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

Abstract

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

Description

Thickener comprising at least one polymer based on associative monomers

The 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 may 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 . Furthermore, the invention relates to a process for producing the thickeners according to the invention and also to surfactant-containing formulations comprising at least one thickener. The invention further provides the use of such surfactant-containing formulations, eg as softeners or liquid detergents, and also the use of such thickeners, eg as viscosity modifiers.

WO 03/102043 relates to monomer mixtures comprising (i) a water-soluble ethylenically unsaturated monomer or comprising at least one cationic monomer, (ii) more than 50 ppm based on component (i) of at least one crosslinking agent and ( iii) Aqueous formulations of cationic polymers prepared with at least one chain transfer agent. The aqueous formulations can be used as thickeners in domestic formulations.

WO2009/019225 relates to aqueous dispersions of alkali-soluble copolymers which are suitable as associative thickeners. The copolymer comprises polymerized units of a) at least one ethylenically unsaturated carboxylic acid, b) at least one nonionic ethylenically unsaturated surfactant monomer, c) at _least one methacrylic acid C - C ₂ alkyl esters and d) at least one C ₂ -C ₄ alkyl acrylate, wherein the average alkyl chain length over the number of alkyl acrylates is 2.1-4.0. The associative thickener can be prepared by emulsion polymerization. The associative thickener is suitable for use in detergents and cleaning agents.

Liquid dispersion polymer (LDP) compositions are disclosed in WO2005/097834. These LDP compositions comprise a hydrophilic, water-soluble or swellable polymer having a neutralization degree of about 25-100%, a non-aqueous carrier phase and an oil-in-water surfactant. The hydrophilic, water-soluble or swellable polymer is preferably obtained by polymerizing eg acrylic or methacrylic acid. The LDP dispersions are suitable for the production of particulate thickeners, for example for use in aqueous or organic compositions, especially in personal care or pharmaceutical formulations.

WO2010/078959 relates to cationic polymer thickeners consisting of crosslinked water-swellable cationic polymers comprising at least one cationic monomer and optionally nonionic or anionic monomers, wherein the polymer is based on the total The weight contains less than 25% water soluble polymer chains. In addition, the polymer contains a crosslinking agent at a concentration of 500-5000 ppm relative to the polymer. The cationic polymer is prepared by inverse emulsion polymerization.

WO2010/079100 discloses fabric softener compositions comprising polymers according to WO2010/078959.

US2008/0312343 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 composition comprises at least 50-80% by weight of at least one linear, branched or crosslinked organic polymer (P), at least 5% to 10% by weight of an emulsifier system of the water-in-oil type, 5- 45% by weight 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 contain up to 5% by weight of an emulsifier system of the oil-in-water type. The inverse latex composition can be prepared by inverse emulsion polymerization.

EP-A172025 relates to dispersions in a continuous liquid phase of polymers prepared by polymerizing ethylenically unsaturated monomers containing hydrophobic groups of at least 8 carbon atoms and ethylenically unsaturated monomers copolymerizable therewith form. The dispersion is stable, substantially anhydrous and contains at least 40% by weight polymer. During the polymerization, for example, anionic monomers can be used as copolymerizable ethylenically unsaturated monomers. The polymerization can be carried out as an inverse emulsion polymerization.

EP-A172724 relates to polymers prepared by copolymerizing a) ethylenically unsaturated monomers comprising hydrophobic groups having at least 8 carbon atoms and b) water-soluble ethylenically unsaturated monomers. All monomers are soluble in water as a mixture and the polymers are prepared by inverse emulsion polymerization. The polymer particles have a dry size of <4 μm. As monomer component b), it is possible to use anionic monomers such as acrylic acid in free acid form or as a water-soluble salt, and also nonionic monomers such as acrylamide.

EP-A172723 relates to a method of flocculating suspensions using water-soluble, substantially linear polymers with a "single point intrinsic viscosity" >3. The polymer is a copolymer of two or more ethylenically unsaturated monomers comprising at least 0.5% by weight of monomers comprising hydrophobic groups. The polymer can also be a cationic polymer.

The problem faced by the present invention was to provide new thickeners. This object is achieved by the thickener of the invention comprising the following components:

i) at least one polymer obtainable by polymerizing:

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) optionally at least one chain transfer agent,

ii) at least one activator,

Wherein the ratio of activator to polymer is >10 to 100 [% by weight/% by weight].

The thickeners according to the invention are characterized by their advantageous properties with regard to deposition, shear thinning, stabilization and/or viscosity (thickening). Deposition is understood to mean the deposition of active ingredients such as fabric softeners on the fibers during the laundering operation. Applied to the present invention, this means that for example the inventive thickener comprising at least one polymer (active ingredient) is present in the fabric softener and that the fabric softener is used during or after the washing operation. The thickeners according to the invention facilitate this deposition of the active ingredient to a considerable extent during or after washing operations. Particularly good properties in terms of deposition can be achieved when using polymers based on predominantly neutral monomers based on at least one associative monomer, nonionic monomers such as acrylamide and optionally anionic monomers .

When evaluating shear thinning, it is important that the thickener or corresponding fabric softener is viscous and dense in its base state and thins when stirred. This improved shear thinning has a positive impact on pump life and performance during fabric softener production, facilitating convenient dispensing for consumers as well as facilitating residue-free use of fabric softener, especially in washing machines with automatic dosing devices middle. The thickeners according to the invention improve the stability of the thickener itself and of the corresponding formulations. Sedimentation or creaming of particles is effectively prevented, irrespective of whether they are on the nano, micro or millimeter scale. The contributing factor here is the favorable yield point of the thickener of the invention. Furthermore, they have the advantage of achieving any required redispersion and thickening very quickly.

Thickeners according to the invention in which a mixture of at least two activators are present have the additional advantage of at least one activator having a high HLB value and at least one activator having a low HLB value. The combination of such activator mixtures with polymers comprising at least one ethylenically unsaturated associative monomer block unit results in a spontaneous phase inversion (within seconds) upon dilution of the thickener with water without requiring the input of additional Energy, for example in the form of stirring.

Furthermore, in the case of the thickeners of the invention it is advantageous if the ratio of associative monomers to total polymer is relatively low. When using the thickener in surfactant-containing formulations, the effect of the associative monomer is optimal even at an amount of about 0.5% by weight (based on the polymer).

If the inventive thickeners are prepared by inverse emulsion polymerization in which the temperature is kept constant at at least 40° C., good homogeneity in the distribution of the associative monomer block units within the polymer can be observed. Especially in the case of small amounts of associative monomers, eg 0.1 to 1% by weight, this is advantageous in all the aforementioned rheological properties such as thickening, shear thinning, stabilization and also the washing and rinsing effect.

This embodiment in which the polymer present in the thickener is prepared with little or no crosslinking agent is also advantageous. Resoiling during laundering operations is reduced due to the relatively high (water) soluble fraction of the polymer. Thus, the articles to be washed have clean fibers from which dirty particles have been effectively removed, even after repeated washing processes, which means that no graying is detectable. No or only very slight adhesion and/or redistribution of soiled particles/polymers on the washed articles is observed.

Within the scope of the present invention, for example, the following definition of the group R ₉ in formula (I) as C ₁ -C ₃₀ alkyl means that the substituent (group) has 1-30 carbon atoms alkyl. The alkyl groups can be linear or branched and also optionally cyclic. Alkyl groups having both cyclic and linear components also fall within this definition. The same applies to other alkyl groups, such as C ₁ -C ₄ -alkyl or C ₁₆ -C ₂₂ -alkyl. Alkyl groups may also optionally be mono- or polysubstituted by functional groups such as amino, quaternary ammonium, hydroxyl, halogen, aryl or heteroaryl. Unless otherwise indicated, the alkyl groups preferably do not have any functional groups as substituents. Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-ethylhexyl, tert-butyl (tert-Bu/t-Bu), cyclohexyl, octanyl base, stearyl or behenyl.

The invention is described below in more precise terms.

The thickeners according to the invention comprise at least one polymer as component i). The polymers can be prepared by polymerizing the following components a) and b) and also optionally c) and d).

As component a), at least one water-soluble ethylenically unsaturated monomer is used which comprises at least one anionic monomer and/or at least one nonionic monomer. Anionic and nonionic monomers are known per se to the person 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 sodium acrylate.

If at least one nonionic monomer is present in component a), esters of the aforementioned anionic monomers are also suitable as nonionic monomers, in addition to the nitrogen-containing monomers described below, such as compounds of the formula (I). Such nonionic monomers are preferably methyl or ethyl esters of acrylic or methacrylic acid, such as ethyl acrylate or methyl acrylate. Preference is also given to the corresponding dimethylamino-substituted esters, such as dimethylaminoethyl (meth)acrylate.

Preferably the nonionic monomer is selected from N-vinylpyrrolidone, N-vinylimidazole or a compound of formula (I):

in

R ₇ is H or C ₁ -C ₄ alkyl,

_R is H or methyl, and

R ₉ and R ₁₀ are independently H or C ₁ -C ₃₀ alkyl.

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

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

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, it is preferred within the scope of the present invention that component a) does not comprise cationic monomers.

As component b), at least one ethylenically unsaturated associative monomer is used in the polymerization to produce the polymer. Associative monomers are known per se to the person skilled in the art. Suitable associative monomers are described, for example, in WO 2009/019225. Associative monomers are also known as surfactant monomers.

Preferably in the polymer the ethylenically unsaturated associative monomer according to component b) is selected from compounds of formula (II):

RO-(CH ₂ -CHR'-O) _n -CO-CR"=CH ₂ (II)

in

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 0-100, preferably 3-50, especially 25.

As component b), particular preference is given to using compounds of the formula (II), wherein

R is C ₁₆ -C ₂₂ alkyl,

R' is H,

R'' is H or methyl, and

n is 25.

The compound of formula (II) is commercially available in solution, for example under the name Plex 6954O from GmbH commercially available. These are methacrylates of fatty alcohol ethoxylates, such as commercially available AT25 (BASF SE, Ludwigshafen, Germany).

The radical R in the compound of formula (II) may also be present as a mixture of radicals with different chain lengths, eg _C16 and _C18 . An example of this is C ₁₆ -C ₁₈ fatty alcohol (ethylene glycol) ₂₅ -ether methacrylate, in which both C ₁₆ and C ₁₈ fatty alcohol groups (in non-negligible amounts) are present as a mixture. In contrast, for example in the compounds (formula (II)) behenyl-25 methacrylate and cetyl-25 methacrylate, the corresponding radical R is present not as a mixture but as a _C22 or the _C16 chain exists. Other chain lengths occur only as impurities. The number "25" in these compounds of formula (II) indicates the magnitude of the variable n.

In the preparation of the polymers by polymerization, at least one crosslinker may optionally be present as component c). Suitable crosslinkers are known to those skilled in the art. Preferably the crosslinking agent according to component c) in the polymer is selected from divinylbenzene, tetraallyl ammonium chloride, allyl acrylate, allyl methacrylate, glycols or polyglycerols Diacrylates and dimethacrylates of alcohols, butadiene, 1,7-octadiene, allyl acrylamide or allyl methacrylamide, bisacrylamidoacetic acid, N,N'- Methylbisacrylamide or polyol polyallyl ethers such as polyallyl sucrose or pentaerythritol triallyl ether. Also suitable as the preferred crosslinking agent are dialkyldimethylammonium chlorides.

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

Polymerization processes suitable for the preparation of the polymers or thickeners of the invention comprising at least one polymer and also any additives or auxiliaries used in the polymerization or the thickener production process are defined in more detail below.

Preferably in the thickener according to the invention at least one polymer is present which can be prepared by polymerizing:

a) 20-99.99% by weight, preferably 95-99.95% by weight (based on the polymer) of at least one water-soluble ethylenically unsaturated monomer comprising at least one anionic monomer and/or at least one nonionic monomer ,

b) 0.01-80% by weight, preferably 0.05-5% by weight, particularly preferably 0.1-1% by weight (based on the polymer), of at least one ethylenically unsaturated associative monomer,

c) 0-0.3% by weight, preferably 0.01-0.1% by weight (based on the polymer) of optionally at least one crosslinker,

d) 0-0.3% by weight, preferably 0.01-0.1% by weight (based on the polymer) of optionally at least one chain transfer agent.

In another embodiment of the invention, the polymer has a water-soluble fraction greater than 25% by weight (based on the total weight of the polymer), especially when little or no cross-linking is used other than the associative monomer. When combining agents. Preferably more than 40% by weight, especially 70-100% by weight, of the polymer is soluble in water. The solubility of the polymer is determined by methods known to those skilled in the art, wherein the polymer present in the thickener of the invention is mixed with a defined amount of water (see for example EP-A 343 840 or preferably according to P. Schuck, "Size-distribution analysis of macromolecules bysedimentation velocity ultracentrifugation and Lamm equation modeling, Biophysical Journal78, (3) (2000), 1606-1619's method for determining the sedimentation coefficient in Svedberg (sved) units).

Preferably in this embodiment the proportion of crosslinker (component c)) used in the polymerization of the polymer is <10% by weight (based on the total amount of components a) to d)). It is particularly preferred not to use any crosslinkers in the polymerization of the polymer.

Furthermore, the thickeners according to the invention comprise at least one activator as component ii). The activators themselves are known in principle to those skilled in the art.

Suitable activators are preferably surfactants, such as anionic, nonionic, cationic and/or amphoteric surfactants, which are disclosed, for example, in WO 2009/019225. Preference is given to using anionic and/or nonionic surfactants.

The nonionic surfactants used are preferably fatty alcohol alkoxylates. Fatty alcohol alkoxylates are also known as polyalkylene glycol ethers. Preferred fatty alcohol alkoxylates are alkoxylated, advantageously ethoxylated, especially primary alcohols preferably having 8 to 18 carbon atoms and an average of 1 to 12 mol of ethylene oxide (EO) per mole of alcohol. Alcohols, wherein the alcohol group can be linear or branched, preferably 2-methyl branched, or can contain linear and methyl branched groups in a mixture, as is usually present in oxo alcohol groups. However, particular preference is given to alcohols having 12 to 18 carbon atoms from natural or industrial sources, for example from coconut alcohol, palmitic alcohol, tallow alcohol or oleyl alcohol - or mixtures, as can be derived, for example, from castor oil - Alcohol ethoxylates with a linear group and an average of 2-8 EOs per mole of alcohol. Preferred 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, with 3 EO, 5 EO, C ₁₃ -C ₁₅ alcohols with 7 EO or 8 EO, C ₁₂ -C ₁₈ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as C ₁₂ -C ₁₄ alcohols with 3 EO Mixtures with C ₁₂ -C ₁₈ alcohols with 7 EOs. The degree of ethoxylation is a statistical average which can be an integer or a fraction for a particular product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with an EO greater than 12 can also be used. Examples thereof are tallow alcohols with 14 EO, 25 EO, 30 EO or 40 EO. It is also possible to use nonionic surfactants which contain EO and PO groups together in the molecule. It is possible here to use block copolymers having EO-PO block units or PO-EO block units, but also EO-PO-EO copolymers or PO-EO-PO copolymers. It is of course also possible to use mixed alkoxylated nonionic surfactants in which the EO and PO units are not distributed in blocks, but in random distribution. Such products can be obtained by the simultaneous action of ethylene oxide and propylene oxide on fatty alcohols.

In addition, alkyl glycosides or alkyl polyglycosides can also be used as other nonionic surfactants. Alkyl glycosides and alkyl polyglycosides are generally understood by those skilled in the art to mean compounds comprising at least one alkyl segment and at least one sugar or polysaccharide segment. The alkyl segments are preferably derived from fatty alcohols having 12 to 22 carbon atoms, while the sugar segments are preferably derived from glucose, sucrose or sorbitan.

For example, alkyl glycosides of general formula (1) can be used:

R ¹ O(G) _x (1)

wherein ^R is a linear or methyl-branched, especially 2-methyl-branched, primary aliphatic group with 8-22, preferably 12-18, carbon atoms, and G is a primary aliphatic group with 5 or 6 A glycosidic unit of carbon atoms, preferably glucose. The degree of oligomerization x defining the distribution of monoglycosides and oligoglycosides is any number between 1-10, preferably x is 1.2-1.4.

Another class of nonionic surfactants which are preferably used as sole nonionic surfactants or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and acrylic Oxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described, for example, in Japanese patent application JP58/217598, or preferably by international patent application WO-A - Prepared by the method described in 90/13533.

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 alkanes Nonionic surfactants of the aldolamide type may also be suitable. The amount of these nonionic surfactants is preferably not more than the amount of ethoxylated fatty alcohols, especially not more than half the amount.

Other suitable surfactants are polyhydroxy fatty acid amides of formula (2):

wherein R ² C(=O) is an aliphatic acyl group having 6-22 carbon atoms, R ³ is hydrogen, an alkyl or hydroxyalkyl group having 1-4 carbon atoms and [Z] is an acyl group having 3-10 Linear or branched polyhydroxyalkyl groups of carbon atoms and 3-10 hydroxyl groups. Polyhydroxy fatty acid amides are known substances which can generally be obtained by reductive amination of reducing sugars with ammonia, alkylamines or alkanolamines and subsequent acylation with fatty acids, fatty acid alkyl esters or fatty acid chlorides.

This group of polyhydroxy fatty acid amides also includes formula (3) compound:

Wherein R ^is a linear or branched alkyl or alkenyl group with 7-12 carbon atoms, ^R is a linear, branched or cyclic alkylene group with 2-8 carbon atoms or has 6-8 The arylene group of carbon atoms and R ⁶ is a linear, branched or cyclic alkyl or aryl or oxyalkyl group with 1-8 carbon atoms, wherein C ₁ -C ₄ alkyl or phenyl is preferred, and [ Z] ¹ is a linear polyhydroxyalkyl group whose alkyl chain is substituted by at least two hydroxyl groups, or an alkoxylated, preferably ethoxylated or propoxylated derivative of this group. [Z] ¹ is preferably obtained by reductive amination of sugars such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can subsequently be converted into the desired polyhydroxy fatty acid amides, for example according to WO-A-95/07331 by reaction with fatty acid methyl esters in the presence of alkoxylates as catalysts .

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are here alkylbenzenesulfonates, preferably _C9 - _C13 alkylbenzenesulfonates, olefinsulfonates, i.e. mixtures of alkene- and hydroxyalkanesulfonates , and also disulfonates, obtained for example from C ₁₂ -C ₁₈ monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent basic or acidic hydrolysis of the sulfonated product. Also suitable are alkanesulfonates, preferably secondary alkanesulfonates, which are obtained, for example, from C ₁₂ -C ₁₈ alkanes by chlorosulfonation or sulfoxidation followed by hydrolysis or neutralization. Esters of α-sulfo fatty acids (ester sulfonates), such as the α-sulfonated methyl esters of hydrogenated coconut fatty acids, palm kernel fatty acids or tallow fatty acids, are likewise suitable.

Other suitable anionic surfactants are sulfated fatty acid glycerides. Glycerides of fatty acids are understood to mean mono-, di- and triesters, and mixtures thereof, which are produced by esterification of monoglycerol with 1-3 mol of fatty acids or in the transesterification of triglycerides with 0.3-2 mol of glycerol get. Preferred sulfated fatty acid glycerides here are saturated fatty acids having 6 to 22 carbon atoms, for example caproic, caprylic, capric, myristic, lauric, palmitic, stearic or behenic acids. Sulfonated products.

Further suitable anionic surfactants are fatty alcohol sulfates, such as alk(en)yl sulfates. Preferred alk(en)yl sulfates are C ₁₂ -C ₁₈ fatty alcohols, such as coco fatty alcohol, tallow fatty alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, or C ₁₀ -C ₂₀ Alkali metal, especially sodium, sulfate monoesters of oxo alcohols and those monoesters of secondary alcohols having these chain lengths. Further preferred are alk(en)yl sulphates of said chain length, comprising synthetic linear alkyl groups produced on a petrochemical basis, with a degradation behavior similar to equivalent compounds based on aliphatic chemical feedstocks. For scrubbing technology, preference is given to C ₁₂ -C _{16 -} and C ₁₂ -C ₁₅ -alkyl sulfates and also C ₁₄ -C ₁₅ -alkyl sulfates. Prepared, for example, according to US patent specification 3,234,258 or 5,075,041 and available as a commercial product from the Shell Oil Company under the name The resulting 2,3-alkyl sulfates are also suitable anionic surfactants.

Linear or branched C ₇ -C ₂₁ alcohols ethoxylated with 1-6 mol ethylene oxide, such as 2-methyl branched C ₉ -C ₁₁ alcohols with an average of 3.5 mol ethylene oxide (EO) or with 1- Sulfate monoesters of 4 EO C ₁₂ -C ₁₈ fatty alcohols are also suitable.

Further suitable anionic surfactants are also salts of alkyl sulfosuccinic acids, which are also known as sulfosuccinates and are monosodium sulfosuccinic acids with alcohols, preferably fatty alcohols, especially ethoxylated fatty alcohols. esters and/or diesters. Preferred sulfosuccinates contain C ₈ -C ₁₈ fatty alcohol groups or mixtures of these. Particularly preferred sulfosuccinates comprise fatty alcohol groups derived from ethoxylated fatty alcohols. In this context, particular preference is again given to sulfosuccinates whose fatty alcohol groups are derived from ethoxylated fatty alcohols with a narrower homolog distribution. It is likewise possible to use alk(en)ylsuccinic acids or salts thereof which preferably have 8 to 18 carbon atoms in the alk(en)yl chain.

Other suitable anionic surfactants are alkyl carboxylates, for example sodium salts of saturated or unsaturated fatty acids, wherein the alkyl group of the alkyl carboxylates is preferably linear.

Within the scope of the present invention, the activator is preferably selected from fatty alcohol alkoxylates, alkyl glycosides, alkyl carboxylates, alkylbenzene sulfonates, secondary alkane sulfonates and fatty alcohol sulfates, in particular It is preferably selected from fatty alcohol alkoxylates. An example of a preferred fatty alcohol alkoxylate is C ₆ -C ₁₇ (secondary)-poly(3-6) ethoxylates.

Furthermore, preference is given within the scope of the invention to using activators with (relatively) high HLB values (hydrophilic-lipophilic balance). Preferably the activator has an HLB of 7-18, more preferably 8-15, especially preferably 9-13.

Activators with high HLB values are preferably i) fatty alcohol alkoxylates formed from secondary alcohols or mixtures of alcohols having 12-18 carbon atoms and ethylene oxide or propylene oxide, and ii) sucrose and C ₈ - Alkyl glycosides formed from _C22 fatty alcohols. Examples of such activators are Synperonic 87K commercially available from Croda GmbH, Herrenpfad-Süd 33, 41334 Nettetal, Germany; Croduret 40 or other ethoxylated hydrogenated castor oils such as Etocas 40 or Crodesta F110, all ex Croda.

In another embodiment of the present invention, preference is given to using a mixture of at least two activators, wherein at least one activator has a high HLB value and at least one activator has a low HLB value. Activators with high HLB values preferably have HLB values >12-20 and activators with low HLB values preferably have HLB values 1-12. In this embodiment, the activator with a high HLB value and the activator with a low HLB value can be present with one another in any desired ratio known to those skilled in the art. Preference is given to using 20-50% by weight of an activator with a high HLB value and 50-80% by weight of an activator with a low HLB value in the mixture. It is further preferred to adjust this ratio of activators with high HLB values to activators with low HLB values so that the overall HLB value is 7-18, more preferably 8-15, particularly preferably 9-13.

In these mixtures of at least two activators, the activators used with high HLB values are preferably alkyl glycosides or polyalkyl glycosides or polyalkyl oligomeric compounds based on sucrose or sorbitan and C ₈ -C ₂₂ fatty alcohols Oxidized ethylene glycosides, such as polyethylene glycol sorbitan monostearate or polyoxyethylene sorbitan monostearate. Examples of such activators are the commercially available Crillet1, Crillet3 or Crodesta F160, all ex Croda. As activators with low HLB values, preference is given to using alkyl glycosides formed from sucrose or sorbitan and _C8 - _C22 fatty alcohols or fatty acids, such as sorbitan laurate or sorbitan stearate . Examples of such activators are the commercially available Crill1, Crill3 or Crodesta F10 from Croda.

According to the invention, the ratio of activator to polymer is >10:100 [wt%/wt%], preferably 10.5-50:100 [wt%/wt%], particularly preferably 11.5-20:100 [wt%/wt% ].

In the thickener according to the invention, other components may be present in addition to the polymer and the activator. Suitable further components are defined in more detail below with regard to the thickener and the preparation of the polymer. Suitable further components are, for example, oils and solvents.

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

The present invention further provides a method for preparing the thickener of the present invention. Thickener preparation methods per se and methods of preparing polymers are known to those skilled in the art. Preferably the polymer is prepared by emulsion polymerization, especially inverse emulsion polymerization. Preferably the polymer is prepared first and the thickener is obtained after polymerization, preferably by adding the activator after inverse emulsion polymerization.

The polymers can be prepared in various ways, preferably by emulsion polymerization, especially inverse emulsion polymerization. Inverse emulsion polymerization is generally understood by those skilled in the art to mean a polymerization process according to the following definition: a hydrophilic monomer is dispersed in a hydrophobic oil phase. Polymerization is carried out directly in these hydrophilic monomer particles by adding an initiator.

Furthermore, preferably after the inverse emulsion polymerization and before adding the activator, at least some water and at least some low-boiling constituents are distilled off from the oil phase, especially by means of LDP (Liquid Dispersion Polymer) technology. The LDP technique itself is known to the person skilled in the art; it is for example described in WO2005/097834.

Unless otherwise stated, the details below apply to all types of emulsion polymerizations, such as emulsion polymerizations in water which then also constitutes the continuous phase, and especially also to inverse emulsion polymerizations in which the hydrophobic oil phase constitutes the continuous phase. A suitable polymerization initiator is used for the polymerization. Preference is given to redox initiators and/or thermally activatable free-radical polymerization initiators.

Suitable thermally activatable free-radical initiators or oxidizing components of redox initiator pairs are primarily those of the peroxy and azo types. These include, inter alia, hydrogen peroxide, peracetic acid, tert-butyl hydroperoxide, di-tert-butyl peroxide, dibenzoyl peroxide, benzoyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-Dimethyl-2,5-di(hydroperoxy)hexane, perbenzoic acid, tert-butyl peroxypivalate, tert-butyl peracetate, dilauroyl peroxide, dilauroyl peroxide Hexanoyl, Distearoyl Peroxide, Dibenzoyl Peroxide, Diisopropyl Peroxydicarbonate, Didecyl Peroxydicarbonate, Di-Eicosyl Peroxydicarbonate, Diperbenzoic Acid tert-butyl ester, azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, ammonium persulfate, potassium persulfate, sodium persulfate and sodium superphosphate.

Most preferred are persulfates (peroxodisulfates), especially sodium persulfate.

When emulsion polymerization is carried out, the initiator is used in an amount sufficient to initiate polymerization. The initiator is generally used in an amount of about 0.01 to 3% by weight, based on the total weight of the monomers used. The amount of initiator is preferably about 0.05 to 2% by weight, especially 0.1 to 1% by weight, based on the total weight of the monomers used.

Emulsion polymerization is usually carried out at 35-100°C. It can be carried out as a batch process or as a feed process. In the feed procedure, at least some of the polymerization initiator and optionally some of the monomers are introduced as an initial charge and heated to the polymerization temperature, followed by continuous or stepwise introduction of the remainder of the polymerization mixture while maintaining the polymerization, usually via a plurality of separate Feeds, one or more of which contain monomer in pure or emulsified form. Preferably the monomer feed is carried out in the form of a monomer emulsion. Parallel to the monomer feed, further polymerization initiators can be metered in.

In a preferred embodiment, the entire amount of initiator is introduced as an initial charge, ie no further initiator is metered in parallel to the monomer feed.

In a preferred embodiment, the heat-activatable free-radical polymerization initiator is therefore introduced entirely as starter charge and added to the monomer mixture, preferably in the form of a monomer emulsion. The initial charge is brought to the activation temperature or higher of the thermally activatable free-radical polymerization initiator prior to commencing the monomer mixture feed. The activation temperature is considered to be the temperature at which at least half of the initiator decomposes after 1 hour.

According to another preferred preparation method, the polymers are obtained by polymerizing monomer mixtures in the presence of redox initiator systems. Redox initiator systems comprise at least one oxidizing agent component and at least one reducing agent component, in which case heavy metal ions are preferably additionally present in the reaction medium as catalysts, for example cerium salts, manganese salts or iron(II) salts.

Suitable oxidizing agents are, for example, peroxides and/or hydroperoxides, such as hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, pinane hydroperoxide, diisopropylbenzene hydroperoxide dicyclohexyl percarbonate, dibenzoyl peroxide, dilauroyl peroxide and diacetyl peroxide. Hydroperoxide and tert-butyl hydroperoxide are preferred.

Suitable reducing agent components are alkali metal sulfites, alkali metal dithionites, alkali metal sulfoxylates, sodium bisulfite, Rongalit C (sodium formaldehyde sulfoxylate), mono- and dihydroxyacetone, Carbohydrates (eg glucose or dextrose), ascorbic acid and its salts, acetone/bisulfite adducts and/or alkali metals of hydroxymethanesulfinic acid, preferably sodium bisulfite or sodium metabisulfite.

Also suitable as reducing agent component or catalyst are iron(II) salts, such as iron(II) sulfate, tin(II) salts, such as tin(II) chloride, titanium(III) salts, such as titanium(III) sulfate.

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

Particularly preferred redox initiator systems are sodium peroxodisulfate/sodium bisulfite systems, for example 0.001-5.0% by weight sodium peroxodisulfate and 0.001-2.0% by weight sodium bisulfite, especially 0.005-1.0% by weight Sodium peroxodisulfate and 0.005-1.0% by weight sodium bisulfite, particularly preferably 0.01-0.5% by weight sodium peroxodisulfate and 0.01-0.5% by weight sodium bisulfite.

A further particularly preferred redox initiator system is the tert-butyl hydroperoxide/hydrogen peroxide/ascorbic acid system, for example 0.001-5.0% by weight tert-butyl hydroperoxide, 0.001-5.0% by weight hydrogen peroxide and 0.001-2.0% by weight % ascorbic acid, especially 0.005-1.0 wt. % tert-butyl hydroperoxide, 0.005-1.0 wt. % hydrogen peroxide and 0.005-1.0 wt. % ascorbic acid, especially preferably 0.01-0.5 wt. % by weight hydrogen peroxide and 0.01-0.5% by weight ascorbic acid.

Preferably, the polymers are prepared by inverse emulsion polymerization, in which the aqueous and oily phases of the water-soluble components are first prepared separately from each other. The two phases are then mixed with each other to obtain a water-in-oil dispersion. The mixture is polymerized by adding a redox initiator system; a thermal initiator can optionally also be added here or activated thermally if it is already present.

In the aqueous phase, chain transfer agents, crosslinkers, anionic monomers and/or neutral monomers and also optionally associative monomers, and also optionally further components are preferably present. Suitable further components are, for example, salt complexing agents such as pentasodium diethylenetriaminepentaacetate.

Emulsifiers, stabilizers, high boiling oils, low boiling oils and/or optional associative monomers are preferably present in the oil phase. In addition, nonionic monomers may optionally be present in the oil phase.

Emulsifiers, stabilizers, low-boiling oils and high-boiling oils are known per se to those skilled in the art. These compounds may be used alone or in admixture.

Typical emulsifiers are anionic emulsifiers such as sodium lauryl sulfate, sodium tridecyl ether sulfate, dioctyl sulfosuccinate sodium salt, and sodium alkylaryl polyether sulfonic acid; and nonionic emulsifiers , such as alkyl aryl polyether alcohols and ethylene oxide/propylene oxide copolymers. Sorbitan trioleate is likewise suitable as emulsifier.

Preferred emulsifiers have the general formula:

RO-(CH ₂ -CHR′-O) _n -X,

Wherein R is C ₆ -C ₃₀ alkyl,

R' is hydrogen or methyl,

X is hydrogen or SO ₃ M,

M is hydrogen or an alkali metal, and

n is an integer of 2-100.

Suitable stabilizers are described, for example, in EP-A172025 or EP-A172724. 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, while suitable low-boiling oils are, for example, dearomatized aliphatic hydrocarbons or low-viscosity 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 the inverse emulsion polymerization.

During the inverse emulsion polymerization the temperature can be kept constant or the temperature can also be increased. The increase in temperature can be carried out continuously or stepwise. Thus, for example, the temperature during the polymerization can be increased by 0.2-10°C/min, preferably 1-3°C/min. The temperature increase is controlled by the rate of addition of the initiator. The temperature starting value may be 0-30°C, preferably 10-20°C.

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

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

If within the scope of the invention the temperature is kept constant during the polymerization, in particular during the inverse emulsion polymerization, this means that the temperature is kept constant from the start of the polymerization. A fluctuation of +/- 5°C, preferably +/- 2°C, especially +/- 1°C during the polymerization process is considered a constant temperature (based on the desired constant temperature value). The temperature is kept constant until the polymerization is complete; this is preferably maintained until after a conversion of greater than 90% of the monomers used, more preferably greater than 95% by weight, particularly preferably after complete conversion (100% by weight). This temperature can be kept constant by dissipating the heat of reaction occurring by cooling. The polymerization is usually initiated by adding a polymerization initiator, preferably a redox initiator system. The system is usually first heated to the desired temperature and waited for constant temperature while stirring. A polymerization initiator is then added, resulting in the initiation of the polymerization process. In one embodiment of the invention, this temperature is kept constant at a value above the melting point of the associative monomer used.

The invention further provides surfactant-containing acidic formulations comprising at least one thickener according to the invention as defined above. The pH of the formulation is from 1 to <7.

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

The surfactant-containing acidic or basic formulations of the invention may contain other ingredients known to those skilled in the art. Suitable ingredients include one or more substances selected from the group consisting of builders, bleaches, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH modifiers, fragrances, fragrance carriers, fluorescers, dyes, water soluble Accelerators, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrinkage agents, anti-wrinkle agents, dye transfer inhibitors, antibacterial active ingredients, bactericides, fungicides, antioxidants , corrosion inhibitors, antistatic agents, ironing aids, thinning and impregnating agents, swelling and anti-slip agents, and UV absorbers.

The invention further provides surfactant-containing acidic formulations according to the invention in hair cosmetics, hair styling, as shampoos, as emollients, as care compositions, as conditioners, as skin creams, as shower gels . Use as a fabric softener for laundry or as an acidic cleaner, preferably an acidic cleaner for toilets or bathtubs.

The invention further provides the use of the surfactant-containing alkaline formulations according to the invention as care compositions, liquid detergents or dishwashing detergents for machine or hand washing.

The present invention further provides thickeners according to the invention as viscosity modifiers for optimized shear thinning, as thickeners for stabilizing suspended components with sizes in the nanometer to millimeter range and/or in surfactant-containing acidic or use in alkaline formulations.

In the description, including all examples, the following abbreviations are used:

monomer

ACM acrylamide

AA acrylic

MAA Methacrylic acid

NaAc sodium acrylate

BEM Behenyl-25 Methacrylate

MBA Methylene bisacrylamide (crosslinking agent)

TAAC Tetraallyl Ammonium Chloride (Crosslinking Agent)

NaHP sodium hypophosphite (chain transfer agent)

C16EO25MAc C ₁₆ -C ₁₈ -Fatty alcohol-(ethylene glycol) ₂₅ ether methacrylate

other

pphm parts per hundred monomers (based on components a) and b))

demin. to soften

The present invention is illustrated below with reference to examples.

Example

Comparative example C1

Synthesis of thickeners/polymers starting from anionic monomers without associative monomers, but using crosslinkers and chain transfer agents and also increasing the polymerization temperature.

Prepare the water phase of the water soluble components by mixing the following components:

250.24g (139.02pphm) water,

0.89g (0.49pphm) pentasodium diethylenetriaminepentaacetate,

11.05g (0.06pphm) methylenebisacrylamide (1%, in water),

180g (100pphm) acrylic acid, and

146.8g (40.78pphm) NaOH (50%, in water)

The aqueous phase was adjusted to pH 5.5 using NaOH (50% in water).

Prepare the oil phase by mixing the following components:

20.62 g (8.59 pphm) sorbitan monooleate (75% in hydrothermal heavy naphtha (petroleum) [Isopar G])

93.19 g (12.27 pphm) polymer stabilizer: stearyl methacrylate-methacrylic acid copolymer (23.7% in hydrothermal heavy naphtha [Isopar G]),

120.24g (66.8pphm) low viscosity mineral oil (Kristol M14) and

236.28 g (131.27 pphm) of hydrothermal heavy naphtha [Isopar G].

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

Polymerization was achieved by adding 13 g (0.014 pphm) of sodium metabisulfite (0.2%, in hydrothermal heavy naphtha (petroleum) [Isopar G]) and 13 g (0.014 pphm) of tert-butyl hydroperoxide (0.2%, in hydrothermal The heavy naphtha (petroleum) [Isopar G]) is achieved by redox pairs. The redox couple was added gradually to increase the temperature by 2°C/min. Once isothermal is reached, the radical initiator (2,2'-azobis(2-methylbutyronitrile), CAS: 13472-08-7) is added in 2 steps (the second step after 45 minutes) and The emulsion was held at 85°C for 75 minutes.

Water and low boiling components of the oil phase (Isopar G) were removed using vacuum distillation.

Low viscosity mineral oil (Kristol M14) was added to the product to achieve a solids content of 54%. To this product was added 8% (based on the total mass fraction of the product) of a fatty alcohol alkoxylate (C12/15 alcohol alkoxylate [Synperonic 87K ^™ ]) to produce a thickener with a polymer solids fraction of 50%. agent (dispersion). The ratio of activator to polymer is thus 16.0:100 [wt%/wt%].

Example 1

Starting from anionic monomers, thickeners/polymers at associative monomers and constant polymerization temperature:

Example 1.1

Prepare the water phase of the water soluble components by mixing the following components:

246.13g (140.65pphm) water,

0.86g (0.49pphm) pentasodium diethylenetriaminepentaacetate,

174.13g (99.5pphm) acrylic acid, and

154.26g (44.07pphm) NaOH (50%, in water)

The aqueous phase was adjusted to pH 5.5 using NaOH (50% in water).

Prepare the oil phase by mixing the following components:

20.05 g (8.59 pphm) sorbitan monooleate (75% in hydrothermal heavy naphtha (petroleum) [Isopar G])

90.6 g (12.27 pphm) polymer stabilizer: stearyl methacrylate-methacrylic acid copolymer (23.7% in hydrothermal heavy naphtha [Isopar G]),

119.03g (68.02pphm) low viscosity mineral oil (Kristol M14) and

229.72g (131.27pphm) hydrothermal heavy naphtha [Isopar G]

1.09 g (0.5 pphm) associative monomer: 60% by weight C16EO25Mac: contained in the commercial product Plex6954-O (containing 20% by weight methacrylic acid, 20% by weight water).

The two phases were mixed using high shear at a ratio of 55.6 parts water to 44.4 parts oil phase to produce a water-in-oil emulsion. The resulting water-in-oil emulsion was introduced into a reactor equipped with a nitrogen sparge line, a stirrer and a thermometer. The emulsion was purged with nitrogen while being heated to 50°C, resulting in the removal of oxygen.

Polymerization was achieved by adding a redox couple consisting of 13.6 g (0.016 pphm) sodium metabisulfite (0.2% in water) and 13.6 g (0.016 pphm) tert-butyl hydroperoxide (0.2% in water). The redox couple was added within 2 h at 50 °C. The mixture was then heated to 85°C and the free radical initiator (2,2'-azobis(2-methylbutyronitrile), CAS: 13472-08 -7) and keep the emulsion at 85°C for 75 minutes.

Water and low boiling components of the oil phase (Isopar G) were removed using vacuum distillation.

Low viscosity mineral oil (Kristol M14) was added to the product to achieve a solids content of 54%. To this product was added 8% (based on the total mass fraction of the product) of a fatty alcohol alkoxylate (C12/15 alcohol alkoxylate [Synperonic 87K ^™ ]) to produce a thickener with a polymer solids fraction of 50%. agent (dispersion). The ratio of activator to polymer is thus 16.0:100 [wt%/wt%].

The following examples according to Table 1 were prepared according to Example 1.1, taking into account the changes in monomer composition. The associative monomer C16EO25Mac was added to the oil phase. The commercially available product Plex6954O was used; this contained 60% by weight of associative monomers with water and MAA as solvents in a ratio of about 1:1. The weight data in Table 1 relate to the amount of associative monomer without solvent. The ratio of activator to polymer in all examples according to Table 1 is in each case 16.0:100 [wt%/wt%]; unless otherwise stated, the polymer solids of the corresponding thickeners (dispersions) The score is 50%.

Table 1

Example C16EO25MAc (pphm) sodium acrylate Acrylamide MBA (pphm) illustrate 1.1 0.38 99.5 - 1.2 0.38 99.5 0.06 1.3 (comp.) - 100 - 1.4 0.38 99.5 -

Example 2

Starting from anionic monomers, thickeners/polymers at associative monomers and also increasing polymerization temperature:

The following examples according to Table 2 were prepared according to comparative example C1, taking into account said changes in monomer composition. The associative monomer C16EO25Mac was added to the oil phase. The commercially available product Plex6954O was used; this contained 60% by weight of associative monomers with water and MAA as solvents in a ratio of about 1:1. The weight data in Table 2 relate to the amount of associative monomer without solvent. The ratio of activator to polymer in all examples according to Table 2 is in each case 16.0:100 [wt%/wt%]; unless otherwise indicated, the polymer solids of the corresponding thickeners (dispersions) The score is 50%.

Table 2

Example C16EO25Mac Acrylic Acrylic MBA illustrate

(pphm) sodium acid Amide (pphm) 2.1 1.5 98 0.06 2.2 0.38 99.5 0.06 2.3 1.5 98 0.06 The starting temperature is 14°C 2.4 1.5 98 -- 2.6 0.38 99.5 - 2.5 (comp.) - 100 0.2 C1 - 100 0.06 2.7 (comp.) - - 100 - 2.8 0.38 - 99.5 -

General measurement method:

Unless otherwise indicated, the following general measurement methods were used in the following examples:

Viscosity determination:

Considering the procedures according to DIN51550, DIN53018, DIN53019, the viscosity mPa*s is measured using a Brookfield DV II type viscometer, unless otherwise indicated in the table below, using spindle No. 6 at a speed of 20 rpm.

Determination of shear dilution

The measurements were carried out in an ASC (Automatic Sample Changer) rotational rheometer from Antonpaar with CC27 cylinder geometry, measuring body with a radius of 13.33 mm and measuring cup with a radius of 14.46 mm. The measurement temperature was 23°C. Samples were measured at steady state shear starting at low shear increasing to high shear (0.01 s ⁻¹ -1000 s ⁻¹ ) and back again (1000 s ⁻¹ -0.01 s ⁻¹ ).

Example 3

Using thickeners/polymers in water

The thickener was slowly added to distilled water according to Table 3 at room temperature and stirred until the formulation was homogenized. The resulting aqueous formulations according to Table 3 comprise 1.0% by weight of polymer to 99.0% by weight of water or 0.5% by weight of polymer to 99.5% by weight of water. The results are summarized in Table 3.

table 3

Rheological properties of thickeners/polymers in water starting from anionic monomers, measured 5 minutes after preparation of the formulations

If increasing amounts of associative monomers are incorporated into the polymer, the thickening effect is significantly enhanced compared to C1 without associative monomers. The lower the onset temperature during the polymerization according to Example 2, the greater the thickening effect. The procedure at a constant polymerization temperature of 50° C. produces an increased thickening effect for an otherwise identical monomer composition. The last four examples of Table 3 relate to acrylamide-containing polymers.

Example 4.1

Use of thickeners/polymers in standard formulations of care compositions

The care composition formulation (P1) comprises the ingredients in Table 4.1. P1 was prepared by heating phases A and B to 80° C. in each case. The two phases were then combined and homogenized. The mixture is then cooled to about 40° C. with stirring, then phase C is added and the mixture is homogenized.

Table 4.1.1: Composition of P1

This thickener was added to care composition formulation P1:

The inventive thickeners listed in Table 4.1.2 or the thickeners according to the comparative example were added slowly to the care composition formulation P1 at room temperature and stirred until the formulation was homogenized. The care composition formulations obtained in this way comprise the stated concentration of thickener in % by weight relative to 100% by weight of the care composition formulation obtained.

Brookfield viscosity was measured 1 day after preparation. The results are summarized in Table 4.1.2.

Table 4.1.2: Thickener properties and shear thinning in care compositions

Rheological properties of fabric softeners comprising thickeners/polymers starting from anionic monomers:

If increasing amounts of associative monomers were incorporated into the polymer, the thickening performance was significantly improved compared to V1 without associative monomers.

Example 4.2

Use of thickener/polymer in standard formulation W3 of fabric softener

W3: Preparation of methyltris(hydroxyethyl)ammonium ditallow fatty acid ester methosulfate, partially hydrogenated fabric softener (5.5% active fraction):

The fabric softener had a pH of 2.7 and contained 5.5% by weight methyltris(hydroxyethyl)ammonium ditallow fatty acid ester methyl sulfate (partially hydrogenated) and 94.5% by weight deionized water.

This thickener was added to fabric softener formulation W3:

The thickeners according to Examples 1 and 2 and the comparative example (see Table 4.2) were slowly added to the corresponding fabric softener formulations at room temperature and stirred until the formulations were homogenized.

Brookfield viscosity was measured 1 day after preparation. The results are summarized in Table 4.2.

Table 4.2. Thickener properties in fabric softener W3

Rheology of fabric softeners containing thickeners/polymers starting from neutral monomers:

When the associative monomer is incorporated into the polymer, the thickening performance is significantly improved compared to the control without the associative monomer.

Example 5

The storage stability of the thickeners according to the invention is investigated in Table 5 below. The thickeners of the invention were found to be significantly more stable.

table 5:

Storage stability of thickeners/polymers starting from anionic monomers:

Example Thickener No. instant sediment Precipitate after 4 days at 40°C 5.1 (comp.) V1 none Significant, non-redispersible 5.2 2.1 none none

A considerable improvement, namely a reduction in sedimentation, is brought about by the thickeners of the invention.

Example 6

Storage stability of care composition formulations (P1) according to example 4 comprising thickeners/polymers starting from anionic monomers:

A considerable improvement, namely a reduction in sedimentation, is brought about by the thickeners of the invention. After almost 3 months, significant settling was visible for the formulation with thickener V1, whereas only minimal settling was visible for the formulation with thickener 2.1 (storage at RT).

Example 7

Thickeners/polymers containing associative monomers starting from anionic monomers and the effect of activators on the thickening rate in aqueous formulations:

Examples 7.1-7.5 listed in Table 6 were prepared according to Example 2.1, varying the amount of activator added after distillation to correspond to the activator concentration (A%) in the thickener given in Table 11 (all data based on this thickener). % by weight of the amount of anionic polymer in the thickener). All thickeners (dispersions) prepared in this way had a polymer solids fraction of 50%. The thickener is then added to the water with stirring. The aqueous formulation obtained in this way comprises 1% by weight of thickener to 99% by weight of water, ie 0.5% by weight of anionic polymer to 99.5% by weight of water. comp. means comparative example.

Table 6

With associative monomers, activators in excess of 10% are required to achieve rapid thickening performance (based on final thickening in excess of 40% in 1 minute).

Claims (20)

1. a thickening material, comprises

I) at least one polymkeric substance that can obtain by the following material of polymerization:

A) at least one water-soluble olefinic unsaturated monomer that comprises at least one anionic monomer and/or at least one non-ionic monomer,

B) the unsaturated associativity monomer of at least one olefinic,

C) optional at least one linking agent,

D) optional at least one chain-transfer agent,

Ii) at least one activator,

Wherein the ratio of activator and polymkeric substance is >10 to 100[% by weight/% by weight].

2. according to the thickening material of claim 1, wherein in described polymkeric substance, component a) comprises at least one anionic monomer, wherein said anionic monomer is selected from vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid or its salt, and especially described anionic monomer is sodium acrylate.

3. according to the thickening material of claim 1 or 2, the described water-soluble fraction of wherein said polymkeric substance is greater than 25 % by weight (based on the gross weight of described polymkeric substance).

4. according to the thickening material of any one in claim 1-3, wherein in described polymkeric substance, component a) comprises at least one non-ionic monomer, and wherein said non-ionic monomer is selected from NVP, N-vinyl imidazole or formula (I) compound:

Wherein

R ₇for H or C ₁-C ₄alkyl,

R ₈for H or methyl, and

R ₉and R ₁₀be H or C independently of each other ₁-C ₃₀alkyl.

5. according to the thickening material of any one in claim 1-4, be wherein selected from formula (II) compound at the unsaturated associativity monomer of olefinic described in described polymkeric substance (components b):

R-O-(CH ₂-CHR’-O) _n-CO-CR”＝CH ₂(II)

Wherein

R is C ₆-C ₅₀alkyl, preferably C ₈-C ₃₀alkyl, especially C ₁₆-C ₂₂alkyl,

R' is H or C ₁-C ₄alkyl, preferably H,

R'' is H or methyl,

N is integer 0-100, preferably 3-50, especially 25.

6. according to the thickening material of any one in claim 1-5, wherein be selected from Vinylstyrene at linking agent described in described polymkeric substance (amount of component b), tetra allyl ammonium chloride, vinylformic acid allyl ester, allyl methacrylate, the diacrylate of glycols or poly-glycol and dimethacrylate, divinyl, 1,7-octadiene, allyl group acrylamide or allyl methyl acrylamide, bisacrylamide guanidine-acetic acid, N, N'-methylene-bisacrylamide or polyvalent alcohol polyenoid propyl ether are as poly-allyl sucrose or pentaerythritol triallyl ether.

7. according to the thickening material of any one in claim 1-6, wherein at chain-transfer agent described in described polymkeric substance, (component d) is selected from mercaptan, lactic acid, formic acid, Virahol or phosphinate.

8. according to the thickening material of any one in claim 1-7, wherein said activator is selected from fatty alcohol alkoxy compound, alkyl glycoside, alkyl carboxylic acid ester, benzene sulfonamide acid esters, secondary bond alkyl sulfonic acid ester and fatty alcohol sulfate, is preferably selected from fatty alcohol alkoxy compound.

9. according to the thickening material of any one in claim 1-8, the mixture that wherein uses at least two kinds of activators, wherein the HLB value (hydrophile-lipophile balance value) of at least one activator is that the HLB value of >12 to 20 and at least one activator is 1-12.

10. according to the thickening material of any one in claim 1-9, wherein said polymkeric substance is present in described oil phase with discrete form, preferably as reverse phase dispersion, water-in-oil dispersion or be dispersed in the anhydrous polymer in oil.

Prepare according to the method for the thickening material of any one in claim 1-10 for 11. 1 kinds, wherein said polymkeric substance, by letex polymerization, especially obtains by inverse emulsion polymerization.

12. according to the method for claim 11, wherein after described inverse emulsion polymerization and before adding activator, from described oil phase, steam except at least some water and at least some low boiling point components, especially by LDP (liquid dispersion polymer) technology.

13. according to the method for claim 11 or 12, wherein in described inverse emulsion polymerization process by components b) add in described oil phase.

14. according to the method for any one in claim 11-13, and wherein the temperature in described inverse emulsion polymerization process keeps constant or improves.

15. according to the method for any one in claim 11-14, and wherein the temperature in described inverse emulsion polymerization process keeps constant and is at least 40 DEG C, preferably 50-90 DEG C.

16. 1 kinds comprise at least one according to the thickening material of any one in claim 1-10 containing the acid preparaton of tensio-active agent, the pH of wherein said preparaton is 1 to <7.

17. according to claim 16 containing the acid preparaton of tensio-active agent in hair cosmetic, Hairsetting, as shampoo, as tenderizer, as care composition, as amendment, as skin ointment, as shower gels, as laundry with fabric softening agent or as acidic cleaning agent, be preferred for the purposes of the acidic cleaning agent of lavatory or bathtub.

18. 1 kinds comprise at least one according to the alkaline preparaton containing tensio-active agent of the thickening material of any one in claim 1-10, and the pH of wherein said preparaton is 7-13.

19. according to claim 18 containing the alkaline preparaton of tensio-active agent as care composition, as liquid washing agent or as machine washing or the purposes of washing dish sanitising agent for hand washing.

20. according to the thickening material of any one in claim 1-10 as viscosity modifier, be used for optimizing shear thinning, as thickening material, be that nanometer is to the suspension composition of millimeter scope and/or in the acidity containing tensio-active agent or the purposes of alkaline preparaton for stable dimensions.