17. according to claim 16 containing the acid preparaton of tensio-active agent in hair cosmetic, Hairsetting, as shampoo, as tenderizer, as care composition, as amendment, as skin ointment, as shower gels, as laundry with fabric softening agent or as acidic cleaning agent, be preferred for the purposes of the acidic cleaning agent of lavatory or bathtub.
18. 1 kinds comprise at least one according to the alkaline preparaton containing tensio-active agent of the thickening material of any one in claim 1-10, and the pH of wherein said preparaton is 7-13.
19. according to claim 18 containing the alkaline preparaton of tensio-active agent as care composition, as liquid washing agent or as machine washing or the purposes of washing dish sanitising agent for hand washing.
20. according to the thickening material of any one in claim 1-10 as viscosity modifier, be used for optimizing shear thinning, as thickening material, be that nanometer is to the suspension composition of millimeter scope and/or in the acidity containing tensio-active agent or the purposes of alkaline preparaton for stable dimensions.
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Application publication date: 20141008