JP2015504455A - Thickener containing at least one polymer based on associative monomers - Google Patents

Abstract

The present invention relates to i) a) at least one water-soluble ethylenically unsaturated monomer comprising at least one anionic monomer and / or at least one nonionic monomer, b) at least one ethylenically unsaturated monomer. A saturated associative monomer, c) optionally at least one crosslinking agent, d) optionally at least one polymer obtainable by polymerization of at least one chain transfer agent, and ii) at least one activator In which the ratio of activator to polymer is greater than 10 to 100 [wt% / wt%]. [Selection figure] None

Description

  The present invention relates to a thickener comprising at least one polymer and at least one active agent, wherein the ratio of active agent to polymer is greater than 10: 100 [wt% / wt%]. The polymer polymerizes 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. Can be prepared. Furthermore, the present invention also relates to a method for producing a thickener according to the present invention and a surfactant-containing formulation comprising at least one thickener. The invention further provides the use of a surfactant-containing formulation, for example as a softener or as a liquid detergent, and also a thickener, for example as a viscosity modifier.

  (Patent Document 1) describes: (i) a water-soluble ethylenically unsaturated monomer or monomer mixture containing at least one cationic monomer, (ii) at least one cross-linking in an amount greater than 50 ppm based on component (i) And (iii) an aqueous formulation comprising a cationic polymer prepared from at least one chain transfer agent. Aqueous formulations can be used as thickeners in household formulations.

(Patent Document 2) relates to an aqueous dispersion of an alkali-soluble copolymer, which is suitable as an associative thickener. The copolymer comprises 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 ) The alkyl chain length comprising at least one polymerized unit of C _{2 to} C ₄ alkyl acrylate and the average number of alkyl groups of the alkyl acrylate is 2.1 to 4.0. Associative thickeners can be prepared by emulsion polymerization. Associative thickeners are suitable for use in detergents and cleaners.

  A liquid dispersion polymer (LDP) composition is disclosed in US Pat. These LDP compositions comprise a hydrophilic, water-soluble or swellable polymer having a neutralization content 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, for example, by polymerization of acrylic acid or methacrylic acid. LDP dispersions are suitable, for example, for the production of particulate thickeners used in aqueous or organic compositions, in particular in personal care or pharmaceutical formulations.

  US Pat. No. 6,057,037 is a crosslinked water-swellable cationic polymer comprising at least one cationic monomer and optionally a nonionic or anionic monomer, 25% based on the total weight of the polymer The present invention relates to a cationic polymer thickener comprising a polymer containing less than water-soluble polymer chains. In addition, the polymer also contains a cross-linking agent at a concentration of 500-5000 ppm relative to the polymer. Cationic polymers are prepared by reverse phase emulsion polymerization.

  (Patent Document 5) discloses a fabric softener composition comprising a polymer according to (Patent Document 4).

  US Pat. No. 6,099,059 relates to reversed-phase latex compositions and their use as thickeners and / or emulsifiers, for example for the production of cosmetic or pharmaceutical preparations. The reverse latex composition comprises at least 50-80% by weight of at least one linear, branched or cross-linked organic polymer (P), at least 5-10% by weight of a water-in-oil emulsifier system, 5-45% by weight. Contains at least one oil and up to 5% water. The polymer P comprises neutral monomers and optionally cationic or anionic monomers. The reverse latex composition can optionally include up to 5% by weight of an oil-in-water emulsifier system. The reverse phase latex composition can be prepared by reverse phase emulsion polymerization.

  (Patent Document 7) disperses, in a continuous liquid phase, a polymer produced by polymerization of an ethylenically unsaturated monomer containing a hydrophobic group having at least 8 carbon atoms and an ethylenically unsaturated monomer copolymerizable therewith. Related to the dispersion. The dispersion is stable and essentially anhydrous and contains at least 40% by weight of polymer. In the polymerization, for example, an anionic monomer can be used as the copolymerizable ethylenically unsaturated monomer. The polymerization can be performed as reverse phase emulsion polymerization.

  (Patent Document 8) relates to a polymer prepared by copolymerization of a) an ethylenically unsaturated monomer containing a hydrophobic group having at least 8 carbon atoms and b) a water-soluble ethylenically unsaturated monomer. All monomers are soluble in water as a mixture and the polymer is prepared by reverse phase emulsion polymerization. The polymer particles have a dry size of less than 4 μm. As monomer component b) it is possible to use anionic monomers such as acrylic acid in the form of the free acid or as water-soluble salts, and also nonionic monomers such as acrylamide.

  (Patent Document 9) relates to a method for agglomerating a suspension using a water-soluble and essentially linear polymer having a “single point intrinsic viscosity” of more than 3. The polymer is a copolymer of two or more ethylenically unsaturated monomers containing at least 0.5% by weight of monomers containing hydrophobic groups. The polymer may be a cationic polymer.

International Publication No. 03/102043 International Publication No. 2009/019225 International Publication No. 2005/097834 International Publication No. 2010/078959 International Publication No. 2010/079100 US Patent Application Publication No. 2008 / 0,312,343 European Patent Application No. 172025 European Patent Application No. 172724 European Patent Application No. 172723

  The problem underlying the present invention is to provide a novel thickener.

This purpose is
i) at least one polymer;
a) at least one water-soluble ethylenically unsaturated monomer comprising at least one anionic monomer and / or at least one nonionic monomer;
b) at least one ethylenically unsaturated associative monomer;
c) optionally at least one crosslinking agent,
d) a polymer optionally prepared by polymerization of at least one chain transfer agent;
ii) Realized by thickeners according to the invention comprising at least one active agent, the ratio of active agent to polymer being greater than 10: 100 [wt% / wt%].

  The thickener according to the invention is characterized in that it has advantageous properties with regard to deposition, shear dilution, stabilization and / or viscosity (thickening). Deposition is understood to mean the deposition of active raw materials, such as fabric softeners, on the fibers during the washing operation. When applied to the present invention, this means, for example, that a thickener according to the invention comprising at least one polymer (active raw material) is present in the fabric softener, which is used during or after the washing operation. Means that The thickener according to the invention accelerates this deposition of active raw materials to a considerable extent during or after the washing operation. Particularly good properties with regard to deposition can be achieved when using polymers based on mostly neutral monomers, based on at least one associative monomer, a nonionic monomer such as acrylamide, and optionally an anionic monomer. .

  When assessing shear dilution, it is important that the thickening agent or the corresponding fabric softener is viscous and thick in its basic state, but becomes less viscous when stirred. Improving shear dilution has a positive effect on the life and characteristics of the pump in the manufacture of fabric softeners, making it easier for consumers to load, especially in washing machines with automatic dosing devices. The residue is less likely to remain. The thickener according to the invention improves the stability of the thickener itself and the corresponding formulation. Particle precipitation or creaming is virtually prevented even if the particles are in the order of nanometers, microns or millimeters. The contributing factor here is the advantageous yield point of the thickener according to the invention. Moreover, the thickener according to the invention has the advantage that any necessary redispersion and thickening can be realized very quickly.

  The thickener according to the invention has a further advantage in that there is a mixture of at least two active agents, in which case the HLB value of at least one active agent is high and the HLB value of at least one active agent is low. ing. When such an active agent mixture is combined with a polymer comprising at least one ethylenically unsaturated associative monomer component, the thickener is diluted with water without requiring additional energy input, for example, in the form of agitation. Spontaneous phase inversion is triggered (within seconds).

  Furthermore, in the case of the thickener according to the invention, it is an advantage that the ratio of associative monomers to total polymer is relatively low. When this thickener is used in a surfactant-containing formulation, the associative monomer effect is optimal even in an amount of about 0.5% by weight (based on polymer).

  When the thickener according to the invention is prepared by reverse phase emulsion polymerization which keeps the temperature at least at 40 ° C., good uniformity of the associative monomer component distribution within the polymer can be observed. In particular, if the amount of associative monomer used is low, for example 0.1 to 1% by weight, this may be due to the above mentioned rheological properties in general, for example thickening, shear dilution, stabilization and even washing and washing out. It is advantageous in terms of effect.

  Embodiments of the present invention in which the polymer present in the thickener is prepared with little or no crosslinker are equally advantageous. Due to the relatively high (water) soluble component of the polymer, soil redeposition during cleaning operations is reduced. As a result, the article to be cleaned has clean fibers with virtually no dirt particles removed, i.e. no graying is detected, even after repeating the cleaning process. No or very little adhesion / redistribution of dirt particles / polymer to the cleaned article is observed.

In the context of the present invention, for example, the definition of C ₁ -C ₃₀ alkyl and the like defined below for radical R ₉ in formula (I) is such that the substituent (radical) is an alkyl having 1 to 30 carbon atoms. Means a radical. Alkyl radicals can be linear or branched, and optionally cyclic. Alkyl radicals having both cyclic and linear components are likewise within the scope of this definition. Other alkyl radicals same, for _example, applies to C 1 -C ₄ alkyl radical or a _C 16 _{-C 22} alkyl radicals, and the like. The alkyl radical may optionally be mono- or polysubstituted by functional groups such as amino, quaternary ammonium, hydroxy, halogen, aryl or heteroaryl. Unless otherwise specified, the alkyl radical preferably has no functional group as a substituent. Examples of alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-ethylhexyl, tert-butyl (tert-Bu / t-Bu), cyclohexyl, octyl, stearyl or behenyl.

  Hereinafter, the present invention will be described more accurately.

  The thickener according to the invention comprises at least one polymer as component i). The polymers can be prepared by polymerization of the following components a) and b), and optionally also components c) and d).

  As component a) at least one water-soluble ethylenically unsaturated monomer comprising at least one anionic monomer and / or at least one nonionic monomer is used. Anionic monomers and nonionic monomers themselves are known to those skilled in the art.

  If at least one anionic monomer is present in component a), it is preferably selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid or salts thereof, in particular the anionic monomer is Na acrylate. It is.

  When at least one nonionic monomer is present in component a), apart from the nitrogen-containing monomers described below, they are esters of the above anionic monomers, for example compounds according to formula (I) are also nonionic Suitable as a monomer. Such nonionic monomers are preferably methyl or ethyl esters of acrylic acid or methacrylic acid, for example ethyl acrylate or methyl acrylate. Corresponding dimethylamino substituted esters such as dimethylaminoethyl (meth) acrylate are also preferred.

The nonionic monomer may be N-vinylpyrrolidone, N-vinylimidazole, or formula (I)

[Where:
R ₇ is H or C ₁ -C ₄ alkyl;
R ₈ is H or methyl, and R ₉ and R ₁₀ are independently of each other H or C ₁ -C ₃₀ alkyl]
Is preferably selected from the compounds according to

  The nonionic monomer is particularly preferably acrylamide, methacrylamide or dialkylaminoacrylamide.

  In a preferred embodiment of the invention, in the polymer, component a) comprises 30 to 99.5% by weight of at least one anionic monomer and 0.5 to 70% by weight of at least one nonionic. Monomer.

  In a further preferred embodiment of the invention, component a) comprises 100% by weight of at least one nonionic monomer.

  In a further preferred embodiment of the invention component a) comprises 100% by weight of at least one anionic monomer.

  Furthermore, in the context of the present invention, it is preferred that component a) does not contain a cationic monomer.

  In the polymerization for producing the polymer, at least one ethylenically unsaturated associative monomer is used as component b). Associative monomers per se 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.

In the polymer, the ethylenically unsaturated associative monomer according to component b) has the formula (II)
R—O— (CH ₂ —CHR′—O) _n —CO—CR ″ ═CH ₂ (II)
[Where:
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,
R ″ is H or methyl;
n is an integer from 0 to 100, preferably from 3 to 50, especially 25]
Is preferably selected from the compounds according to

Component b) is represented by the formula (II)
[Wherein R is C ₁₆ -C ₂₂ alkyl;
R ′ is H,
R ″ is H or methyl;
n is 25]
Particular preference is given to using compounds according to

  The compounds according to formula (II) are commercially available as solutions, for example under the name Plex 6554 O from Evonik Rohm GmbH. These are methacrylates of fatty alcohol ethoxylates, for example, commercially available Lutensol® AT 25 (BASF SE, Ludwigshafen, Germany).

Radical R in the compounds according to formula (II) may also be present as C ₁₆ and C _18, etc., a mixture of different chain length radicals. An example of this is C ₁₆ -C ₁₈ fatty alcohol- (ethylene glycol) ₂₅ -ether methacrylate, in which both a non-negligible amount of C ₁₆ and C ₁₈ fatty alcohol radicals are present as a mixture. . In contrast, for example, in the compounds behenyl-25 methacrylate and cetyl-25 methacrylate (according to formula (II)), the respective radicals R are not present as a mixture but are present as C ₂₂ or C ₁₆ chains. . Other chain lengths occur only in the form of impurities. The number “25” in these compounds according to formula (II) represents the size of the variable n.

  In the preparation of the polymer by polymerization, at least one crosslinking agent may optionally be present as component c). Suitable crosslinkers are well known to those skilled in the art. In the polymer, the crosslinkers according to component c) are divinylbenzene, tetraallylammonium chloride, allyl acrylate, allyl methacrylate, glycol or polyglycol diacrylate and dimethacrylate, butadiene, 1,7-octadiene, allyl acrylamide. Or preferably selected from allyl methacrylamide, bisacrylamide acetic acid, N, N′-methylenebisacrylamide, or polyol polyallyl ethers such as polyallyl sucrose or pentaerythritol triallyl ether. Dialkyldimethylammonium chloride is also suitable as a suitable crosslinking agent.

  Furthermore, in the preparation of polymers by polymerization, at least one chain transfer agent can be used as component d). Suitable chain transfer agents are known to those skilled in the art. Suitable chain transfer agents according to component d) are selected from mercaptans, lactic acid, formic acid, isopropanol or hypophosphite.

  Any of the additives or auxiliaries used in the polymerization process suitable for the preparation of a polymer comprising at least one polymer or a thickener according to the invention, as well as in a process for the preparation of the polymerization or thickener, are defined in more detail below Is done.

In the thickener according to the invention,
a) at least one comprising 20 to 99.99% by weight, preferably 95 to 99.95% by weight (based on the polymer) of at least one anionic monomer and / or at least one nonionic monomer A species of water-soluble ethylenically unsaturated monomer,
b) 0.01 to 80% by weight, preferably 0.05 to 5% by weight, particularly preferably 0.1 to 1% by weight (based on the polymer) of at least one ethylenically unsaturated associative monomer;
c) 0 to 0.3% by weight, preferably 0.01 to 0.1% by weight (based on the polymer), optionally at least one crosslinking agent,
d) 0 to 0.3% by weight, preferably 0.01 to 0.1% by weight (based on polymer), optionally of at least one polymer which can be prepared by polymerization of at least one chain transfer agent Preferably it is present.

  In a further embodiment of the invention, the water-soluble fraction of the polymer is more 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. It is preferred that more than 40% by weight of the polymer, especially 70-100% by weight, is water soluble. The solubility of the polymer is determined by methods known to those skilled in the art, i.e. the polymer present in the thickener according to the invention is mixed with a defined amount of water (e.g. EP-A-343840). Or preferably, P.Schuck, “Size-distribution analysis of macromolecules by sedimentation velocity ultracentrifugation and Lamm equation modeling”, Biophysical Journal 78, (3) (2000), 1606-1619). (See Judgment method).

  In this embodiment, the fraction of the crosslinking agent (component c)) used for polymerisation of the polymer is preferably less than 10% by weight (based on the total amount of components a) to d)). It is particularly preferred that no crosslinker is used for polymerisation.

  The thickener according to the invention further comprises at least one active agent as component ii). Activators themselves are in principle known to those skilled in the art.

  Suitable activators are preferably surfactants, for example anionic, nonionic, cationic and / or amphoteric surfactants, as disclosed, for example, in WO 2009/019225. The use of anionic surfactants and / or nonionic surfactants is preferred.

The nonionic surfactant used is preferably a fatty alcohol alkoxylate. Fatty alcohol alkoxylates are also referred to as polyalkylene glycol ethers. Suitable fatty alcohol alkoxylates are alkoxylated, advantageously ethoxylated, especially preferably primary having an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol and 8 to 18 carbon atoms. Alcohols, wherein the alcohol radicals in the alcohol can be linear or branched, preferably 2-methyl branched, or are typically present in oxoalcohol radicals as linear radicals and methyl branched radicals. An alcohol that can be included in the mixture. Particularly suitable, however, are obtained from natural or industrial alcohols having 12 to 18 carbon atoms, such as coconut alcohol, palm alcohol, tallow fatty alcohol or oleyl alcohol, or, for example, castor oil Alcohol ethoxylates having a linear radical generated from a mixture that can be derived from and having an average of 2 to 8 EO per mole of alcohol. Suitable ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ alcohols with 3 EO, 4 EO or 7 EO, C ₉ -C ₁₁ alcohols with 7 EO, 3 EO , _C 13 _{-C 15} alcohol with five of EO, 7 EO or 8 of EO, _C 12 _{-C 18} alcohols with 3 EO, 5 EO or 7 of EO, and their mixture, for example, a mixture of _C 12 _{-C 18} alcohols with _C 12 _{-C 14} alcohol with 7 EO, with three EO. The displayed degree of ethoxylation is a statistical average and may be an integer or a fraction in the case of a specific product. Suitable alcohol ethoxylates are those with a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples are tallow fatty alcohols with 14 EO, 25 EO, 30 EO, or 40 EO. It is also possible to use a nonionic surfactant containing both EO groups and PO groups in the molecule. Here, not only block copolymers having EO-PO block units or PO-EO block units, but also EO-PO-EO copolymers or PO-EO-PO copolymers can be used. Of course, it is also possible to use mixed alkoxylated nonionic surfactants in which EO units and PO units are distributed randomly rather than in blocks. Such products can be obtained by simultaneously acting ethylene oxide and propylene oxide on fatty alcohols.

  Furthermore, alkyl glycosides or alkyl polyglycosides can also be used as further nonionic surfactants. Alkyl glycosides and alkyl polyglycosides are generally understood by those skilled in the art to mean compounds composed of at least one alkyl fragment and at least one sugar fragment or polysaccharide fragment. The alkyl fragment is preferably derived from a fatty alcohol having 12 to 22 carbon atoms, and the sugar fragment is preferably derived from glucose, sucrose or sorbitan.

For example, the general formula (1)
R ¹ O (G) _x (1)
[Wherein R ¹ is a primary linear or methyl branched, especially 2-methyl branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms, and G is 5 or 6 A glycoside unit having carbon atoms, preferably glucose]
Can be used. The degree of oligomerization x describes the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10, and x is preferably 1.2 to 1.4.

  A further class of nonionic surfactants that are preferably used are those used as a single nonionic surfactant or in combination with other nonionic surfactants, preferably in the alkyl chain. Alkoxylated, preferably ethoxylated, or ethoxylated propoxylated fatty acid alkyl esters having 1 to 4 carbon atoms, in particular fatty acid methyl esters, for example the features of Japanese patent applications Those described in Japanese Utility Model Publication No. 58-217598, or preferably prepared by the method described in International Patent Application No. 90/13533, which is an international patent application.

  Nonionic surfactants of the amine oxide type, such as N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and fatty acid alkanolamide type nonionic surfactants Agents may be suitable. The amount of these nonionic surfactants is preferably not more than the amount of ethoxylated fatty alcohol, particularly not more than half thereof.

Further suitable surfactants are those of formula (2)

[Wherein R ² C (═O) is an aliphatic acyl radical having 6 to 22 carbon atoms, and R ³ is hydrogen, an alkyl radical having 1 to 4 carbon atoms or a hydroxyalkyl radical. [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups]
Is a polyhydroxy fatty acid amide. This polyhydroxy fatty acid amide is a well-known substance and can usually be obtained by reductive amination of reducing sugars with ammonia, alkylamines or alkanolamines followed by acylation with fatty acids, fatty acid alkyl esters or fatty acid chlorides. .

The group of polyhydroxy fatty acid amides has the formula (3)

[Wherein R ⁴ is a linear or branched alkyl radical or alkenyl radical having 7 to 12 carbon atoms, and R ⁵ is a linear, branched or cyclic alkylene radical having 2 to 8 carbon atoms or 6 An arylene radical having ˜8 carbon atoms, wherein R ⁶ is a linear, branched or cyclic alkyl radical or aryl radical, or an oxyalkyl radical having 1-8 carbon atoms, preferably C ₁ ˜ C ₄ alkyl radical or phenyl radical, [Z] ¹ is a linear polyhydroxyalkyl radical in which the alkyl chain is substituted by at least two hydroxyl groups, or alkoxylation of this radical, preferably ethoxylation or propoxyl Is a derivatized derivative]
Further included are: [Z] ¹ is preferably obtained by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. Thereafter, the N-alkoxy substituted compound or the N-aryloxy substituted compound is converted into the desired polyhydroxy fatty acid amide by reaction with a fatty acid methyl ester in the presence of an alkoxide as a catalyst, for example, according to WO 95/07331. can do.

Anionic surfactants used are, for example, those of sulfonate type and sulfate type. Suitable sulfonate-type surfactants here are alkylbenzene sulfonates, preferably C ₉ -C ₁₃ alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene sulfonates and hydroxyalkane sulfonates, and also, for example, terminal Alternatively, it is a disulfonate obtained by sulfonation of a C _{12 to} C ₁₈ monoolefin having an internal double bond with gaseous sulfur trioxide and subsequent alkali hydrolysis or acid hydrolysis of the sulfonation product. Also suitable are alkane sulfonates, preferably secondary alkane sulfonates, which are obtained, for example, from C ₁₂ -C ₁₈ alkanes by sulfochlorination or sulfooxidation followed by hydrolysis or neutralization. Equally suitable are esters of α-sulfo fatty acids (ester sulfonates), for example α-sulfonated methyl esters of hydrogenated coconut fatty acids, palm kernel fatty acids or tallow fatty acids.

  Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are monoesters, diesters and triesters obtained during the preparation by esterification of monoglycerol with 1 to 3 moles of fatty acid or transesterification of triglycerides with 0.3 to 2 moles of glycerol, and It is understood to mean a mixture thereof. Suitable sulfated fatty acid glycerol esters herein are saturated fatty acids having 6 to 22 carbon atoms, such as caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid, or behenic acid. The sulfated product of

Further suitable anionic surfactants are fatty alcohol sulfates, for example alkyl (alkenyl) sulfates. Suitable alkyl (alkenyl) sulfates are C ₁₂ -C ₁₈ fatty alcohols such as coconut fatty alcohol, tallow fatty alcohol, lauryl alcohol, myristyl alcohol, sulfuric monoester of cetyl alcohol or stearyl alcohol, or C ₁₀ -C ₂₀ oxo. Alkali metal salts of sulfuric acid monoesters of alcohols and secondary alcohols of these chain lengths, especially sodium salts. Further preferred are alkyl (alkenyl) sulphates of the said chain length comprising synthetic linear alkyl radicals produced on the basis of petrochemicals, which sulphates similar to the corresponding compounds based on lipochemical raw materials. . For cleaning techniques, C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates, and even C ₁₄ -C ₁₅ alkyl sulfates are preferred. For example, 2,3-alkyl sulfates prepared according to US Pat. Nos. 3,234,258 or 5,075,041 and obtained commercially from the Shell Oil Company under the name DAN® Suitable anionic surfactant.

1-6 moles of linear ethoxylated with ethylene oxide or branched _C 7 _{-C 21} alcohols, for example, on average 3.5 moles of ethylene oxide (EO) 2-methyl-branched _C 9 _{-C 11} alcohols having, or 1 Also suitable are sulfuric acid monoesters of C ₁₂ -C ₁₈ fatty alcohols having ˜4 EO.

Further suitable anionic surfactants are also salts of alkylsulfosuccinic acids, also called sulfosuccinates or sulfosuccinates, monoesters of sulfosuccinic acid and alcohols, preferably fatty alcohols, in particular ethoxylated fatty alcohols and / or Or a diester. Preferred sulfosuccinates contain a C ₈ -C ₁₈ fatty alcohols radical or mixtures thereof. Particularly preferred sulfosuccinates contain fatty alcohol radicals derived from ethoxylated fatty alcohols. In this connection, sulfosuccinates in which the fatty alcohol radicals are derived from ethoxylated fatty alcohols with a narrower homolog distribution are also particularly preferred. Similarly, it is also possible to use alkyl (alkenyl) succinic acids, or salts thereof, preferably having 8 to 18 carbon atoms in the alkyl (alkenyl) chain.

  Further suitable anionic surfactants are alkyl carboxylates, for example sodium salts of saturated or unsaturated fatty acids, in which case the alkyl radicals of the alkyl carboxylates are preferably linear.

In the context of the present invention, the active agent is preferably selected from fatty alcohol alkoxylates, alkyl glycosides, alkyl carboxylates, alkylbenzene sulfonates, secondary alkane sulfonates, and fatty alcohol sulfates. Particular preference is given to selecting from lath. An example of a suitable fatty alcohols _alkoxylates, C 6 _{-C 17} (secondary) poly (3-6) is ethoxylates.

  Furthermore, in the context of the present invention, it is also suitable to use active agents having a (relatively) high HLB value (hydrophilic lipophilic balance value). The activator preferably has an HLB value of 7-18, more preferably 8-15, particularly preferably 9-13.

The activator with a high HLB value is preferably i) a fatty alcohol alkoxylate produced from a secondary alcohol or a mixture of alcohols having 12 to 18 carbon atoms and ethylene oxide or propylene oxide, and ii) sucrose. And alkyl glycosides produced from C _{8 to} C ₂₂ fatty alcohols. Examples of such active agents are Croda GmbH, Herrenpfad-Sud 33, 41334 Nettal, Synperonic 87K, marketed by Germany, Croderet 40, all sold by Croda, or other ethoxylated hydrogenated castor oil (ricinous oil), for example Etocas 40 or Crodesta F110.

  In a further embodiment of the invention it is preferred to use a mixture of at least two active agents, in which case at least one active agent has a high HLB value and at least one active agent is Has a low HLB value. The active agent having a high HLB value preferably has an HLB value of more than 12 to 20, and the active agent having a low HLB value preferably has an HLB value of 1 to 12. In this embodiment, the active agent with a high HLB value and the active agent with a low HLB value can be present in any desired ratio relative to each other known to those skilled in the art. Preferably, the active agent with a high HLB value of 20-50% by weight and an active agent with a low HLB value of 50-80% by weight are used in the mixture. Furthermore, the ratio of the active agent with a high HLB value to the active agent with a low HLB value is adjusted so that the overall HLB value is preferably 7-18, more preferably 8-15, particularly preferably 9-13. The

In a mixture of at least two active agents, high active agent of HLB values used are sucrose or sorbitan, C ₈ -C ₂₂ fatty alcohols, for example with polyethylene glycol sorbitan monostearate or polyoxyethylene sorbitan monostearate Preferred are alkyl glycosides or polyalkyl glycosides based on the above, or polyalkyl oligoethylene oxide glycosides. Examples of such activators are commercially available Crillet 1, Crillet 3 or Crodesta F160, all obtained from Croda. Less active agent having HLB value used is sucrose or sorbitan, it is preferred C ₈ -C ₂₂ fatty alcohols or fatty acids, alkyl glycosides produced from, for example, sorbitan monolaurate or sorbitan stearate. Examples of such activators are commercially available Crill 1, Crill 3 or Crodesta F10 obtained from Croda.

  According to the invention, the ratio of activator to polymer is greater than 10: 100 [wt% / wt%], preferably 10.5 to 50: 100 [wt% / wt%], particularly preferably 11. 5 to 20: 100 [wt% / wt%].

  In addition to the polymer and the active agent, further components may be present in the thickener according to the invention. Suitable further components are defined in more detail in the following text in the context of thickener and polymer preparation. Suitable further components may be, for example, oils and solvents.

  In the thickener according to the invention, the polymer can be present in the form dispersed in the oil phase, preferably as a reverse dispersion, a water-in-oil dispersion or as an anhydrous polymer dispersed in oil.

  The present invention further provides a method for preparing a thickener according to the present invention. Methods for preparing thickeners per se and methods for preparing polymers are known to those skilled in the art. The polymer is preferably obtained by emulsion polymerization, particularly reverse phase emulsion polymerization. Preferably a polymer is first prepared and after polymerization, an activator is added, preferably by reverse emulsion polymerization, to obtain a thickener.

  The polymer can be prepared by various methods, and emulsion polymerization, particularly reverse phase emulsion polymerization is preferred. Reverse phase emulsion polymerization is generally understood by those skilled in the art to mean a polymerization process according to the following definitions. A hydrophilic monomer is dispersed in the hydrophobic oil phase. Polymerization occurs directly in these hydrophilic monomer particles by the addition of an initiator.

  Furthermore, after reverse phase emulsion polymerization, before adding the activator, at least a portion of the water and at least a portion of the low boiling point constituents can be distilled off from the oil phase, especially by LDP (liquid dispersion polymer) technology. Is preferred. The LDP technique itself is known to those skilled in the art and is described, for example, in WO 2005/097834.

  The following details, unless stated otherwise, are all types of emulsion polymerization, for example, emulsion polymerization in water where a continuous phase is also formed later, and in particular, reverse phase emulsion polymerization in which a hydrophobic oil phase constitutes the continuous phase. Also applies. A suitable polymerization initiator is used for the polymerization. Redox initiators and / or thermally activatable free radical polymerization initiators are preferred.

  Suitable thermal activatable free radical initiators or oxidation components of a redox initiator pair are mainly of the peroxy and azo types. 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-butylperoxypivalate, t-butylperacetate, dilauroyl peroxide, dicapryloyl peroxide, distearoyl peroxide, dibenzoyl peroxide, diisopropylperoxydicarbonate, di Decylperoxydicarbonate, diecosylperoxydicarbonate, di-t-butylperbenzoate, azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, ammonium Rusurufato, potassium peroxide sulfate, sodium per sulfate and sodium peroxide phosphate.

  Persulfate (peroxodisulfate), especially sodium persulfate, is most preferred.

  When performing emulsion polymerization, an amount of initiator sufficient to initiate the polymerization reaction is used. The initiator is typically used in an amount of 0.01 to 3% by weight, based on the total weight of monomers used. The amount of initiator is preferably about 0.05-2% by weight, in particular 0.1-1% by weight, based on the total weight of the monomers used.

  Emulsion polymerization typically occurs at 35 ° C to 100 ° C. Emulsion polymerization can be carried out as a batch process or in the form of a feed process. In the feed procedure, at least a portion of the polymerization initiator, and optionally a portion of the monomer, is introduced as the first charge and heated to the polymerization temperature, after which the remainder of the polymerization mixture is typically maintained while maintaining the polymerization. Divided into several times, one or more of them are introduced continuously or stepwise so that they contain monomers in pure or emulsified form. It is preferred that the monomer feed occurs in the form of a monomer emulsion. In parallel with the monomer feed, the polymerization initiator can be further metered in.

  In a preferred embodiment, the total amount of initiator is introduced as the first charge. That is, no further metering of the initiator occurs in parallel with the monomer feed.

  Thus, in a preferred embodiment, all heat activatable free radical polymerization initiators are introduced as the initial charge and the monomer mixture is preferably poured in the form of a monomer emulsion. Prior to initiating the monomer mixture feed, the initial charge is brought to the activation temperature of the heat-activatable free radical polymerization initiator or higher. The activation temperature is considered to be a temperature at which at least half of the initiator decomposes after 1 hour.

  According to another preferred preparation method, the polymer is obtained by polymerization of a monomer mixture in the presence of a redox initiator system. The redox initiator system includes at least one oxidant component and at least one reductant component, wherein heavy metal ions, such as cerium salts, manganese salts or iron (II) salts, are present in the reaction medium. It is preferably further present as a catalyst.

  Suitable oxidant components include, 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 include alkali metal sulfites, alkali metal dithionates, alkali metal hyposulfites, sodium bisulfite, Rongalit C (sodium formaldehyde sulfoxylate), mono and dihydroxyacetones, sugars (eg glucose or dextrose) ), Ascorbic acid and its salts, acetone bisulfite adducts, and / or alkali metal salts of hydroxymethanesulfinic acid. Sodium bisulfite or sodium metabisulfite is preferred.

  Iron (II) salts, such as iron (II) sulfate, tin (II) salts, such as tin (II) chloride, titanium (III) salts, such as titanium (III) sulfate, are also suitable reducing agent components or catalysts. is there.

  The amount of the oxidizing agent used is 0.001 to 5.0% by weight, preferably 0.005 to 1.0% by weight, particularly preferably 0.01 to 0.5% by weight, based on the total weight of the monomers used. %. The reducing agent is in an amount of 0.001 to 2.0% by weight, preferably 0.005 to 1.0% by weight, particularly preferably 0.01 to 0.5% by weight, based on the total weight of the monomers used. Is used.

  A particularly suitable redox initiator system is a sodium peroxodisulfate / sodium bisulfite system, such as 0.001-5.0 wt% sodium peroxodisulfate and 0.001-2.0 wt% sodium bisulfite. 0.005 to 1.0% by weight sodium peroxodisulfate and 0.005 to 1.0% by weight sodium hydrogen sulfite, particularly preferably 0.01 to 0.5% by weight sodium peroxodisulfate and 0%. 0.01-0.5 wt% sodium bisulfite.

  More particularly preferred redox initiator systems are t-butyl hydroperoxide / hydrogen peroxide / ascorbic acid systems, such as 0.001 to 5.0% by weight t-butyl hydroperoxide and 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 and 0.005 to 1.0% by weight of hydrogen peroxide. 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 ~ 0.5 wt% ascorbic acid.

  The polymer is preferably prepared by reverse phase emulsion polymerization by first preparing the water phase and the oil phase of the water soluble component separately. The two phases are then mixed to obtain a water-in-oil dispersion. The mixture is polymerized by adding a redox initiator system. A thermal initiator can then optionally be added or, if already present, thermally activated.

  In the aqueous phase, it is preferred that a chain transfer agent, a crosslinking agent, an anionic monomer and / or a neutral monomer, further an associative monomer is optionally present, and further an additional component is optionally present. Suitable further components are, for example, complexing agents for salts, such as pentasodium diethylenetriaminepentaacetate.

  In the oil phase, it is preferred that emulsifiers, stabilizers, high-boiling oils, low-boiling oils and / or optionally associative monomers are present. Further, in some cases, a nonionic monomer may be present in the oil phase.

  Emulsifiers, stabilizers, low-boiling oils and high-boiling oils themselves are well known to those skilled in the art. These compounds can be used individually or in the form of mixtures.

  Typical emulsifiers are anionic emulsifiers such as sodium lauryl sulfate, sodium tridecyl ether sulfate, dioctyl sulfosuccinate sodium salt and sodium salt of alkylaryl polyether sulfonate, and nonionic emulsifiers such as Alkyl aryl polyether alcohols and ethylene oxide-propylene oxide copolymers. Sorbitan trioleate is also suitable as an emulsifier.

Suitable emulsifiers have the following general formula R—O— (CH ₂ —CHR′—O) _n —X
[Where:
R is a _C 6 _{-C 30} alkyl,
R ′ is hydrogen or methyl;
X is hydrogen or SO ₃ M;
M is hydrogen or an alkali metal,
n is an integer from 2 to 100]
Have

  Suitable stabilizers are described, for example, in EP 1 725 025 or EP 1 724 724. A preferred stabilizer is a copolymer of stearyl methacrylate and methacrylic acid.

  Suitable high boiling oils are, for example, 2-ethylhexyl stearate and also hydroheated heavy naphtha, suitable low boiling oils are, for example, low viscosity dearomatic aliphatic hydrocarbons or mineral oils. .

  In a preferred embodiment of the invention, component b) (at least one ethylenically unsaturated associative monomer) is added to the oil phase during reverse phase emulsion polymerization.

  In reverse emulsion polymerization, the temperature can be kept constant or can be raised. The temperature increase can be performed continuously or in stages. Thus, for example, during polymerization, the temperature can be increased by 0.2 to 10 ° C. per minute, preferably 1 to 3 ° C. per minute. The increase in temperature is controlled by the rate at which the initiator is added. The initial value of the temperature can be 0 to 30 ° C., preferably 10 to 20 ° C.

  In another embodiment of the invention, the temperature during inverse emulsion polymerization is kept constant (cold procedure). The temperature is 0-30 ° C, preferably 10-20 ° C. In a further embodiment of the invention, the temperature is kept in a higher temperature range (hot procedure). The temperature during the polymerization is 40 to 150 ° C, preferably 70 to 120 ° C.

  In a particularly preferred embodiment of the invention, the temperature is kept constant during the inverse emulsion polymerization, and the temperature is at least 40 ° C, preferably 50-90 ° C.

  In the context of the present invention, if the temperature during the polymerization, especially the inverse emulsion polymerization, is kept constant, it means that the temperature is kept constant from the start of the polymerization. If the upper and lower temperatures during the polymerization process are +/− 5 ° C., preferably +/− 2 ° C., especially +/− 1 ° C., it is considered to be a constant temperature (based on the desired constant temperature value). It is done. The temperature is kept constant until the polymerization is complete, preferably after more than 90%, more preferably more than 95% by weight of the monomers used have been converted, especially preferably until complete conversion (100% by weight). . The temperature can be kept constant by dissipating the rising reaction heat by cooling. The initiation of the polymerization is usually the addition of a polymerization initiator, preferably the addition of a redox initiator system. Usually, the system is first heated to the desired temperature and waits for a constant temperature while stirring. A polymerization initiator is then added, resulting in a polymerization process. In one embodiment of the invention, the temperature is kept at a constant value above the melting point of the associative monomer used.

  The present invention further provides a surfactant-containing acidic formulation comprising at least one thickener according to the invention according to the above definition. The pH of the formulation is less than 1-7.

  The invention further provides a surfactant-containing alkaline formulation comprising at least one thickener according to the invention according to the above definition. The pH of the formulation is 7-13.

  The surfactant-containing acidic or alkaline preparation according to the present invention may further comprise raw materials known to those skilled in the art. Suitable raw materials are builders, bleaches, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH regulators, fragrances, fragrance carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, anti-redeposition agents , Optical brightener, anti-greying agent, anti-shrink agent, anti-wrinkle agent, dye migration inhibitor, antibacterial active ingredient, bactericidal agent, fungicide, antioxidant, corrosion inhibitor, antistatic agent, ironing Includes one or more materials from the group of auxiliaries, sparse agents and impregnants, swelling and anti-slip agents, and UV absorbers.

  The present invention relates to hair fabric styling, hair styling agent, shampoo, softener, care composition, conditioner, skin cream, shower gel, shower fabric softener in hair cosmetics. Further provided is the use of the surfactant-containing acidic formulation according to the invention as an agent or preferably as an acidic cleaner for toilets or bathrooms.

  The present invention further provides the use of a surfactant-containing alkaline formulation as a care composition, as a liquid detergent, or as a machine laundry or hand dishwashing detergent.

  The present invention is a viscosity modifier for optimization of shear dilution, as a thickener for stabilizing suspended raw materials in the size range of nanometers to millimeters, and / or interfaces. Further provided is the use of the thickener according to the invention in an active or acid-containing alkaline or alkaline formulation.

In descriptions including examples, the following abbreviations are used.

  The invention is illustrated below with reference to examples.

[Comparative Example C1]
Synthesis of thickeners / polymers starting from anionic monomers, with no associative monomers but with crosslinkers and chain transfer agents and increased polymerization temperature The aqueous phase of the water-soluble component by mixing the following components To prepare.

250.24 g (139.02 pphm) of water,
0.89 g (0.49 pphm) diethylenetriaminepentaacetic acid pentasodium,
11.05 g (0.06 pphm) of methylenebisacrylamide (1% aqueous solution),
180 g (100 pphm) acrylic acid and 146.8 g (40.78 pphm) NaOH (50% aqueous solution).

Adjust the aqueous phase to pH 5.5 using NaOH (50% aqueous solution).

  An oil phase is prepared by mixing the following ingredients.

20.62 g (8.59 pphm) of sorbitan monooleate (75% hydroheated heavy naphtha (petroleum) [Isopar G] solution),
93.19 g (12.27 pphm) polymeric stabilizer: stearyl methacrylate-methacrylic acid copolymer (23.7% hydrothermal heavy naphtha [Isopar G] solution),
120.24 g (66.8 pphm) of low viscosity mineral oil (Kristol M14) and 236.28 g (131.27 pphm) of hydrothermal heavy naphtha [Isopar G].

  The two phases are mixed at a high shear in a ratio of 55.6 parts of water phase and 44.4 parts of oil phase to produce a water-in-oil emulsion. The resulting water-in-oil emulsion is introduced into a reactor equipped with a nitrogen spray tube, a stirrer, and a thermometer. The emulsion is purged with nitrogen to remove oxygen and cooled to 20 ° C.

Polymerization is
13 g (0.014 pphm) sodium metabisulfite (0.2% hydrothermal heavy naphtha (petroleum) [Isopar G] solution);
13 g (0.014 pphm) tert-butyl hydroperoxide (0.2% hydrothermal heavy naphtha (petroleum) [Isopar G] solution)
This is realized by adding a redox pair composed of

The redox pair is added stepwise so that a temperature increase of 2 ° C./min occurs. When the isotherm is reached, a free radical initiator (2,2′-azobis (2-methylbutyronitrile), CAS: 13472-08-7) is added in two portions (the second time after 45 minutes) Keep the emulsion at 85 ° C. for 75 minutes.

  Vacuum distillation is used to remove low boiling constituents of water and oil phase (Isopar G).

  A low viscosity mineral oil (Kristol M14) is added to the product to achieve 54% solids. To this product was added 8% (based on the total mass fraction of this product) of a fat-containing alcohol alkoxylate (C12 / 15 alcohol alkoxylate [Synperonic 87K ™]) to give a polymer solid fraction. A 50% thickener (dispersion) is produced. Accordingly, the ratio of active agent to polymer is 16.0: 100 [wt% / wt%].

[Example 1]
A thickener / polymer starting from an anionic monomer containing an associative monomer and having a constant polymerization temperature:
[Example 1.1]
An aqueous phase of a water-soluble component is prepared by mixing the following components.

246.13 g (140.65 pphm) of water,
0.86 g (0.49 pphm) diethylenetriaminepentaacetic acid pentasodium,
174.13 g (99.5 pphm) acrylic acid and 154.26 g (44.07 pphm) NaOH (50% aqueous solution).

Adjust the aqueous phase to pH 5.5 using NaOH (50% aqueous solution).

  An oil phase is prepared by mixing the following ingredients.

20.05 g (8.59 pphm) sorbitan monooleate (75% hydrothermal heavy naphtha (petroleum) [Isopar G] solution),
90.6 g (12.27 pphm) of polymeric stabilizer: stearyl methacrylate-methacrylic acid copolymer (23.7% hydrothermal heavy naphtha [Isopar G] solution),
119.03 g (68.02 pphm) low viscosity mineral oil (Kristol M14), and 229.72 g (131.27 pphm) hydrothermal heavy naphtha [Isopar G],
1.09 g (0.5 pphm) associative monomer: 60% by weight C16EO25Mac: contained in the commercial product Plex 6954-O (with 20% by weight methacrylic acid, 20% by weight water).

  The two phases are mixed at a high shear in a ratio of 55.6 parts of water phase and 44.4 parts of oil phase to produce a water-in-oil emulsion. The resulting water-in-oil emulsion is introduced into a reactor equipped with a nitrogen spray tube, a stirrer, and a thermometer. While heating to 50 ° C., the emulsion is purged with nitrogen to remove oxygen.

Polymerization is
13.6 g (0.016 pphm) sodium metabisulfite (0.2% aqueous solution)
13.6 g (0.016 pphm) tert-butyl hydroperoxide (0.2% aqueous solution)
This is realized by adding a redox pair composed of

  The redox pair is added at 50 ° C. over 2 hours. The mixture is then heated to 85 ° C. and then free radical initiator (2,2′-azobis (2-methylbutyronitrile), CAS: 13472-08-7) in two stages (second stage after 45 minutes). And keep the emulsion at 85 ° C. for 75 minutes.

  Vacuum distillation is used to remove low boiling constituents of water and oil phase (Isopar G).

  Low viscosity mineral oil (Kristol M14) is added to the product to achieve 54% solids. To this product was added 8% (based on the total mass fraction of this product) of a fat-containing alcohol alkoxylate (C12 / 15 alcohol alkoxylate [Synperonic 87K ™]) to give a polymer solid fraction. A 50% thickener (dispersion) is produced. Accordingly, the ratio of active agent to polymer is 16.0: 100 [wt% / wt%].

The following examples as in Table 1 are prepared as in Example 1.1, taking into account the indicated changes in monomer composition. Associative monomer C16EO25MAc is added to the oil phase. The commercial product Plex 6554 O is used. This contains 60% by weight associative monomer and water and MAA as a solvent in a ratio of about 1: 1. The weight data in Table 1 is the amount of associative monomer without solvent. The ratio of active agent to polymer in all examples in Table 1 is 16.0: 100 [wt% / wt%] in all cases, and unless otherwise specified, each thickener (dispersion) is a polymer. The solid fraction is 50%.

[Example 2]
Thickener / polymer starting from an anionic monomer containing an associative monomer and further with increasing polymerization temperature The following examples as in Table 2 take into account the indicated changes in monomer composition as in Comparative Example C1 Prepare. Associative monomer C16EO25MAc is added to the oil phase. The commercial product Plex 6554 O is used. This contains 60% by weight associative monomer and water and MAA as a solvent in a ratio of about 1: 1. The weight data in Table 2 is the amount of associative monomer without solvent. The ratio of activator to polymer in all examples in Table 2 is 16.0: 100 [wt% / wt%] in all cases. Unless otherwise stated, each thickener (dispersion) has a polymer solid fraction of 50%.

General Test Methods Unless otherwise noted, the following general test methods are used in the following examples.

Judgment of viscosity In consideration of the procedure described in DIN 51550, DIN 53018, DIN 53519, a Brookfield DV type II viscometer was used. Unless otherwise specified, in the table below, spindle no. 6 is used to measure the viscosity displayed in units of mPa · s.

Determination of shear dilution In an ASC (automatic sample changer) rotary rheometer manufactured by Antonpaar, measurement is performed using a CC27 cylindrical shape, that is, a measurement body radius of 13.33 mm and a measurement cup radius of 14.46 mm. The measurement temperature is 23 ° C. Samples were starting from a low shear increased to high shear ^{(0.01s -1 ~1000s} -1), measured at a shear of a return to the original ^{(1000s -1 ~0.01s} -1) steady state.

[Example 3]
Use of thickener / polymer in water Thickener as shown in Table 3 is slowly added to distilled water at room temperature and stirred until the formulation is homogeneous. The resulting aqueous formulation according to Table 3 contains 1.0% polymer by weight with respect to 99.0% water or 0.5% by weight with respect to 99.5% water. Either containing a polymer. The results are summarized in Table 3.

  As the amount of the associative monomer incorporated into the polymer is increased, the thickening performance is steadily improved as compared with C1 not containing the associative monomer. According to Example 2, the viscosity increase performance increases as the starting temperature during polymerization decreases. When the polymerization temperature is set to a constant 50 ° C., the thickening performance is improved even when the monomer composition is the same. The last four examples in Table 3 relate to acrylamide-containing polymers.

[Example 4.1]
Use of Thickener / Polymer in Standard Formulation of Care Composition The care composition formulation (P1) includes raw materials as shown in Table 4.1. P1 is prepared by heating Phase A and Phase B to 80 ° C. in each case. The two phases are then combined and homogenized. The mixture is then cooled to about 40 ° C. with stirring and immediately after that phase C is added to homogenize the mixture.

Addition of thickener to care composition formulation P1:
The thickener according to the invention listed in Table 4.1.2 or the thickener according to the comparative example is slowly added to the care composition formulation P1 at room temperature and stirred until the formulation is homogenized. The care composition thus obtained contains a thickener at a concentration expressed in% by weight with respect to 100% by weight of the resulting care composition.

One day after preparation, the Brookfield viscosity is measured. The results are summarized in Table 4.1.2.

  As the amount of associative monomer incorporated into the polymer is increased, the thickening performance is steadily improved as compared with V1 not containing the associative monomer.

[Example 4.2]
Use of thickener / polymer in standard formulation of fabric softener W3: W3: partially hydrogenated methyltris (hydroxyethyl) ammonium-di-tallow-fatty acid ester methosulphate fabric softener (active fraction 5) The fabric softener has a pH of 2.7 and 5.5% by weight of methyltris (hydroxyethyl) ammonium-di-tallow-fatty acid ester methosulphate (partially hydrogenated). And 94.5% by weight of deionized water.

Addition of thickener to fabric softener formulation W3:
Thickeners according to Examples 1 and 2 and the comparative example (see Table 4.2) are slowly added to each fabric softener formulation at room temperature and stirred until the formulation is homogenized.

One day after preparation, the Brookfield viscosity is measured. The results are summarized in Table 4.2.

  When the associative monomer is incorporated into the polymer, the thickening performance is continuously improved as compared with the comparative example not containing the associative monomer.

[Example 5]
In Table 5 below, the storage stability of the thickener according to the invention is investigated. It can be seen that the thickener according to the invention is very stable.

  With the thickener according to the invention, a marked improvement is seen, i.e. a reduction in sediment.

[Example 6]
Storage stability of the care composition formulation (P1) according to Example 4 comprising a thickener / polymer starting from an anionic monomer:
With the thickener according to the invention, a marked improvement is seen, i.e. a reduction in sediment. After approximately 3 months, the formulation containing Thickener V1 shows significant sedimentation, and the formulation containing Thickener 2.1 shows minimal sedimentation (storage at room temperature).

[Example 7]
Effect of active agent amount on thickener / polymer starting from anionic monomers including associative monomers and thickening rate in aqueous formulations:
Examples 7.1-7.5 listed in Table 6 were prepared according to Example 2.1, and the amount of active agent added after distillation was determined by the concentration of active agent in the thickener listed in Table 11 ( A%) (all data expressed in weight percent based on the amount of anionic polymer in the thickener). All thickeners (dispersions) thus prepared have a polymer solid fraction of 50%. The thickener is then added to the water with stirring. The aqueous formulation thus obtained comprises 1% by weight thickener for 99% by weight water, ie 0.5% by weight anionic polymer for 99.5% by weight water. “Comparison (comp.)” Means a comparative example.

  In the case of associative monomers, more than 10% of the active agent is required to achieve rapid thickening performance (greater than 40% within 1 minute based on final thickening).

Claims (20)

i) at least one polymer,
a) at least one water-soluble ethylenically unsaturated monomer comprising at least one anionic monomer and / or at least one nonionic monomer;
b) at least one ethylenically unsaturated associative monomer;
c) optionally at least one crosslinking agent,
d) said at least one polymer optionally prepared by polymerization of at least one chain transfer agent;
ii) A thickener comprising at least one active agent, wherein the ratio of active agent to polymer is greater than 10: 100 [wt% / wt%].   In the polymer, component a) comprises at least one anionic monomer, the anionic monomer is selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid or salts thereof, in particular the anionic monomer is Na acrylate The thickener according to claim 1.   The thickener according to claim 1 or 2, wherein the water-soluble fraction of the polymer is greater than 25% by weight (based on the total weight of the polymer). In the polymer, component a) comprises at least one nonionic monomer, the nonionic monomer being N-vinylpyrrolidone, N-vinylimidazole, or formula (I)

[Where:
R ₇ is H or C ₁ -C ₄ alkyl;
R ₈ is H or methyl;
R ₉ and R ₁₀ are each independently H or C ₁ -C ₃₀ alkyl]
The thickener according to any one of claims 1 to 3, which is selected from the compounds by In the polymer, the ethylenically unsaturated associative monomer (component b) has the formula (II)
R—O— (CH ₂ —CHR′—O) _n —CO—CR ″ ═CH ₂ (II)
[Where:
R is C ₆ -C ₅₀ alkyl, preferably C ₈ -C ₃₀ alkyl, especially C ₁₆ -C ₂₂ alkyl,
R ′ is H or C ₁ -C ₄ alkyl, preferably H,
R ″ is H or methyl;
n is an integer from 0 to 100, preferably from 3 to 50, especially 25]
Thickener according to any one of claims 1 to 4, selected from compounds according to   In the polymer, the crosslinker (component c) is divinylbenzene; tetraallylammonium chloride; allyl acrylate; allyl methacrylate; glycol or polyglycol diacrylate and dimethacrylate; butadiene; 1,7-octadiene, allylacrylamide or 6. The method according to any one of claims 1 to 5, selected from allyl methacrylamide; bisacrylamide acetic acid; N, N'-methylenebisacrylamide, or polyol polyallyl ether, such as polyallyl sucrose or pentaerythritol triallyl ether. Thickener.   The thickener according to any one of claims 1 to 6, wherein in the polymer, the chain transfer agent (component d) is selected from mercaptans, lactic acid, formic acid, isopropanol or hypophosphite.   The activator is selected from fatty alcohol alkoxylates, alkyl glycosides, alkyl carboxylates, alkylbenzene sulfonates, secondary alkane sulfonates, and fatty alcohol sulfates, preferably selected from fatty alcohol alkoxylates. The thickener in any one of -7.   A mixture of at least one active agent having an HLB value (hydrophilic / lipophilic balance value) of more than 12 to 20 and at least two active agents having an HLB value of 1 to 12 is used. The thickener according to any one of claims 1 to 8.   10. Thickener according to any of claims 1 to 9, wherein the polymer is present in a form dispersed in the oil phase, preferably as a reverse dispersion, a water-in-oil dispersion or as an anhydrous polymer dispersed in oil. .   A process for preparing a thickener according to any of claims 1 to 10, wherein the polymer is obtained by emulsion polymerization, in particular by reverse phase emulsion polymerization.   12. At least some water and at least some low-boiling constituents are distilled off from the oil phase, especially by LDP (liquid dispersion polymer) technology, after reverse phase emulsion polymerization and before adding the activator. The method described.   13. A process according to claim 11 or 12, wherein component b) is added to the oil phase during reverse phase emulsion polymerization.   14. A method according to any of claims 11 to 13, wherein the temperature is kept constant or rises during the reverse emulsion polymerization.   15. A process according to any of claims 11 to 14, wherein the temperature is kept constant during reverse emulsion polymerization and is at least 40 <0> C, preferably 50-90 <0> C.   A surfactant-containing acidic preparation comprising at least one thickener according to any one of claims 1 to 10, wherein the pH is less than 1 to 7.   In hair cosmetics, in hair styling agents, as shampoos, as softeners, as care compositions, as conditioners, as skin creams, as shower gels, as laundry fabric softeners, or Use of a surfactant-containing acidic formulation according to claim 16, preferably as an acidic cleaner for toilets or bathrooms.   A surfactant-containing alkaline preparation comprising at least one thickener according to any one of claims 1 to 10, wherein the surfactant-containing alkaline preparation has a pH of 7 to 13.   Use of a surfactant-containing alkaline preparation according to claim 18 as a care composition, as a liquid detergent or as a machine laundry or hand dishwashing detergent.   As a viscosity modifier for optimization of shear dilution, as a thickener for stabilization of suspended raw materials in the size range of nanometers to millimeters, and / or with surfactant-containing acidity Or use of the thickener in any one of Claims 1-10 in an alkaline formulation.