KR20140089535A - Thickener containing at least one polymer based on associative monomers - Google Patents

Abstract

The present invention relates to thickeners comprising:
i) one or more polymers obtainable by the following polymerization
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 one or more crosslinking agents,
d) optionally one or more chain transfer agents,
ii) a thickener containing at least one activator,
The ratio between the activator and the polymer is > 10: 100 [wt% / weight%].

Description

[0001] THICKENER CONTAINING AT LEAST ONE POLYMER BASED ON ASSOCIATIVE MONOMERS [0002]

The present invention relates to thickeners comprising at least one polymer and at least one activator, wherein the ratio of activator to polymer is > 10: 100 [wt% / wt%]. 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. In addition, the invention relates to a process for the preparation of thickeners according to the invention and also to surfactant-containing formulations comprising one or more thickeners. The invention further provides the use of surfactant-containing formulations, for example as softeners or liquid detergents, and also the use of thickeners, for example as viscosity modifiers.

WO 03/102043 discloses a composition comprising (i) a water-soluble ethylenically unsaturated monomer or monomer mixture comprising at least one cationic monomer, (ii) at least one crosslinker in an amount in excess of 50 ppm based on component (i), and (iii) Lt; RTI ID = 0.0 > cationic < / RTI > polymer. The aqueous formulation may be used as a thickener in household formulations.

WO 2009/019225 relates to aqueous dispersions of alkali-soluble copolymers suitable as associative thickeners. Said copolymer comprising as polymerized units a) at least one ethylenically unsaturated carboxylic acid, b) at least one nonionic ethylenically unsaturated surfactant monomer, c) at least one C ₁ -C ₂ -alkyl methacrylate and d) at least one C ₂ - C ₄ -alkylacrylate, wherein the alkyl chain length averaged over the number of alkyl groups of the alkyl acrylate is from 2.1 to 4.0. The associative thickener may be prepared by emulsion polymerization. The associative thickener is suitable for use in detergents and cleaners.

Liquid dispersion polymer (LDP) compositions are disclosed in WO 2005/097834. Such LDP compositions include hydrophilic, water-soluble or swellable polymers having a neutralization content of from about 25 to about 100%, non-aqueous carrier phases and oil-in-water surfactants. The hydrophilic, water-soluble or swellable polymer is preferably obtained, for example, by polymerization of acrylic acid or methacrylic acid. The LDP dispersion is suitable for producing microparticulate thickeners, for example, used in aqueous or organic compositions, in particular personal care or pharmaceutical formulations.

WO 2010/078959 relates to cationic polymer thickeners comprising a crosslinked water-swellable cationic polymer comprising at least one cationic monomer and optionally a nonionic or anionic monomer, wherein the polymer is present in an amount of from 25 % Water soluble polymer chain. In addition, the polymer comprises a crosslinking agent in a concentration of from 500 to 5000 ppm with respect to the polymer. The cationic polymer is prepared by inverse emulsion polymerization.

WO 2010/079100 discloses a fabric softener composition comprising a polymer according to WO 2010/078959.

US 2008/0312343 relates to inverse latex compositions and their use as thickeners and / or emulsifiers, for example for the production of cosmetic or pharmaceutical formulations. The inverse latex composition comprises from 50 to 80% by weight of at least one linear, branched or crosslinked organic polymer (P), from 5 to 10% by weight of a water-in-oil type emulsifier system, from 5 to 45% And 5% by weight or less of water. The polymer P comprises a neutral monomer and optionally a cationic or anionic monomer. The inverse latex composition may optionally comprise up to 5% by weight of an oil-in-water type emulsifier system. The inverse latex composition may be prepared by inverse emulsion polymerization.

EP-A 172 025 relates to a continuous liquid phase dispersion of an ethylenically unsaturated monomer comprising a hydrophobic group containing at least 8 carbon atoms and a polymer formed by the polymerization of ethylenically unsaturated monomers copolymerizable therewith. The dispersion is stable, essentially anhydrous, and comprises at least 40 weight percent polymer. During the polymerization, anionic monomers can be used, for example, as copolymerized, ethylenically unsaturated monomers. The polymerization can be carried out as an inverse emulsion polymerization.

EP-A 172 724 relates to a polymer prepared by copolymerizing a) an ethylenically unsaturated monomer comprising a hydrophobic group containing at least 8 carbon atoms and b) a water-soluble ethylenically unsaturated monomer. All of the above monomers are soluble in water as a mixture, and the polymer is prepared by inverse emulsion polymerization. The polymer particles have a dry size of < 4 탆. As monomer component b), acrylic acid in the form of anionic monomers such as free acid or water-soluble salts, and also nonionic monomers such as acrylamide can be used.

EP-A 172 723 relates to a process for flocculating a suspension using a water-soluble, inherently linear polymer having "single-point intrinsic viscosity" > The polymer is a copolymer of two or more ethylenically unsaturated monomers comprising at least 0.5% by weight of monomers containing hydrophobic groups. The polymer may also be a cationic polymer.

It is an object of the present invention to provide a novel thickener. This object is achieved by a thickener according to the invention comprising:

i) one or more polymers which can be prepared by the following polymerization

   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 one or more crosslinking agents,

   d) optionally one or more chain transfer agents,

ii) at least one activator,

The ratio of activator to polymer is > 10: 100 [wt% / weight%].

The thickeners according to the invention are characterized by their advantageous properties with respect to deposition, shear dilution, stabilization and / or viscosity (thickening). Deposition is understood to mean, for example, deposition on the fibers of the active component of the fabric softener during the cleaning operation. When applied to the present invention, this means that, for example, a thickener according to the present invention comprising at least one polymer (active ingredient) is present in the fabric softener and the fabric softener is used during or after the cleaning operation. The thickener according to the invention promotes the immersion of the active component to a great extent during or after such a cleaning operation. Particularly good properties with respect to deposition can be achieved when polymers based on one or more associative monomers, nonionic monomers such as acrylamide, and optionally neutral monomers based on anionic monomers are used.

When evaluating shear thinning, it is important that the thickener or the corresponding fabric softener is viscous and thick in its basic state, but diluted during stirring. Improved shear thinning has a positive effect on the life and properties of the pump during the production of the fabric softener, promotes a convenient amount of input to the consumer, and is particularly useful for residue-free use of the fabric softener in a cleaner, . The thickeners according to the invention improve the stability of the thickeners themselves and the corresponding formulations. Precipitation or creaming of particles is effectively prevented regardless of whether the particles are in the nanometer, micrometer or millimeter range. The contributing factor here is the advantageous yield point of the thickener according to the invention. Moreover, they have the advantage that any desired redispersion and enrichment are achieved very quickly.

A thickener according to the present invention having a mixture of two or more activators, one or more activators having a high HLB value and one or more activators having a low HLB value has an additional advantage. The combination of such an activator mixture with a polymer comprising one or more ethylenically unsaturated associative monomer building blocks can be achieved by diluting the thickener with water, for example, in the form of agitation, without spontaneous addition of energy, .

In addition, in the case of thickeners according to the invention, it is advantageous that the proportion of associative monomer to total polymer is relatively low. When using a thickener in a surfactant-containing formulation, the effect of the associative monomer is optimal in an amount of about 0.5 wt.% (Based on the polymer).

When a thickener according to the present invention is prepared by inverse emulsion polymerization in which the temperature is kept constant above 40 ° C, a very uniform distribution of the associative monomer building blocks in the polymer can be observed. Particularly when using small amounts, for example from 0.1 to 1% by weight, of associative monomers, this is advantageous with regard to the overall flow properties such as enrichment, shear dilution, stabilization and also the cleaning and rinsing effects.

Embodiments of the present invention in which the polymer present in the thickener is prepared with little or no cross-linking agent are likewise associated with these. Because of the relatively high (water-) soluble component of the polymer, recontamination during the cleaning operation is reduced. As a result, the article to be cleaned has clean fibers with dirt particles effectively removed even after repeated washing steps, which means that no graying is detected. No adherence and / or redistribution of dust particles / polymer to the cleaned article is observed at all or very little is observed.

In the context of the present invention, for example, a definition such as C ₁ -C ₃₀ -alkyl, as defined for the radical R ₉ in the formula (I) below, means that such a substituent (radical) Radical. &Lt; / RTI &gt; Alkyl radicals may be linear or branched and optionally also cyclic. Alkyl radicals having both cyclic and linear components are likewise included in this definition. The same applies to other alkyl radicals such as, for example, C ₁ -C ₄ -alkyl radicals or C ₁₆ -C ₂₂ -alkyl radicals. The alkyl radicals can optionally also be mono- or polysubstituted with functional groups such as amino, quaternary ammonium, hydroxy, halogen, aryl or heteroaryl. Unless otherwise stated, the alkyl radical preferably does not have a functional group as a substituent. Examples of alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-ethylhexyl, tert-Bu / t-Bu, cyclohexyl, Behenyl.

The present invention is described more fully below.

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

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

When one or more anionic monomers are 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.

When one or more nonionic monomers are present in component a), in addition to the nitrogen-containing monomers described below, for example the compounds according to formula (I), the esters of the abovementioned anionic monomers are also suitable as nonionic monomers Do. Such nonionic monomers are preferably methyl or ethyl esters of acrylic acid or methacrylic acid such as ethyl acrylate or methyl acrylate. Also suitable are the corresponding dimethylamino-substituted esters such as dimethylaminoethyl (meth) acrylate.

Preferably, the non-ionic monomer is selected from N-vinylpyrrolidone, N-vinylimidazole or a compound according to the formula (I)

[Wherein,

Alkyl, - R ₇ is H or C ₁ -C ₄

R &lt; ₈ &gt; is H or methyl,

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

The nonionic monomers are particularly preferably acrylamide, methacrylamide or dialkylaminoacrylamide.

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

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 one or more anionic monomers.

In addition, in the context of the present invention, it is preferred that component a) does not comprise a cationic monomer.

As component b), one or more ethylenically unsaturated associative monomers are used in the polymerization for polymer production. The associative monomers themselves are known to those skilled in the art. Suitable associative monomers are described, for example, in WO 2009/019225. The associative monomer is also referred to as a surfactant monomer.

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

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

[Wherein,

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

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

R "is H or methyl,

n is an integer from 0 to 100, preferably from 3 to 50, in particular from 25;

As component b), it is particularly preferred to use a compound according to formula (II) as follows:

Alkyl, - R is a C ₁₆ -C ₂₂

R 'is H,

R "is H or methyl,

n is 25.

Compounds according to formula (II) are commercially available as solutions, for example under the name Plex 6954 O from Evonik Rohm GmbH. These are methacrylates of fatty alcohol ethoxylates, such as the commercially available Lutensol ^® AT 25 (BASF SE, Ludwigshafen, Germany).

In compounds according to formula (II), the radical R may also be present as a mixture of radicals of different chain lengths, such as C ₁₆ and C ₁₈ . One example of this is the C ₁₆ -C ₁₈ -fatty alcohol (ethylene glycol) ₂₅ -ether methacrylate, wherein both the C ₁₆ and C ₁₈ fatty alcohol radicals are present in admixture (in a negligible amount). In contrast, for example, in compound behenyl-25 methacrylate (according to formula (II)) and cetyl-25 methacrylate, each radical R is not present as a mixture and is present as a C ₂₂ or C ₁₆ chain exist. Other chain lengths exist only in impurity form. The number "25" in the compound according to the formula (II) represents the size of the variable n.

In the preparation of the polymer by polymerization, one or more cross-linking agents may optionally be present as component c). Suitable cross-linking agents are known to those skilled in the art. Preferably, in the polymer, the crosslinking agent according to component c) is divinyl benzene; Tetraallylammonium chloride; Allyl acrylate; Allyl methacrylate; Diacrylates and dimethacrylates of glycols or polyglycols; butadiene; 1,7-octadiene, allylacrylamide or allylmethacrylamide; Bis acrylamidoacetic acid; N, N'-methylenebisacrylamide or polyol polyallyl ethers such as polyallyl sucrose or pentaerythritol triallyl ether. Also suitable as preferred crosslinking agents are dialkyldimethylammonium chloride.

In addition, during the preparation of the polymer by polymerization, one or more chain transfer agents can be used as component d). 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 thickeners according to the invention comprising polymers or one or more polymers and also any additives or adjuvants used in the polymerization or thickener production process are defined in more detail below.

Preferably, in the thickener according to the present invention, there is at least one polymer which can be prepared by the following polymerization

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

b) from 0.01 to 80% by weight, preferably from 0.05 to 5% by weight, particularly preferably from 0.1 to 1% by weight (based on the polymer) of one or more ethylenically unsaturated associative monomers,

c) 0 to 0.3% by weight, preferably 0.01 to 0.1% by weight (based on the polymer) of one or more crosslinking agents,

d) 0 to 0.3% by weight, preferably 0.01 to 0.1% by weight (based on the polymer) of one or more chain transfer agents.

In a further embodiment of the invention, the water soluble fraction of the polymer is greater than 25% by weight (based on the total weight of the polymer), particularly when little or no cross-linking agent is used in addition to the associative monomer. Preferably, more than 40% by weight, in particular 70 to 100% by weight, of the polymer is soluble in water. The solubility of the polymer is determined by a method known to the person skilled in the art by mixing the polymer present in the thickener according to the invention with water in the prescribed amount (for example EP-A 343 840 or preferably P. Schuck, " Size distribution analysis of macromolecules by sedimentation velocity ultracentrifugation and Lamm equation modeling, Biophysical Journal 78, (3) (2000), 1606-1619).

Preferably, in this embodiment, the fraction of the cross-linking agent (component c)) used in the polymerization of the polymer is < 10 wt% (based on the total amount of components a) to d). It is particularly preferable that the crosslinking agent is not used in the polymerization of the polymer.

The thickener according to the invention furthermore comprises as component ii) at least one activator. The activating agent itself is known to the person skilled in the art.

Suitable activating agents are preferably surfactants, for example anionic, nonionic, cationic and / or amphoteric surfactants, for example as disclosed in WO 2009/019225. It is preferred to use anionic and / or nonionic surfactants.

The nonionic surfactant used is preferably a fatty alcohol alkoxylate. Fatty alcohol alkoxylates are also referred to as polyalkylene glycol ethers. Preferred fatty alcohol alkoxylates are those which are preferably alkoxylated, advantageously ethoxylated, in particular from 1 to 12 mol of ethylene oxide (EO) per mole of alcohol and from a primary alcohol having from 8 to 18 carbon atoms In which the alcohol radical may be linear or branched, preferably 2-methyl-branched, or may comprise linear and methyl-branched radicals, as is customary in oxoalcohol radicals. However, it has been found that an average of from 2 to 8 EO per mole of alcohol and a linear from an alcohol of natural or technological origin having from 12 to 18 carbon atoms, for example from coconut alcohol, palmalcohol, tallow fatty alcohol or oleyl alcohol Particular preference is given to alcohol ethoxylates having radicals or mixtures, for example from castor oil. Preferred ethoxylated alcohols are, for example, C ₁₂ -C ₁₄ -alcohols of 3 EO, 4 EO or 7 EO, C ₉ -C ₁₁ -alcohols of 7 EO, 3 EO, 5 EO, 7 EO or 8 EO the C ₁₃ -C ₁₅ - alcohol, 3 EO, 5 EO or 7 EO of C ₁₂ -C ₁₈ - C ₁₂ -C ₁₄ alcohol and mixtures thereof, for example 3 EO - C ₁₂ -C ₁₈ alcohol and 7 EO - a mixture of alcohols. The degree of ethoxylation referred to is a statistical average value, and may be an integer or fraction for a particular product. Preferred alcohol ethoxylates have a narrowed homologous distribution (narrow range ethoxylate, NRE). In addition to these nonionic surfactants, fatty alcohols in excess of 12 EO may also be used. Examples thereof are tallow fatty alcohols of 14 EO, 25 EO, 30 EO or 40 EO. It is also possible to use non-ionic surfactants containing EO and PO groups in the molecule. Here it is possible to use block copolymers with EO-PO block units or PO-EO block units, as well as EO-PO-EO copolymers or PO-EO-PO copolymers. It is of course also possible to use a mixed alkoxylated nonionic surfactant in which the EO and PO units are not blockwise but randomly distributed. Such products are obtainable by the simultaneous action of ethylene oxide and propylene oxide on fatty alcohols.

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

For example, an alkyl glycoside of the following general formula (1) may be used:

R ¹ O (G) _x (1)

Wherein R ¹ is a primary straight or methyl-branched, especially 2-methyl-branched, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms, G is a glycoside of 5 or 6 carbon atoms, And oligomerization x, which specifies the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; Preferably, x is 1.2 to 1.4.

A further class of preferred nonionic surfactants used as the sole nonionic surfactant or in combination with other nonionic surfactants is preferably an alkoxylated, preferably alkoxylated, alkyl of 1 to 4 carbon atoms in the alkyl chain Ethoxylated and propoxylated fatty acid alkyl esters, especially fatty acid methyl esters, such as those described in Japanese Patent Application JP 58/217598, or preferably those described in International Patent Application WO-A-90/13533 And the like.

Nonionic interfaces 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 Active agents may also be suitable. The amount of these nonionic surfactants is preferably less than or equal to the amount of ethoxylated fatty alcohol, especially less than half of its amount.

A further suitable surfactant is a polyhydroxy fatty acid amide of the formula (2)

Wherein, R ² C (= O) is an aliphatic acyl radical having a carbon number of 6 ~ 22, R ³ is hydrogen, alkyl or hydroxy alkyl radical of carbon number 1 ~ 4, [Z] is a 3 to 10 carbon atoms and hydroxy Is a linear or branched polyhydroxyalkyl radical having from 3 to 10 radicals. Polyhydroxy fatty acid amides are known materials that can be obtained by reductive amination of reducing sugars, typically by ammonia, alkylamine or alkanolamine, and subsequent acylation with fatty acids, fatty acid alkyl esters or fatty acid chlorides.

The group of the polyhydroxy fatty acid amide also includes a compound of the formula (3)

Wherein R ⁴ is a linear or branched alkyl 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 an arylene radical having 6 to 8 carbon atoms , R ⁶ is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical of 1 to 8 carbon atoms, wherein C ₁ -C ₄ -alkyl or phenyl radicals are preferred, and [Z] ¹ is an alkyl chain A linear polyhydroxyalkyl radical substituted with at least two hydroxy groups, or an alkoxylated, preferably ethoxylated or propoxylated derivative of such a radical. [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 compound is then reacted with a fatty acid methyl ester in the presence of an alkoxide, for example as a catalyst according to WO-A-95/07331, Lt; / RTI &gt; fatty acid amides.

The anionic surfactants used are, for example, sulfonate and sulfate types. Suitable surfactants of the sulfonate type here are alkylbenzenesulfonates, preferably C ₉ -C ₁₃ -alkylbenzenesulfonates, olefin sulfonates, that is mixtures of alkene- and hydroxyalkanesulfonates, and also disulfonates , Which is obtained, for example, by subsequent alkaline or acidic hydrolysis of sulfonated and sulfonated products with gaseous sulfur trioxide from C ₁₂ -C ₁₈ -monoolefins having terminal or internal double bonds. Also suitable are alkanesulfonates, preferably secondary alkanesulfonates, which are obtained, for example, from C ₁₂ -C ₁₈ -alkanes by sulfolatination or sulfoxidation and subsequent hydrolysis or neutralization. The esters of alpha -sulfo fatty acids (ester sulphonates), such as hydrogenated coconut fatty acids, palm kernel fatty acids or alpha-sulfonated methyl esters of tallow fatty acids, are likewise suitable.

Further suitable anionic surfactants are fatty acid glycerol esters which are sulfated. Fatty acid glycerol esters are understood to mean mono-, di-, and triesters, and mixtures thereof, which are prepared by esterification of monoglycerol with 1 to 3 mol of fatty acid during manufacture such that triglycerides and 0.3-2 mol of glycerol trans Esterification. The preferred sulfated fatty acid glycerol esters herein are saturated fatty acids having from 6 to 22 carbon atoms such as caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid Lt; / RTI &gt;

Further suitable anionic surfactants are fatty alcohol sulphates, for example, alk (en) yl sulphate. Preferred alk (en) yl sulfates are C ₁₂ -C ₁₈ - fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, or C ₁₀ -C ₂₀ -oxoalcohols, and monoesters of secondary alcohols of these chain lengths, in particular the sodium salt. Further preferred are chain length alk (en) yl sulphates comprising synthetic straight-chain alkyl radicals based on petrochemical products having similar collapse behavior to equivalent compounds based on fatty chemical feedstocks. For cleaning techniques, C ₁₂ -C ₁₆ -alkyl sulfates and C ₁₂ -C ₁₅ -alkyl sulfates, and also C ₁₄ -C ₁₅ -alkyl sulfates, are preferred. Also, 2,3-alkyl sulfates, for example, which are produced according to U.S. Pat. No. 3,234,258 or 5,075,041 and obtainable as a product under the name DAN ^® from Shell Oil Company, are suitable anionic surfactants.

1 to 6 mol of a 2-methyl-branched C ₉ -C ₁₁ -alcohol having an ethylene oxydroethoxylated linear or branched C ₇ -C ₂₁ -alcohol such as an average of 3.5 mol of ethylene oxide (EO) or Sulfuric acid monoesters of C ₁₂ -C ₁₈ -fatty alcohols of 1 to 4 EO are also suitable.

Further suitable anionic surfactants are also the alkylsulfates, which are referred to as sulfosuccinates or sulfosuccinic acid esters, which are monoesters and / or diesters of sulfosuccinic acids and alcohols, preferably fatty alcohols, especially ethoxylated fatty alcohols It is a salt of succinic acid. A preferred sulfosuccinate is a C ₈ -C ₁₈ - fatty alcohol radicals or mixtures thereof. Particularly preferred sulfosuccinates include fatty alcohol radicals derived from ethoxylated fatty alcohols. In this regard, it is particularly preferred that the fatty alcohol radical is a sulfosuccinate derived from an ethoxylated fatty alcohol having a narrower homologous distribution. Likewise, it is also possible to use alk (en) succinic acid or a salt thereof having 8 to 18 carbon atoms in the alk (en) yl chain.

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

In the context of the present invention, the activator is preferably selected from fatty alcohol alkoxylates, alkyl glycosides, alkylcarboxylates, alkylbenzenesulfonates, secondary alkanesulfonates and fatty alcohol sulfates, particularly preferably Fatty alcohol alkoxylates. One example of a preferred fatty alcohol alkoxylate is C ₆ -C ₁₇ (secondary) -poly (3-6) ethoxylate.

In addition, in the context of the present invention, it is preferable to use a (relatively) high activating agent with an HLB value (hydrophilic-lipophilic balance value). Preferably, the activator has an HLB value of 7 to 18, more preferably 8 to 15, particularly preferably 9 to 13.

Activator the HLB value is high, preferably, i) having a carbon number of 12 to 18 second rate, and ii alkoxyl fatty alcohols Al formed from alcohols or mixtures of ethylene oxide or propylene oxide in alcohol) sucrose and C ₈ ~ _C22 -fatty alcohols. Examples of such activators are commercially available Synperonic 87K (from Croda GmbH, Herrenpfad-Sud 33, 41334 Nettetal, Germany); Croduret 40 or other ethoxylated hydrogenated castor oil (lycinus oil) such as Etocas 40 or Crodesta F110 (all from Croda).

In a further embodiment of the present invention, it is preferred to use a mixture of two or more activators, wherein at least one activator has a high HLB value and at least one activator has a low HLB value. The activator having a high HLB value preferably has an HLB value of > 12 to 20, and the activator having a low HLB value preferably has an HLB value of 1 to 12. [ In this embodiment, the activator with a high HLB value and the activator with a low HLB value may be present in any desired ratio known to one skilled in the art. Preferably, as the mixture, an activator having a high HLB value of 20 to 50 wt% and an activator having a low HLB value of 50 to 80 wt% are used. Further preferably, this ratio of activator with a high HLB value to that with a low HLB value is adjusted such that the overall HLB value is 7 to 18, more preferably 8 to 15, particularly preferably 9 to 13 .

In mixtures of two or more activators, a high HLB value is used an activator is preferably sucrose or sorbitan, and C ₈ ~ C ₂₂ - oligonucleotide alkyl glycoside or poly alkyl glycosides or polyalkyl based on fatty alcohols Ethylene oxide glycosides such as polyethylene glycol sorbitan monostearate or polyoxyethylene sorbitan monostearate. Examples of such activators are commercially available Crillet 1, Crillet 3 or Crodesta F160 (all available from Croda). A low HLB value activators, sucrose or sorbitan, and C ₈ ~ C ₂₂ - it is preferable to use the alkyl glycoside formed from fatty alcohols or fatty acids such as sorbitan monolaurate or sorbitan stearate. Examples of such activators are commercially available Crill 1, Crill 3 or Crodesta F10 (from Croda).

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

In the thickener according to the invention, in addition to the polymer and activator, additional components may also be present. Suitable further components are defined in more detail in the context of the manufacture of thickeners and polymers in the text below. Suitable further components are, for example, oils and solvents.

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

The present invention further provides a process for preparing a thickener according to the present invention. Methods of manufacturing thickeners themselves and methods of making polymers are known to those skilled in the art. Preferably, the polymer is obtained by emulsion polymerization, in particular by inverse emulsion polymerization. Preferably, the polymer is first prepared and, after polymerization, preferably by inverse emulsion polymerization, the activator is added to obtain a thickener.

The polymer may be prepared in various ways, preferably by emulsion polymerization, in particular by inverse emulsion polymerization. Inverse emulsion polymerization is understood by the person skilled in the art to mean a polymerization process generally as defined below: The hydrophilic monomers are dispersed in a hydrophobic phase. The polymerization takes place directly by the addition of an initiator in these hydrophilic monomer particles.

In addition, preferably, after the inverse emulsion polymerization and before the activator is added, at least some of the water and at least some of the low-cost components are distilled off from the oil phase, in particular using the LDP (liquid dispersion polymer) technique. LDP technology itself is known to those skilled in the art; For example in WO 2005/097834.

Unless otherwise stated, the following details are intended to include all types of emulsion polymerization, such as, for example, emulsion polymerization in water (which then also constitutes a continuous phase), and in particular inverse emulsion polymerization wherein the hydrophobic phase To form a continuous phase). Suitable polymerization initiators are used in the polymerization. Redox initiators and / or thermally activated free-radical polymerization initiators are preferred.

Suitable oxidative components of the thermally activated free-radical initiator or redox initiator pair are predominantly peroxy and azo types. These include, in particular, hydrogen peroxide, peracetic acid, t-butyl hydroperoxide, di-t-butyl peroxide, dibenzoyl peroxide, benzoyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5- , 5-bis (hydroperoxy) hexane, perbenzoic acid, t-butyl peroxypivalate, t-butyl peracetate, dilauryl peroxide, dicapriloyl peroxide, distearoyl peroxide, di Benzoyl peroxide, diisopropyl peroxydicarbonate, didecyl peroxydicarbonate, diescosuryl peroxydicarbonate, di-t-butyl perbenzoate, azobisisobutyronitrile, 2,2'- Azobis-2,4-dimethyl valeronitrile, ammonium persulfate, potassium persulfate, sodium persulfate and sodium perphosphate.

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

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

The emulsion polymerization is usually carried out at 35 to 100 占 폚. It may be carried out as a batch process or in the form of a feed process. In a feed procedure, at least a portion of the polymerization initiator and optionally a portion of the monomer are introduced as an initial charge and heated to the polymerization temperature, and the remainder of the polymerization mixture is subsequently passed through a plurality of separate feeds Of the feedstock comprise monomers in pure or emulsified form) and are introduced continuously or stepwise while maintaining the polymerization. Preferably, the monomer feed is carried out in the form of a monomer emulsion. In parallel with the monomer feed, additional polymerization initiators may be metered and introduced.

In a preferred embodiment, the total amount of initiator is introduced as an initial charge, i.e. no additional metering of the initiator is performed in parallel with the monomer feed.

In a preferred embodiment, therefore, the thermally activated free-radical polymerization initiator is all introduced as an initial charge, and the monomer mixture is preferably introduced in the form of a monomer emulsion. Prior to the start of the monomer mixture feed, the initial charge becomes the activation temperature or higher temperature of the thermally activated free-radical polymerization initiator. The activation temperature is considered to be the temperature at which more than half of the initiator decomposes after 1 hour at that temperature.

According to another preferred production process, the polymer is obtained by polymerization of the monomer mixture in the presence of a redox initiator system. The redox initiator system comprises at least one oxidizing agent component and at least one reducing agent component, wherein preferably a heavy metal ion such as a cerium salt, manganese salt or iron (II) salt is additionally present as catalyst in the reaction medium do.

Suitable oxidant components include, for example, peroxides and / or hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, pyranhydroperoxide, diisopropylphenyl hydroperoxide, dicyclohexyl Percarbonate perchlorate, dibenzoyl peroxide, dilauryl peroxide and diacetyl peroxide. Hydroperoxide and tert-butyl hydroperoxide are preferred.

Suitable reducing agent components include, but are not limited to, alkali metal sulfites, alkali metal dithionites, alkali metal hypophosphite, sodium hydrosulfite, Rongalit C (sodium formaldehyde sulfoxylate), mono- and dihydroxyacetone, Glucose or dextrose), ascorbic acid and its salts, acetone bisulfite adducts and / or alkali metal salts of hydroxymethanesulfinic acid, sodium hydrosulfite or sodium metabisulfite.

Also suitable as reducing agent components or catalysts are iron (II) salts such as iron (II) sulfate, tin (II) salts such as tin (II) chloride, Lt; / RTI &gt;

The amount of the oxidizing agent to be 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 amount of the reducing agent to be used is 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.

A particularly preferred redox initiator system is a sodium peroxodisulfate / sodium hydrosulfite system, for example 0.001-5.0 wt.% Sodium peroxodisulfate and 0.001-2.0 wt.% Sodium hydrosulfite, especially 0.005-1. 0 wt. % Sodium peroxodisulfate and 0.005-1. 0% sodium hydrosulfite, particularly preferably 0.01-0.5% sodium peroxodisulfate and 0.01-0. 5% sodium hydrosulfite.

Further particularly preferred redox initiator systems are t-butyl hydroperoxide / hydrogen peroxide / ascorbic acid systems, for example 0.001 to 5.0 wt.% T-butyl hydroperoxide, 0.001 to 5.0 wt.% Hydrogen peroxide and 0.001 to 2.0% by weight of ascorbic acid, in particular 0.005 to 1.0% by weight of t-butyl hydroperoxide, 0.005 to 1.0% by weight of hydrogen peroxide and 0.005 to 1.0% by weight of ascorbic acid, particularly preferably 0.01 to 0.5% % T-butyl hydroperoxide, 0.01-0.5 wt% hydrogen peroxide, and 0.01-0.5 wt% ascorbic acid.

Preferably, the polymer is prepared by inverse emulsion polymerization by first preparing the aqueous phase of the water soluble component and the oil phase separately therefrom. Subsequently, the two phases are mixed with each other to obtain a water dispersion. The mixture is polymerized by adding a redox initiator system; Optionally, a thermal initiator may then be added or, if it is already present, thermally activated.

In the aqueous phase, preferably chain transfer agents, crosslinking agents, anionic monomers and / or neutral monomers and optionally also associative monomers are present, and optionally further components are present. Suitable further components are, for example, complexing agents for salts such as pentasodium diethylene-triamine pentaacetic acid.

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

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

Typical emulsifiers include anionic emulsifiers such as sodium lauryl sulfate, sodium tridecyl ether sulfate, sodium salt of dioctyl sulfosuccinate sodium salt and alkylaryl polyether sulfonate; And nonionic emulsifiers such as, for example, alkylaryl polyether alcohols and ethylene oxide-propylene oxide copolymers. Sorbitan trioleates are likewise suitable as emulsifiers.

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,

n is an integer from 2 to 100;

Suitable stabilizers are described, for example, in EP-A 172 025 or EP-A 172 724. Preferred stabilizers are copolymers of stearyl methacrylate and methacrylic acid.

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

In a preferred embodiment of the invention, during inverse emulsion polymerization, component b) (one or more ethylenically unsaturated associative monomers) is added to the oil phase.

During inverse emulsion polymerization, the temperature may remain constant or increase. The temperature increase can be carried out continuously or stepwise. Thus, for example, the temperature during polymerization may increase by 0.2 to 10 DEG C per minute, preferably by 1 to 3 DEG C per minute. The temperature increase is controlled at the rate at which the initiator is added. The temperature starting value may be 0 to 30 캜, preferably 10 to 20 캜.

In another embodiment of the present invention, the temperature during the inverse emulsion polymerization is kept constant (cold procedure) and the temperature is 0-30 占 폚, preferably 10-20 占 폚. In a further embodiment of the present invention, the temperature remains constant over the higher temperature range (warm procedure). The temperature during the polymerization is from 40 to 150 캜, preferably from 70 to 120 캜.

In a particularly preferred embodiment of the present invention, the temperature is maintained constant during the inverse emulsion polymerization and the temperature is not lower than 40 캜, preferably between 50 and 90 캜.

In the context of the present invention, when the temperature is kept constant during the polymerization, in particular the inverse emulsion polymerization, this means that the temperature is maintained at a constant value from the beginning of the polymerization. Variations of +/- 5 [deg.] C, preferably +/- 2 [deg.] C, especially +/- 1 [deg.] C (based on the desired constant temperature value) during the polymerization process are considered constant. The temperature remains constant until polymerization is complete; Preferably, the temperature is kept constant until more than 90% by weight, more preferably more than 95% by weight of the monomers used are converted, particularly preferably completely converted (100% by weight). The temperature can be kept constant by dispersing the generated reaction heat by cooling. The polymerization is usually initiated by addition of a polymerization initiator, preferably by addition of a redox initiator system. Typically, the system is first heated to the desired temperature and a constant temperature is expected with stirring. Thereafter, a polymerization initiator is added, and as a result, the polymerization process is started. In embodiments of the present invention, the temperature is held constant at a temperature above the melting point of the associative monomer used.

The present invention also provides surfactant-containing acidic formulations comprising one or more thickeners according to the invention as defined above. The pH of the formulation is from 1 to < 7.

The present invention also provides surfactant-containing alkaline formulations comprising one or more thickeners according to the invention as defined above. The pH of the formulation is 7-13.

Surfactant-containing acidic or alkaline formulations according to the present invention may comprise additional ingredients known to those skilled in the art. Suitable ingredients include, but are not limited to, builders, bleaches, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH adjusters, fragrances, perfume carriers, fluorescent agents, dyes, hydrotropes ), Foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, wrinkle inhibitors, dye transfer inhibitors, antimicrobial active ingredients, , One or more substances from the group of fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, phobicization and impregnation agents, swelling and antislip agents, and UV absorbers .

The present invention also relates to a hair cosmetic composition comprising at least one compound selected from the group consisting of shampoos, softeners, care compositions, conditioners, skin creams, shower gels, laundry fabric softeners, Of an acidic cleaner according to the present invention.

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

The present invention also relates to a viscosity modifier for the optimization of shear thinning, as thickening agent for stabilization of suspension components of nanometer to millimeter size, and / or in surfactant-containing acidic or alkaline formulations, It provides usages.

In the specification including the embodiments, the following abbreviations are used:

Monomer

ACM acrylamide

AA Acrylic acid

MAA methacrylic acid

NaAc sodium acrylate

BEM Behenyl-25 methacrylate

MBA methylene bisacrylamide (crosslinking agent)

TAAC tetraallylammonium chloride (crosslinking agent)

NaHP sodium hypophosphite (chain transfer agent)

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

Etc

Based on the parts per hundred parts (components a) and b) of the pphm monomer,

you are. Desalted

The present invention will be described below with reference to examples.

Example

Comparative Example C1

Synthesis of thickeners / polymers starting from anionic monomers and not using associative monomers, but using cross-linking agents and chain transfer agents and also increasing the polymerization temperature.

The aqueous phase of the water-soluble components is prepared by mixing the following components:

250.24 g (139.02 pphm) of water,

0.89 g (0.49 pphm) of pentasodium diethylenetriamine pentaacetic acid,

11.05 g (0.06 pphm) of methylene bisacrylamide (1% in water),

180 g (100 pphm) of acrylic acid and

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

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

The oil phase is prepared by mixing the following ingredients:

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

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

Mineral oil (Kristol M14) with a low viscosity of 120.24 g (66.8 pphm) and

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

The two phases are mixed in a high shear at a ratio of 55.6 parts of aqueous phase to 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 atomization line, a stirrer and a thermometer. The emulsion is purged with nitrogen, resulting in the removal of oxygen and cooling to 20 占 폚.

The polymerization is achieved by adding an oxidation-reduction pair consisting of:

13 g (0.014 pphm) of sodium metabisulfite (0.2% in hydrotreated heavy naphtha (petroleum) [Isopar G]) and

13 g (0.014 pphm) tert-butyl hydroperoxide (0.2% in hydroheaded naphtha naphtha (petroleum) [Isopar G]).

Redox pairs are added stepwise to allow a temperature increase of 2 ° C / min to occur. When the isotherm is reached, the free radical initiator (2,2'-azobis (2-methylbutyronitrile), CAS: 13472-08-7) is added in two steps (45 min and then in the second step) Keep at 85 ° C for 75 minutes.

Vacuum distillation is used to remove low cost components of water and oil (Isopar G).

A low viscosity mineral oil (Kristol M14) is added to these products to achieve a solids content of 54%. To this product was added a fat-containing alcohol alkoxylate (C12 / 15 alcohol alkoxylate [Synperonic 87K ™]) of 8% (based on the total mass fraction of such product) to obtain a thickener Water). The ratio of activator to polymer is accordingly 16.0: 100 [wt% / wt%].

Example 1

Thickeners / polymers starting from anionic monomers, using associative monomers and a constant polymerization temperature:

Example 1.1

The aqueous phase of the water-soluble components is prepared by mixing the following components:

246.13 g (140.65 pphm) of water,

0.86 g (0.49 pphm) of pentasodium diethylenetriamine pentaacetic acid,

174.13 g (99.5 pphm) of acrylic acid and

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

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

The oil phase is prepared by mixing the following ingredients:

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

90.6 g (12.27 pphm) of a polymeric stabilizer: stearyl methacrylate-methacrylic acid copolymer (23.7% in the hydrotreated heavy naphtha [Isopar G]),

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

229.72 g (131.27 pphm) of a hydrotreated heavy naphtha [Isopar G]

1.09 g (0.5 pphm) of associative monomer: 60 wt% C16EO25Mac: Commodity Plex 6954-O (containing 20 wt% methacrylic acid, 20 wt% water).

The two phases are mixed in a high shear at a ratio of 55.6 parts of aqueous phase to 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 atomization line, a stirrer and a thermometer. The emulsion is heated to 50 DEG C while purging with nitrogen, resulting in the removal of oxygen.

The polymerization is achieved by adding an oxidation-reduction pair consisting of:

13.6 g (0.016 pphm) of sodium metabisulfite (0.2% in water) and

13.6 g (0.016 pphm) of tert-butyl hydroperoxide (0.2% in water).

The redox couple is added at 50 &lt; 0 &gt; C over 2 hours. The mixture was then heated to 85 ° C and then a free radical initiator (2,2'-azobis (2-methylbutyronitrile), CAS: 13472-08- 7) is added and the emulsion is maintained at 85 DEG C for 75 minutes.

Vacuum distillation is used to remove low cost components of water and oil (Isopar G).

A low viscosity mineral oil (Kristol M14) is added to these products to achieve a solids content of 54%. To this product was added a fat-containing alcohol alkoxylate (C12 / 15 alcohol alkoxylate [Synperonic 87K ™]) of 8% (based on the total mass fraction of such product) to obtain a thickener Water). The ratio of activator to polymer is accordingly 16.0: 100 [wt% / wt%].

The examples according to the following Table 1 are prepared as in Example 1.1, taking into consideration the changes in the monomer composition mentioned. The associative monomer C16EO25MAc is added to the oil phase. Uses goods Plex 6954 O; It contains 60% by weight of associative monomer and, as solvent, water and MAA in a ratio of about 1: 1. The weight data in Table 1 represents the amount of associative monomer except solvent. In all the examples according to Table 1 the ratio of activator to polymer is 16.0: 100 [wt% / wt%] in each case; Unless otherwise stated, each thickener (dispersion) has a 50% polymer solids fraction.

Table 1

Example 2

Thickeners / polymers starting from anionic monomers, using associative monomers and increasing the polymerization temperature:

The examples according to the following Table 2 are prepared as in Comparative Example C1, taking into consideration the changes in the above-mentioned monomer composition. The associative monomer C16EO25MAc is added to the oil phase. Uses goods Plex 6954 O; It contains 60% by weight of associative monomer and, as solvent, water and MAA in a ratio of about 1: 1. The weight data in Table 2 represents the amount of associative monomer except solvent. The ratio of activator to polymer in all examples according to Table 2 is 16.0: 100 [wt% / wt%] in each case; Unless otherwise stated, each thickener (dispersion) has a 50% polymer solids fraction.

Table 2

General measurement method:

Unless otherwise stated, the following general method of measurement is used in the following examples:

Measurement of viscosity

Considering the procedure according to DIN 51550, DIN 53018, DIN 53019, using a Brookfield model DV II viscometer (using spindle No. 6 at the rate of 20 revolutions per minute in the following table unless otherwise stated) Is measured in mPa * s.

Measurement of shear dilution

Measurements are made on an ASC (automatic sample changer) rotary flowmeter (Antonpaar, CC27 cylinder geometry, 13.33 mm radius of measuring body and 14.46 mm radius of measuring cup). The measurement temperature is 23 占 폚. The sample is started at low shear, increased to high shear (0.01 s ^-1 - 1000 s ^-1 ), returned to its original state (1000 s ^-1 - 0.01 s ^-1 ) and measured at steady state shear.

Example 3

Use of thickeners / polymers in water

The thickener is slowly added to distilled water according to Table 3 at room temperature and stirred until the formulation is homogenized. The resulting aqueous formulation comprises 1.0 wt.% Polymer to 99.0 wt.% Water or 0.5 wt.% Polymer to 99.5 wt.% Water, according to Table 3. The results are summarized in Table 3.

Table 3

Rheology of thickeners / polymers starting from anionic monomers in water, measured 5 minutes after the formulation is made

When an increasing amount of associative monomer is included in the polymer, the enrichment performance increases more and more significantly compared to C1 without using the associative monomer. The lower the starting temperature during the polymerization according to Example 2, the higher the enrichment performance. The procedure at a constant polymerization temperature of 50 캜 results in increased enrichment performance, if not for the same 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

Care composition formulation (P1) includes the ingredients listed in Table 4.1. P1 is prepared by heating phases A and B to 80 DEG C in each case. Thereafter, the two phases are combined and homogenized. Then, while stirring, the mixture is cooled to about 40 캜, phase C is added thereto, and the mixture is homogenized.

Table 4.1.1: Components of P1

Addition of thickening agent to Care composition Formulation P1:

The thickeners according to the invention listed in Table 4.1.2 or the thickeners according to the comparative examples are slowly added to the care composition formulation P1 at room temperature and stirred until the formulations are homogenized. The care composition formulations obtained in this way comprise the concentration (wt.%) Of thickener referred to the 100% by weight of the resulting care composition formulation.

The Brookfield viscosity is measured one day after manufacture. The results are summarized in Table 4.1.2.

Table 4.1.2: Thickener Performance and Shear Dilution in Care Compositions

Rheology of fabric softener containing thickener / polymer starting from anionic monomers:

When increasing amounts of associative monomers are included in the polymer, the enrichment performance increases more and more significantly compared to V1 without the associative monomer.

Example 4.2

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

W3: Preparation of methyl tris (hydroxyethyl) ammonium-di-tallow-fatty acid ester methosulfate, partially hydrogenated fabric softener (5.5% active fraction)

The fabric softener contains a methyl tris (hydroxyethyl) ammonium-de-tallow-fatty acid ester methosulfate (partially hydrogenated) and 94.5 wt% demineralized water at pH 2.7 and 5.5 wt%.

Addition of thickener to fabric softener formulation W3:

The thickeners according to Examples 1 and 2 and Comparative Example (see Table 4.2) are slowly added to the respective fabric softener formulations at room temperature and stirred until the formulations are homogenized.

The Brookfield viscosity is measured one day after manufacture. The results are summarized in Table 4.2.

Table 4.2. Thickener performance of fabric softener W3

Rheology of fabric softener containing thickener / polymer starting from neutral monomer:

When incorporating the associative monomer into the polymer, the enrichment performance increases more and more significantly than the comparative example without the associative monomer.

Example 5

In Table 5, the storage stability of the thickener according to the present invention is examined. The thickener according to the invention is found to be considerably more stable.

Table 5:

Storage stability of thickener / polymer starting from anionic monomers:

Significant improvement by the thickener according to the invention, namely reduction of settling.

Example 6

Storage stability of care composition formulation (P1) according to Example 4 comprising a thickener / polymer starting from anionic monomer:

Significant improvement by the thickener according to the invention, namely reduction of settling. After almost three months, significant sedimentation is apparent in formulations containing thickener V1, and only minimal sedimentation is apparent in formulations containing the thickener 2.1 (stored at RT).

Example 7

The effect of activator amount on thickening agent / polymer and aqueous formulation, starting from anionic monomers and using associative monomers:

Examples 7.1 to 7.5 listed in Table 6 were used to determine the amount of activator added after distillation according to Example 2.1, based on the activator concentration (A%) in the thickener given in Table 11 (all data indicate the amount of anionic polymer in the thickener By weight based on the weight of the base material). All thickeners (dispersions) produced in this manner have a polymer solids fraction of 50%. The thickener is then added to the water with stirring. The aqueous formulation obtained in this way contains 1% by weight of thickener to 99% by weight of water, i.e. 0.5% by weight of anionic polymer to 99.5% by weight of water. (Comparative) means a comparative example.

Table 6

When using associative monomers, an amount of activator in excess of 10% is required to achieve rapid enrichment performance (greater than 40% based on final enrichment within one minute).

Claims (20)

A thickener comprising:
i) one or more polymers which can be prepared by the following polymerization
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 one or more crosslinking agents,
d) optionally one or more chain transfer agents,
ii) at least one activator,
The ratio of activator to polymer is > 10: 100 [wt% / weight%]. The polymer of claim 1, wherein 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 a salt thereof, Acrylate. 3. A thickener as claimed in 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). 4. The polymer according to any one of claims 1 to 3, wherein in the polymer, component a) comprises at least one non-ionic monomer and the non-ionic monomer is selected from the group consisting of N-vinylpyrrolidone, N-vinylimidazole, 0.0 &gt; (I) &lt; / RTI &gt;

[Wherein,
Alkyl, - R ₇ is H or C ₁ -C ₄
R &lt; ₈ &gt; is H or methyl,
R ₉ and R ₁₀ are, independently of each other, H or C ₁ -C ₃₀ -alkyl. 5. A polymer according to any one of claims 1 to 4, wherein the ethylenically unsaturated associative monomer (component b) is selected from compounds according to formula (II): &lt; EMI ID =
RO- (CH ₂ -CHR'-O) _n -CO-CR "= CH ₂ (II)
[Wherein,
R is C ₆ -C ₅₀ -alkyl, preferably C ₈ -C ₃₀ -alkyl, especially C ₁₆ -C ₂₂ -alkyl,
Alkyl, preferably H, - R 'is H or C ₁ -C ₄
R "is H or methyl,
n is an integer from 0 to 100, preferably from 3 to 50, in particular from 25; 6. The polymer according to any one of claims 1 to 5, wherein the crosslinking agent (component c) is selected from the group consisting of:
Divinylbenzene; Tetraallylammonium chloride; Allyl acrylate; Allyl methacrylate; Diacrylates and dimethacrylates of glycols or polyglycols; butadiene; 1,7-octadiene, allylacrylamide or allylmethacrylamide; Bis acrylamidoacetic acid; N, N'-methylenebisacrylamide or polyols Polyallyl ethers such as polyallyl sucrose or pentaerythritol triallyl ether. 7. 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 hypophosphites. 8. The process according to any one of claims 1 to 7, wherein the activator is selected from fatty alcohol alkoxylates, alkyl glycosides, alkyl carboxylates, alkylbenzenesulfonates, secondary alkanesulfonates and fatty alcohol sulfates, Preferably a fatty alcohol alkoxylate. 9. The composition of any one of claims 1 to 8, wherein a mixture of at least two activators is used, wherein at least one activator has an HLB value (hydrophilic-lipophilic balance value) > Thickener with an HLB value of 1 to 12. 10. A thickener according to any one of claims 1 to 9, wherein the polymer is present in the form of an oil-in-water dispersion, preferably as an inverse dispersion, as a water-in-oil dispersion or as an anhydrous polymer dispersed in an oil. A process for the preparation of a thickener according to any one of claims 1 to 10, wherein the polymer is obtained by emulsion polymerization, in particular by inverse emulsion polymerization. 12. The method of claim 11, wherein after the inverse emulsion polymerization and before the activator is added, at least some of the water and at least some of the low-cost components are distilled off from the oil phase, in particular using LDP (liquid dispersion polymer) technology. 13. The process according to claim 11 or 12, wherein during inverse emulsion polymerization, component b) is added to the oil phase. 14. The method according to any one of claims 11 to 13, wherein the temperature is maintained or increased during the inverse emulsion polymerization. 15. The process according to any one of claims 11 to 14, wherein the temperature is kept constant during the inverse emulsion polymerization and is at least 40 DEG C, preferably from 50 to 90 DEG C. 10. A surfactant-containing acidic formulation comprising at least one thickener according to any one of claims 1 to 10 and having a pH of from 1 to < 7. In hair cosmetics, hair styling can be carried out in the styling of hair, as a shampoo, as a softener, as a care composition, as a conditioner, as a skin cream, as a shower gel, as a fabric softener for laundry, &Lt; / RTI &gt; The use of a surfactant-containing acidic formulation according to claim 16, 10. A surfactant-containing alkaline formulation comprising at least one thickener according to any one of claims 1 to 10 and having a pH of from 7 to 13. Use of a surfactant-containing alkaline formulation according to claim 18 as a care composition, as a liquid detergent or as a dishwashing detergent for machine wash or hand wash. 10. A viscosity modifier for optimizing shear thinning, as a thickener for stabilizing suspended components of nanometer to millimeter size and / or as surfactant-containing acidic or alkaline formulation in any one of claims 1 to 10 Use of thickeners according to paragraph.