EP2776478A1 - Épaississant contenant au moins un polymère à base de monomères associatifs - Google Patents

Épaississant contenant au moins un polymère à base de monomères associatifs

Info

Publication number
EP2776478A1
EP2776478A1 EP12783989.2A EP12783989A EP2776478A1 EP 2776478 A1 EP2776478 A1 EP 2776478A1 EP 12783989 A EP12783989 A EP 12783989A EP 2776478 A1 EP2776478 A1 EP 2776478A1
Authority
EP
European Patent Office
Prior art keywords
polymer
monomer
thickener
alkyl
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12783989.2A
Other languages
German (de)
English (en)
Inventor
Reinhold J. Leyrer
Christofer Arisandy
Ouidad Benlahmar
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP12783989.2A priority Critical patent/EP2776478A1/fr
Publication of EP2776478A1 publication Critical patent/EP2776478A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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

Definitions

  • the present invention relates to a thickener comprising at least one polymer and at least one activator, wherein the ratio of activator to polymer is> 10: 100 [% by weight /% by weight].
  • the polymer can be prepared by polymerizing at least one water-soluble, ethylenically unsaturated monomer comprising at least one anionic monomer and / or at least one nonionic monomer and at least one ethylenically unsaturated associative monomer.
  • the present invention relates to a process for the preparation of the thickener according to the invention and to surfactant-containing formulations comprising at least one thickener. Further subject matters of the invention are the use of the surfactant-containing formulations, for example as fabric softeners or as liquid detergents, and the use of the thickener, for example as a viscosity modifier.
  • WO 03/102043 relates to aqueous formulations comprising a cationic polymer prepared from (i) a water-soluble, ethylenically unsaturated monomer or a monomer mixture comprising at least one cationic monomer, (ii) at least one crosslinker in an amount of more than 50 ppm based on the component (i), and (iii) at least one chain transfer agent.
  • the aqueous formulations can be used as thickeners in household formulations.
  • WO 2009/019225 relates to an aqueous dispersion of an alkali-soluble copolymer which is suitable as an associative thickener.
  • the copolymer comprises copolymerized units of a) at least one ethylenically unsaturated carboxylic acid, b) at least one nonionic ethylenically unsaturated surfactant monomer, c) at least one C 1 -C 2 -alkyl methacrylate, and d) at least one C 2 -C 4 -alkyl acrylate, wherein the the number of alkyl groups of the alkyl acrylate averaged alkyl chain length is 2.1 to 4.0.
  • the associative thickeners can be prepared by emulsion polymerization. The associative thickeners are suitable for use in detergents and cleaners.
  • Liquid dispersion polymer (LDP) compositions are disclosed in WO 2005/097834. These LDP compositions comprise a hydrophilic, water-soluble or swellable polymer having a neutralization level of about 25 to about 100%, a non-aqueous carrier phase, and an oil-in-water surfactant.
  • the hydrophilic, water-soluble or swellable polymer is preferably obtained by polymerization, for example of acrylic acid or methacrylic acid.
  • the LDP Dispersions are suitable for the preparation of microparticulate thickeners, as used for example in aqueous or organic compositions, in particular in personal care or pharmaceutical formulations.
  • WO 2010/078959 relates to cationic polymer thickeners consisting of a crosslinked water-swellable cationic polymer containing at least one cationic monomer and optionally nonionic or anionic monomers, the polymer comprising less than 25% of water-soluble polymer chains based on the total weight of the polymer. Furthermore, the polymer contains a cross-linker in a concentration of 500 to 5000 ppm relative to the polymer.
  • the cationic polymer is prepared by inverse emulsion polymerization.
  • WO 2010/079100 discloses softener compositions containing polymers according to WO 2010/078959.
  • US 2008/0312343 relates to inverse latex compositions and their use as thickeners and / or emulsifiers, for example for the production of cosmetic or pharmaceutical formulations.
  • the inverse latex compositions comprise at least 50 to 80% by weight of at least one linear, branched or cross-linked organic polymer (P), at least 5 to 10% by weight of a water-in-oil type emulsifier system, 5 to 45 Wt .-% of at least one oil and up to 5% water.
  • the polymer P comprises neutral monomers and optionally cationic or anionic monomers.
  • the inverse latex composition may optionally comprise up to 5% by weight of an emulsifier system of the oil-in-water type.
  • the inverse latex compositions can be prepared by inverse emulsion polymerization.
  • EP-A 172 025 relates to a dispersion in a continuous liquid phase of a polymer which is formed by polymerization of an ethylenically unsaturated monomer containing a hydrophobic group of at least 8 carbon atoms and a copolymerizable ethylenically unsaturated monomer.
  • the dispersion is stable, substantially anhydrous and contains at least 40% by weight of polymer.
  • anionic monomers may be used as the copolymerizable, ethylenically unsaturated monomer.
  • the polymerization can be carried out as an inverse emulsion polymerization.
  • EP-A 172 724 relates to polymers obtained by copolymerization of a) an ethylenically unsaturated monomer containing a hydrophobic group having at least 8 carbon atoms and b) water-soluble ethylenically unsaturated monomers getting produced. All monomers are soluble in water as a mixture and the polymer is prepared by inverse emulsion polymerization. The polymer particles have a dry size of ⁇ 4 ⁇ .
  • anionic monomers such as acrylic acid in the form of the free acid or as a water-soluble salt and nonionic monomers such as acrylamide can be used.
  • EP-A 172 723 relates to a process for flocculating a suspension using a water-soluble, substantially linear polymer having a "one-point intrinsic viscosity" of> 3.
  • the polymer is a copolymer of two or more ethylenically unsaturated monomers comprising at least 0 5% by weight of a monomer containing hydrophobic groups
  • the polymer may also be a cationic polymer.
  • the object underlying the present invention is to provide new thickeners.
  • the object is achieved by the thickeners according to the invention comprising i) at least one polymer preparable by polymerization of a) at least one water-soluble, ethylenically unsaturated monomer comprising at least one anionic monomer and / or at least one nonionic monomer,
  • the thickeners according to the invention are characterized in that they have advantageous properties with regard to deposition, shear thinning, stabilization and / or viscosity (thickening).
  • Depositioning is understood to mean the deposition of the active ingredients of, for example, a fabric softener on a fiber during a washing process.
  • the thickeners of the invention promote this deposition of the active ingredient during or after the washing process to a considerable extent. Particularly good deposition properties can be achieved when using polymers based on predominantly neutral monomers based on at least one associative monomer, a nonionic monomer such as acrylamide, and optionally an anionic monomer.
  • the thickener or fabric softener is creamy and thick in its ground state, while it is thin when stirred.
  • the improved shear thinning has a positive effect on the service life and properties of pumps in the production of fabric softener, promotes the comfortable dosing at the customer and promotes the residue-free use of fabric softener, especially in the washing machines, which have an automatic dosing device.
  • the thickeners according to the invention increase the stability of the thickener itself and that of the corresponding formulation. The settling or creaming of particles is effectively prevented, regardless of whether they are on the order of nanometers, microns or millimeters. This contributes to the advantageous yield point of the thickener according to the invention. In addition, they have the advantage that the redispersion and thickening that may be required are achieved very quickly.
  • Thickeners according to the invention in which a mixture of at least two activators are contained, wherein at least one activator has a high HLB value and at least one activator a low HLB value, are associated with an additional advantage.
  • the combination of such an activator mixture with polymers containing at least one ethylenically unsaturated associative monomer building block results in spontaneous phase inversions (within seconds) of diluting a thickener with water without requiring additional energy input, for example in the form of agitation.
  • the action of the associative monomers is optimal even at about 0.5% by weight (based on the polymer).
  • the thickeners according to the invention are prepared by inverse emulsion polymerization, in which the temperature is kept constant at at least 40 ° C., a good uniform distribution of the associative monomer components in the polymer can be observed. This is advantageous in particular in the case of small amounts of, for example, 0.1 to 1% by weight of associative monomers all of the above theological properties such as thickening, shear thinning, stabilization and washing and rinsing effects.
  • Embodiments of the present invention in which the polymers contained in the thickener are prepared using little or no crosslinker are also associated with advantages. Due to the higher (in water) soluble portions of the polymer, redeposition during a wash is reduced. Consequently, the object to be washed even after repeated washing processes, pure fibers that are effectively removed from dirt particles, so that no graying is found. There is no or very little adhesion or redistribution of dirt particles / polymers observed on the washed items.
  • CiC mean 3 of o-alkyl, as for example defined below for the radical R 9 in the formula (I) that this substituent (radical) is an alkyl group having a carbon atom number of 1 to 30
  • the alkyl radical can be both linear and branched and optionally cyclic.
  • Alkyl radicals which have both a cyclic and a linear component are also covered by this definition. The same applies to other alkyl radicals, such as, for example, a C 1 -C 4 -alkyl radical or a C 16 -C 2 -alkyl radical.
  • the alkyl radicals may also be monosubstituted or polysubstituted by functional groups such as amino, quaternary ammonium, hydroxy, halogen, aryl or heteroaryl. Unless stated otherwise, the alkyl radicals preferably have no functional groups as substituents. Examples of alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-ethylhexyl, tertiary-butyl (tert-Bu / t-Bu), cyclohexyl, octyl, stearyl or behenyl.
  • functional groups such as amino, quaternary ammonium, hydroxy, halogen, aryl or heteroaryl.
  • the alkyl radicals preferably have no functional groups as substituents. Examples of alkyl radicals are methyl, ethyl, n-propyl, isopropyl,
  • the thickener according to the invention contains as component i) at least one polymer.
  • the polymer can be prepared by polymerization of the following components a) and b) and optionally c) and d).
  • At least one water-soluble, ethylenically unsaturated monomer comprising at least one anionic monomer and / or at least one nonionic monomer is used as component a).
  • Anionic and nonionic monomers as such are known to those skilled in the art.
  • component a is preferably selected from acrylic acid, methacrylic acid, itaconic acid, Maleic acid or a salt thereof, in particular, the anionic monomer is para-acrylate.
  • esters of the anionic monomers described above are suitable as nonionic monomers, in addition to the nitrogenous monomers described below, such as, for example, the compounds of the formula (I).
  • nonionic monomers are preferably the methyl or ethyl esters of acrylic or methacrylic acid such as ethyl acrylate or methyl acrylate. Further preferred are the corresponding dimethylamino-substituted esters, such as dimethylaminoethyl (meth) acrylate.
  • the nonionic monomer is selected from N-vinylpyrrolidone, N-vinylimidazole or a compound of the formula (I)
  • R 7 is H or d - C 4 alkyl
  • R 8 is H or methyl
  • R 9 and R-io independently of one another are H or C 1 -C 30 -alkyl.
  • the nonionic monomer is acrylamide, methacrylamide or dialkylaminoacrylamide.
  • component a) in the polymer comprises from 30 to 99.5% by weight of at least one anionic monomer and from 0.5 to 70% by weight of at least one nonionic monomer.
  • component a) comprises 100% by weight of at least one nonionic monomer.
  • component a) comprises 100% by weight of at least one anionic monomer. Furthermore, it is preferred in the context of the present invention that component a) comprises no cationic monomer.
  • component b) at least one ethylenically unsaturated associative monomer is used for the preparation of the polymer in the polymerization. Associative monomers as such are known to those skilled in the art. Suitable associative monomers are described, for example, in WO 2009/019225. Associative monomers are also referred to as surfactant monomers.
  • the ethylenically unsaturated associative monomer according to component b) is selected from a compound according to formula (II)
  • R is C 6 -C 50 -alkyl, preferably C 8 -C 30 -alkyl, in particular C 16 -C 22 -alkyl,
  • R ' is H or C 1 -C 4 -alkyl, preferably H,
  • n is an integer from 0 to 100, preferably from 3 to 50, in particular 25. Particular preference is given to using as component b) a compound of the formula (II) in which
  • R is C 16 -C 22 -alkyl
  • n 25.
  • the radical R may also be present in the compounds of the formula (II) as a mixture of radicals having different chain lengths, such as C 16 and C 18 .
  • An example of this is Cie-Cie-fatty alcohol-ethylene glycol ether s-methacrylate, where both C 16 and C 18 fatty alcohol radicals (in non-negligible amounts) are present as a mixture.
  • the compounds (according to formula (II)) behenyl-25-methacrylate and cetyl-25-methacrylate, the respective radical R is not present as a mixture but as C 22 or C 16 chain. Other chain lengths only come in Form of impurities.
  • the number "25" in these compounds according to formula (II) stands for the size of the variable n.
  • At least one crosslinker may be present as component c).
  • Suitable crosslinkers are known to the person skilled in the art.
  • the crosslinker according to component c) is preferably selected from divinylbenzene; Tetraallyl ammonium chloride; allyl acrylates; Allylmethacrylaten; Diacrylates and dimethacrylates of glycols or polyglycols; butadiene; 1, 7-octadiene, allyl acrylamides or allyl methacrylamides; bisacrylamidoacetic; ⁇ , ⁇ '-methylene-bisacrylamide or Polyolpolyallylethern such as polyallylsucrose or pentaerythritol triallyl ether.
  • dialkyldimethylammonium chloride is also suitable as a preferred crosslinker.
  • At least one chain transfer agent can be used in the preparation of the polymer by polymerization as component d).
  • Suitable chain transfer agents are known to the person skilled in the art.
  • Preferred chain transfer agents according to component d) are selected from mercaptan, lactic acid, formic acid, isopropanol or hypophosphites.
  • Suitable polymerization processes for the preparation of the polymer or of the thickener according to the invention comprising at least one polymer and any additives or auxiliaries optionally used in the polymerization or the thickener production process are defined in more detail below in the text.
  • the thickener according to the invention preferably contains at least one polymer which can be prepared by polymerization of a) from 20 to 99.99% by weight, preferably from 95 to 99.95% by weight (based on the polymer), of at least one water-soluble ethylenically unsaturated one Monomers comprising at least one anionic monomer and / or at least one nonionic monomer, b) 0.01 to 80 wt .-%, preferably 0.05 to 5 wt .-%, particularly preferably 0.1 to 1 wt .-% (based on the polymer) of at least one ethylenically unsaturated associative monomer, c) 0 to 0.3 wt .-%, preferably 0.01 to 0.1 wt .-% (based on the polymer) of optionally at least one crosslinking agent, d) 0 to 0.3 wt .-%, preferably 0.01 to 0.1 wt .-% (based on the polymer) optionally at
  • the water-soluble moieties of the polymer are greater than 25% by weight (based on the total weight of the polymer), especially when little or no crosslinker is used in addition to the associative monomer.
  • more than 40% by weight, in particular 70 to 100% by weight, of the polymer is soluble in water.
  • solubility of the polymer is determined by methods known to the person skilled in the art, the polymer contained in the thickener according to the invention being admixed with a defined amount of water (see, for example, EP-A 343 840 or preferably the determination method of the sedimentation coefficient in the dimension Svedberg (sved) according to P Schuck, Size distribution analysis of macromolecules by sedimentation velocity ultracentrifugation and lamb equation modeling, Biophysical Journal 78, (3) (2000), 1606-1619).
  • the proportion of crosslinker (component c) used in the polymerization of the polymer is preferably ⁇ 10% by weight (based on the total amount of components a) to d)). With particular preference, no crosslinker is used in the polymerization of the polymer.
  • the thickener according to the invention also contains as components ii) at least one activator.
  • Activators as such are known in principle to the person skilled in the art. Suitable activators are preferably surfactants, for example anionic, nonionic, cationic and / or amphoteric surfactants, which are disclosed, for example, in WO 2009/019225. Preferably, anionic and / or nonionic surfactants are used. As nonionic surfactants preferably fatty alcohol alkoxylates are used. Fatty alcohol alkoxylates are also referred to as polyalkylene glycol ethers.
  • Preferred fatty alcohol alkoxylates are alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or branched, preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of native or technical origin having 12 to 18 carbon atoms, for example, from coconut, palm, tallow or oleyl - or mixtures, such as castor oil, derivable - and an average of 2 to 8 EO per mole of alcohol preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO, 4 EO or 7 EO, C 9 -Cn-alcohol with 7 EO, C 13 -C 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci 2 -Ci 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants containing EO and PO groups together in the molecule can also be used.
  • block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • nonionic surfactants mixed alkoxylated nonionic surfactants
  • EO and PO units are not randomly distributed but randomly distributed
  • Such products are obtainable by simultaneous action of ethylene oxide and propylene oxide on fatty alcohols.
  • alkyl glycosides or alkyl polyglycosides can be used.
  • alkyl glycosides or alkyl polyglycosides the skilled person generally understands compounds which are composed of at least one alkyl fragment and at least one sugar or poly-sugar fragment.
  • the alkyl fragments are preferably derived from fatty alcohols having a carbon atom number of 12 to 22 and the sugar fragments preferably from glucose, sucrose or sorbitan.
  • alkyl glycosides of the general formula (1) 10 (G) x (1) in which R 1 is a primary straight-chain or methyl-branched, in particular methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms. Atoms is and G is a glycoside unit having 5 or 6 carbon atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese Patent Application JP 58/217598 or preferably prepared according to the method described in International Patent Application WO-A-90/13533 become.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • surfactants are polyhydroxy fatty acid amides of the formula (2),
  • R 3 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (3)
  • R 4 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 5 is a linear, branched or cyclic alkylene radical having 2 to 8 carbon atoms or an arylene radical having 6 to 8 carbon atoms
  • R 6 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1 -C 4 -alkyl or phenyl radicals being preferred
  • [Z] 1 being a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] 1 is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides according to WO-A-95/07331, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • anionic surfactants are, for example, those of the sulfonate-type and sulfates type.
  • the surfactants of the sulfonate type are alkylbenzenesulfonates, preferably C 9 -C 13 -alkylbenzenesulfonates, olefin-sulfonates, ie mixtures of alkene- and hydroxyalkanesulfonates and disulfonates.
  • alkanesulfonates suitable for example from C 12 -C 18 monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products are also suitable alkanesulfonates, preferably secondary alkanesulfonates, for example, from C 12 C 18 -alkanes can also be obtained by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, likewise suitable are the esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids Further suitable anionic surfactant e are sulfated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • fatty alcohol sulfates for example alk (en) ylsulfates.
  • Alk (en) yl sulfates are the alkali and especially the sodium salts of Schwefelhoffreraumester the C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or Cio-C 2 o-oxoalcohols and those half-esters of secondary alcohols of these chain lengths are preferred.
  • alk (en) ylsulfates of the mentioned Chain length which contain a synthetic, petrochemical-based straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and Ci4-Ci 5 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • sulfuric acid monoesters of straight-chain or branched C 7 -C 2 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 1 -C 4 -n alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 -C 18 - Fatty alcohols with 1 to 4 EO are suitable.
  • alkylsulfosuccinic acid which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 -C 18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • alkyl carboxylates for example the sodium salts of saturated or unsaturated fatty acids, wherein the alkyl radical of the alkyl carboxylate is preferably linear.
  • the activator is preferably selected from fatty alcohol alkoxylates, alkyl glycosides, alkyl carboxylates, alkyl benzene sulfonates, secondary alkane sulfonates and fatty alcohol sulfates, more preferably selected from fatty alcohol alkoxylates.
  • fatty alcohol alkoxylates C 6 -C 17 (secondary) poly (3-6) ethoxylate.
  • an activator which has a (relatively) high HLB value (hydrophilic-lipophilic balance value).
  • the activator has an HLB value of 7 to 18, more preferably 8 to 15, and most preferably 9 to 13.
  • Activators with a high HLB value are preferably i) fatty alcohol alkoxylates of secondary alcohols or mixtures of alcohols having 12 to 18 carbon atoms and ethylene oxide or propylene oxide and ii) alkyl glycosides of sucrose and C 8 to C 2 fatty alcohols.
  • activators are the commercially available Synperonic 87K from Croda GmbH,dorfpfad-Süd 33, 41334 Nettetal, Germany; Croduret 40 or other ethoxylated hydrogenated castor oils (castor oils) such as Etocas 40 or Crodesta F1 10, all from Croda.
  • the high HLB activator preferably has an HLB value of> 12 to 20, and the low HLB activator preferably has an HLB value of 1 to 12.
  • the high HLB activator may have a high HLB value. Value and the activator with a low HLB value in any known to those skilled ratios to each other. Preferably, 20 to 50% by weight of high HLB activator and 50 to 80% by weight of low HLB activator are employed in the blend. Further preferably, this ratio of high HLB activator to low HLB activator is adjusted so that the total HLB is 7 to 18, more preferably 8 to 15 and most preferably 9 to 13.
  • activators are preferably used as activators with a high HLB value alkyl glycosides or Polyalkylglykoside or Polyalkyloligoethylenoxidglykosid based on sucrose or sorbitan and C 8 to C 2 2- fatty alcohols such as Polyethylenglykolsorbitanmonostearat or Polyoxyethylensorbitan- monostearat.
  • activators are the commercially available Crillet 1, Crillet 3 or Crodesta F160, all available from Croda.
  • activators with a low HLB value preference is given to using alkyl glycosides of sucrose or sorbitan and C 8 to C 2 fatty alcohols or fatty acids, such as sorbitan laurate or sorbitan stearate.
  • Examples of such activators are the commercially available Crill 1, Crill 3 or Crodesta F10 from Croda.
  • the ratio of activator to polymer is> 10: 100 [% by weight /% by weight], preferably 10.5 to 50: 100 [% by weight /% by weight], more preferably 1 1, 5 to 20: 100 [% by weight /% by weight].
  • the thickeners according to the invention may be present in the thickeners according to the invention. Suitable additional components are in the text below in the production of the thickener or the polymer defined in more detail. Suitable further components may be, for example, oils and solvents.
  • the polymer can be dispersed in the oil phase, preferably as an inverse dispersion, water-in-oil dispersion or as dispersed anhydrous polymer in oil.
  • Another object of the present invention is a process for the preparation of the thickener according to the invention.
  • Thickener production processes as such and processes for the preparation of a polymer are known to the person skilled in the art.
  • the polymer is obtained by an emulsion polymerization, in particular by an inverse emulsion polymerization.
  • the polymer is first prepared and following the polymerization, preferably by inverse emulsion polymerization, the activator is added to obtain the thickener.
  • the polymer can be prepared in various ways, preferably by emulsion polymerization, in particular by inverse emulsion polymerization.
  • emulsion polymerization By inverse emulsion polymerization, one skilled in the art will generally understand polymerization processes as defined below:
  • the hydrophilic monomers are dispersed in a hydrophobic oil phase.
  • the polymerization takes place directly in these hydrophilic monomer particles by addition of initiator.
  • At least a portion of water and at least a portion of the low-boiling components of the oil phase are distilled off, in particular by means of LDP technology (Liquid Dispersion Polymer Technology).
  • LDP technology Liquid Dispersion Polymer Technology
  • emulsion polymerization such as for emulsion polymerization in water, which then also represents the continuous phase, and in particular also for inverse emulsion polymerization, in which the hydrophobic oil phase is the continuous phase.
  • a suitable polymerization initiator is used for polymerization. Redox initiators and / or thermally activatable radical polymerization initiators are preferred.
  • Suitable thermally activatable radical initiators or the oxidative component of the redox initiator pair are especially those of the peroxy and Azo type. These include, among others, hydrogen peroxide, peracetic acid, t-butyl hydroperoxide, di-t-butyl peroxide, dibenzoyl peroxide, benzoyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethyl-2,5-bis (hydroperoxy) hexane, perbenzoic acid, t-butyl Butyl peroxypivalate, t-butyl peracetate, dilauroyl peroxide, dicapryloyl peroxide, distearoyl peroxide, dibenzoyl peroxide, diisopropyl peroxydicarbonate, didecyl peroxydicarbonate,
  • the initiator is used in an amount sufficient to initiate the polymerization reaction.
  • the initiator is usually used in an amount of about 0.01 to 3 wt .-%, based on the total weight of the monomers used.
  • the amount of initiator is preferably about 0.05 to 2 wt .-% and in particular 0.1 to 1 wt .-%, based on the total weight of the monomers used.
  • the emulsion polymerization is usually carried out at 35 to 100 ° C. It can be carried out both as a batch process and in the form of a feed process.
  • the polymerization initiator and optionally a portion of the monomers are heated to the polymerization temperature and then the remainder of the polymerization batch, usually via a plurality of separate feeds, one or more of which contains the monomers in pure or emulsified form, continuously or stepwise while maintaining the polymerization.
  • the monomer feed takes place in the form of a monomer emulsion. Additional polymerization initiator can be added in parallel to the monomer feed.
  • the total amount of initiator is given, i. H. no additional initiator feed takes place parallel to the monomer feed.
  • the thermally activatable radical polymerization initiator is completely introduced, and the monomer mixture, preferably in the form of a monomer emulsion, is allowed to run in.
  • the monomer mixture preferably in the form of a monomer emulsion
  • the template Before starting the feed of the monomer mixture, bringing the template on the activation temperature of the thermally activated radical polymerization initiator or a higher temperature.
  • activation temperature the temperature at which at least half of the initiator has decomposed after one hour is considered.
  • the polymer is obtained by polymerization of a monomer mixture in the presence of a redox initiator system.
  • a redox initiator system comprises at least one oxidizer component and at least one reductant component, with heavy metal ions as catalyst being additionally present in the reaction medium, for example cerium, manganese or iron (II) salts.
  • Suitable oxidizing agent components are, for example, peroxides and / or hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, pinane hydroperoxide, diisopropylphenyl hydroperoxide, dicyclohexyl percarbonate, dibenzoyl peroxide, dilauroyl peroxide and diacetyl peroxide. Hydrogen peroxide and tert-butyl hydroperoxide are preferred.
  • Suitable reducing agent components are alkali metal sulfites, alkali metal dithionites, alkali metal hyposulfites, sodium hydrogen sulfite, Rongalit C
  • iron (II) salts e.g. Iron (II) sulfate, stannous salts, e.g. Tin (II) chloride, titanium (III) salts such as titanium (III) sulfate.
  • the amounts of oxidizing agent are from 0.001 to 5.0 wt .-%, preferably from 0.005 to 1, 0 wt .-% and particularly preferably from 0.01 to 0.5 wt .-%, based on the total weight of the monomers used.
  • Reducing agents are used in amounts of 0.001 to 2.0 wt .-%, preferably from 0.005 to 1, 0 wt .-% and particularly preferably from 0.01 to 0.5 wt .-%, based on the total weight of the monomers used .
  • a particularly preferred redox initiator system is the system sodium peroxodisulfate / sodium bisulfite, e.g. B.
  • 0.001 to 5.0 wt .-% sodium peroxodisulfate and 0.001 to 2.0 wt .-% sodium bisulfite in particular 0.005 to 1, 0 wt .-% sodium peroxodisulfate and 0.005 to 1, 0 wt .-% sodium bisulfite, particularly preferably 0 , 01 to 0.5 wt .-% sodium peroxodisulfate and 0.01 to 0.5 wt .-% sodium hydrogen sulfite.
  • Another particularly preferred redox initiator system is the system t-butyl hydroperoxide / hydrogen peroxide / ascorbic acid, e.g.
  • t-butyl hydroperoxide 0.001 to 5.0% by weight of t-butyl hydroperoxide, 0.001 to 5.0% by weight of hydrogen peroxide and 0.001 to 2.0% by weight of ascorbic acid, in particular 0.005 to 1.0% by weight of t-butyl hydroperoxide , 0.005 to 1, 0 wt .-% hydrogen peroxide and 0.005 to 1, 0 wt .-% ascorbic acid, particularly preferably 0.01 to 0.5 wt .-% t-butyl hydroperoxide, 0.01 to 0.5 wt. % Hydrogen peroxide and 0.01 to 0.5% by weight ascorbic acid.
  • the polymer is prepared by inverse emulsion polymerization by first preparing an aqueous phase of the water-soluble components and an oil phase separately from each other. The two phases are then mixed together to give a water-in-oil dispersion. The mixture is polymerized by adding a redox initiator system, optionally thereafter a thermal initiator may be added or, if already present, thermally activated.
  • aqueous phase preferably a chain transfer agent, a crosslinker, an anionic monomer and / or a neutral monomer and optionally the associative monomer and optionally further components.
  • Suitable further components are, for example, complexing agents for salts such as pentasodium diethylenetriaminepentaacetic acid.
  • an emulsifier, a stabilizer, a high-boiling oil, a low-boiling oil and / or optionally the associative monomer are preferably contained. Furthermore, in the oil phase may optionally be contained a non-ionic monomer.
  • Emulsifiers, stabilizers, low-boiling oils and high-boiling oils as such are known to the person skilled in the art. These compounds can be used singly or in the form of mixtures.
  • Typical emulsifiers are anionic emulsifiers such. Sodium lauryl sulfate, sodium tridecyl ether sulfates, dioctyl sulfosuccinate sodium salt and sodium salts of alkylaryl polyether sulfonates; and nonionic emulsifiers such.
  • Preferred emulsifiers have the following general formula: R-O- (CH 2 -CHR'-O) n -X, wherein R is C 6 -C 30 -alkyl,
  • R ' is hydrogen or methyl
  • X is hydrogen or S0 3 M
  • M is hydrogen or an alkali metal
  • n is an integer from 2 to 100
  • Suitable stabilizers are described, for example, in EP-A 172 025 or EP-A 172 724.
  • Preferred stabilizers are copolymers of stearyl methacrylate and methacrylic acid.
  • suitable high-boiling oils are 2-ethylhexyl stearate and hydroheated heavy naphtha, and as low-boiling oils, for example, dearomatized aliphatic hydrocarbons or mineral oils of low viscosity.
  • component b) (at least one ethylenically unsaturated associative monomer) is added to the oil phase.
  • the temperature can be kept constant or it can also increase.
  • the increase in temperature can be carried out continuously or in stages.
  • the temperature during polymerization may increase by 0.2 to 10 ° C per minute, preferably from 1 to 3 ° C per minute.
  • the temperature rise is controlled by the rate of initiator addition.
  • the temperature output may be 0 to 30 ° C, preferably 10 to 20 ° C.
  • the temperature in the inverse emulsion polymerization is kept constant (cold mode), the temperature is 0 to 30 ° C, preferably 10 to 20 ° C.
  • the temperature is kept constant in a higher temperature range (warm mode).
  • the temperature in the polymerization is 40 to 150 ° C, preferably 70 to 120 ° C.
  • the temperature during the inverse emulsion polymerization is kept constant, wherein the temperature is at least 40 ° C, preferably 50 to 90 ° C. If the temperature is kept constant in the context of the present invention in a polymerization, in particular in an inverse emulsion polymerization, this means that from the beginning of the polymerization, the temperature is maintained at a constant value. Fluctuations of +/- 5 ° C, preferably +/- 2 ° C and especially +/- 1 ° C during the polymerization process are considered to be a constant temperature (based on the desired constant temperature value).
  • the temperature is kept constant until the polymerization is complete, this is preferably the case after a conversion of more than 90% of the monomers used, more preferably more than 95 wt .-% and particularly preferably at full conversion (100 wt .-% ).
  • the temperature can be kept constant by the resulting heat of reaction is removed by cooling.
  • the start of the polymerization is normally the addition of the polymerization initiator, preferably the addition of a redox initiator system. Normally, the system is first heated to the desired temperature and maintained under stirring until the temperature is constant. Subsequently, the addition of the polymerization initiator, whereby the polymerization process is started.
  • the temperature is kept constant at a value which is above the melting point of the associative monomer employed.
  • Another object of the present invention are surfactant-containing acidic formulations containing at least one thickener according to the invention according to the above definitions.
  • the pH of the formulation is 1 to ⁇ 7.
  • surfactant-containing alkaline formulations containing at least one thickener according to the invention according to the above definitions are surfactant-containing alkaline formulations containing at least one thickener according to the invention according to the above definitions.
  • the pH of the formulation is 7 to 13.
  • further ingredients may be present which are known to the person skilled in the art. Suitable ingredients include one or more of builders, bleaches, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotropes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents , Anti-crease agents,
  • Another object of the present invention is the use of a surfactant-containing acidic formulation according to the invention in hair cosmetics, hair styling, as a shampoo, as a fabric softener, as a conditioner, as a skin cream, as a shower gel, as a softener for laundry, or as an acidic cleaner , preferably for the toilet or the bathroom.
  • Another object of the present invention is the use of a surfactant-containing alkaline formulation as a care agent, as a liquid detergent or dishwashing detergent for machine or hand washing.
  • Another object of the present invention is the use of the thickener according to the invention as a viscosity modifier, to optimize the shear thinning, as a thickener, for stabilizing suspended ingredients with a size in the range of nanometers to millimeters and / or in surfactant-containing acidic or alkaline formulations.
  • An aqueous phase of water-soluble components is prepared by admixing the following components:
  • An oil phase is prepared by admixing the following components:
  • the two phases are mixed in a ratio of 55.6 parts aqueous phase to 44.4 parts oil phase under high shear to produce a water-in-oil emulsion.
  • the resulting water-in-oil emulsion is added to a reactor equipped with nitrogen spray, stirrer and thermometer. The emulsion is purged with nitrogen to remove the oxygen and cooled to 20 ° C.
  • the polymerization is accomplished by adding a redox couple
  • the redox couple is gradually added so that the temperature increase of 2 ° C / min takes place.
  • a free radical initiator (2,2'-azobis (2-methylbutyronitrile), CAS: 13472-08-7) is added in 2 steps (the 2nd step after 45 minutes) and the emulsion is added for 75 minutes kept at 85 ° C.
  • Vacuum distillation removes water and low boiling components of the oil phase (Isopar G).
  • Mineral oil of low viscosity Kristol M14 is added to this product to achieve a solids content of 54%.
  • Thickener / polymers starting from anionic monomers with associative monomer and constant polymerization temperature :
  • An aqueous phase of water-soluble components is prepared by admixing the following components:
  • An oil phase is prepared by admixing the following components:
  • the two phases are mixed in a ratio of 55.6 parts aqueous phase to 44.4 parts oil phase under high shear to produce a water-in-oil emulsion.
  • the resulting water-in-oil emulsion is added to a reactor equipped with nitrogen spray, stirrer and thermometer. The emulsion is purged with nitrogen during heating to 50 ° C, whereby the oxygen is removed.
  • the polymerization is accomplished by adding a redox couple
  • the redox couple is added at 50 ° C within 2 hours. It is then heated to 85 ° C and then in 2 steps (the 2nd step after 45 min), a free radical initiator (2,2'-azobis (2-methylbutyronitrile), CAS: 13472-08-7) is added and the emulsion Held at 85 ° C for 75 minutes.
  • Vacuum distillation removes water and low boiling components of the oil phase (Isopar G).
  • Mineral oil of low viscosity Kristol M14
  • Kristol M14 Mineral oil of low viscosity
  • To this product is added 8% (by total weight of this product) of a fatty alcohol alkoxylate (C12 / 15 alcohol alkoxylate [Synperonic 87K TM]) to make a thickener (dispersion) with 50% polymer solids.
  • the ratio of activator to polymer is thus 16.0: 100 [wt .-% / wt .-%].
  • Example 1 The following examples according to Table 1 are prepared as Example 1 .1, taking into account the specified changes in the monomer composition.
  • the associative monomer C16E025MAc is added to the oil phase.
  • the commercial product Plex 6954 O is used which contains 60% by weight of associative monomer and, as solvent, water and MAA in a ratio of about 1: 1.
  • the weights in Table 1 refer to the amount of associative monomer without solvent.
  • the ratio of activator to polymer in all examples according to Table 1 is 16.0: 100 [wt .-% / wt .-%], unless otherwise stated, the respective thickener (dispersion) 50% polymer solids content.
  • Thickener / polymers starting from anionic monomers with associative monomer and increasing polymerization temperature :
  • the following examples according to Table 2 are prepared in the same way as Comparative Example C1 taking into account the stated changes in the monomer composition.
  • the associative monomer C16E025MAc is added to the oil phase.
  • the commercial product Plex 6954 O is used which contains 60% by weight of associative monomer and, as solvent, water and MAA in a ratio of about 1: 1.
  • the weights in Table 2 refer to the amount of associative monomer without solvent.
  • the ratio of activator to polymer in all examples according to Table 2 is 16.0: 100 [% by weight /% by weight], unless stated otherwise, the respective thickeners (dispersion) have 50% polymer solids content.
  • the rotational rheometer ASC (automatic sample changer) from Fa. Antonzip is used, with the cylinder geometry CC27, the radius of the measuring body of 13.33 mm and the radius of the measuring cup of 14.46 mm.
  • the measuring temperature is 23 ° C.
  • the samples are measured in stationary shear starting with small shearing towards large (0.01 S “1 - 1000 S “ 1 ) and back again (1000 S “1 - 0.01 S " 1 ).
  • the thickeners are slowly added to distilled water at room temperature according to Table 3 and stirred until the formulation is homogenized.
  • the resulting aqueous formulations contain according to Table 3 either 1, 0 wt .-% polymer to 99.0 wt .-% water or 0.5 wt .-% polymer to 99.5 wt .-% water. The results are summarized in Table 3.
  • Example 4.1 When an increasing amount of associative monomer is incorporated into the polymer, the thickening performance increases significantly more vis-a-vis V1 without associative monomer.
  • the procedure at constant polymerization temperature of 50 ° C provides an increased thickening power with otherwise the same monomer composition.
  • the last four examples of Table 3 relate to acrylamide-containing polymers. Example 4.1
  • the conditioner formulation (P1) contains the ingredients according to Table 4.1. P1 is prepared by heating phases A and B each at 80 ° C. Thereafter, the two phases are added together and homogenized. Subsequently, it is cooled with stirring to about 40 ° C, whereupon the phase C is added and homogenized.
  • the thickeners or thickeners according to the comparative examples according to the invention listed in Table 4.1. 2 are slowly added at room temperature to the conditioner formulation P1 and stirred until the formulation is homogenized.
  • the care formulations thus obtained contain the stated concentration of thickener in% by weight to 100% by weight of the resulting care formulations.
  • Example 4.2 Application of thickeners / polymers in standard formulations of fabric softener W3 W3: Preparation of a methyltris (hydroxyethyl) ammonium di-tallow fatty acid ester methosulfate, partially hydrogenated fabric softener (5.5% active ingredient):
  • the fabric softener has a pH of 2.7 and contains 5.5% by weight.
  • Softener formulation is added and stirred until the formulation is homogenized.
  • Brookfield viscosity is measured one day after preparation. The
  • Example 6 Storage stability of care formulation (P1) according to Example 4 containing thickener / polymers starting from anionic monomers:
  • thickener according to the invention. After almost three months with formulation with thickener V1 more clearly and with formulation with thickener 2.1 only minimal sediment can be detected (storage at RT).
  • Example 7 Thickener / polymers starting from anionic monomers with associative monomer and influence of the amount of activator on the rate of thickening in aqueous formulations:
  • the examples 7.1 to 7.5 listed in Table 6 are prepared according to Example 2.1, wherein the amount of activator added after the distillation is as shown in Table 1 1 activator concentration (A%) is varied in the thickener (all data in wt .-% based on the amount of anionic polymer in the thickener). All thickeners (dispersion) thus produced have 50% polymer solids content. The thickeners are then added to the water with stirring.
  • aqueous formulations obtained contain 1 wt .-% thickener to 99 wt .-% water, ie 0.5 wt .-% of anionic polymer to 99.5 wt .-% water.
  • Comp. Means comparative example.

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Abstract

L'invention concerne un épaississant contenant i) au moins un polymère pouvant être obtenu par polymérisation de a) au moins un monomère hydrosoluble éthyléniquement insaturé comprenant au moins un monomère anionique et/ou au moins un monomère non ionique, b) au moins un monomère associatif éthyléniquement insaturé, c) éventuellement au moins un agent de réticulation, d) éventuellement au moins un agent de transfert de chaîne, ii) au moins un activateur, le rapport entre l'activateur et le polymère étant de > 10 à 100 [% en poids/% en poids].
EP12783989.2A 2011-11-11 2012-11-07 Épaississant contenant au moins un polymère à base de monomères associatifs Withdrawn EP2776478A1 (fr)

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EP12783989.2A EP2776478A1 (fr) 2011-11-11 2012-11-07 Épaississant contenant au moins un polymère à base de monomères associatifs
PCT/EP2012/072016 WO2013068392A1 (fr) 2011-11-11 2012-11-07 Épaississant contenant au moins un polymère à base de monomères associatifs

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FR3024736B1 (fr) * 2014-08-06 2016-08-26 Snf Sas Utilisation dans des compositions detergentes de polymeres obtenus par polymerisation en emulsion inverse basse concentration avec un faible taux de monomeres neutralises
WO2017205339A1 (fr) * 2016-05-23 2017-11-30 Ecolab Usa Inc. Compositions acides de nettoyage, d'aseptisation et de désinfection à faible embuage par l'utilisation de polymères en émulsion d'eau dans l'huile à masse moléculaire élevée
WO2017205334A1 (fr) 2016-05-23 2017-11-30 Ecolab Usa Inc. Compositions alcalines et neutres de nettoyage, d'aseptisation et de désinfection à faible embuage par l'utilisation de polymères en émulsion d'eau dans l'huile à masse moléculaire élevée
CN107099001B (zh) * 2017-04-19 2019-08-02 广州天赐高新材料股份有限公司 一种羧酸共聚物增稠剂及其制备方法
WO2019016336A1 (fr) 2017-07-21 2019-01-24 Basf Se Polymère à base de monomères anioniques ou non ioniques présentant une distribution au moins bimodale des masses moléculaires
WO2019016334A1 (fr) 2017-07-21 2019-01-24 Basf Se Procédé d'obtention d'un polymère à base de monomères anioniques ou non ioniques présentant une distribution de poids moléculaires au moins bimodale
CN115362248A (zh) * 2020-04-07 2022-11-18 巴斯夫欧洲公司 适合作为洗涤剂制剂中的抗灰化剂的聚合物组合物
CN113372505B (zh) * 2021-06-28 2022-04-08 浙江震东新材料有限公司 一种耐盐增稠剂共聚物及其制备方法

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MX2014005533A (es) 2014-05-30
RU2014123615A (ru) 2015-12-20
CA2853243A1 (fr) 2013-05-16
BR112014011314A2 (pt) 2017-05-09
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