EP1400583B1 - Liquid washing and cleaning agents with viscosity modifying polymers - Google Patents

Description

The present invention relates to liquid washing, cleaning, disinfecting and bleaching agents containing hydrophobically modified copolymers based on acryloyldimethyltaurine. The finished formulations are characterized by a favorable rheological behavior, as well as by a good compatibility with other components. They have a high storage stability, in particular high stability of hydrolysis-sensitive components, for example oxidizing agents in the formulations, preferably in acidic formulations and are UV stable.

High demands are placed on modern liquid detergents and disinfectants, which are closely linked to the rheology of the products: in addition to a good and rapid cleaning ability against dirt and grease or disinfecting power, they must be easy to use, safe, very well tolerated by the skin but also environmentally friendly be. In order to improve consumer handling and appearance, liquid products of higher viscosities are increasingly being marketed, so that thickeners and gelling agents play a major role.

As consistency regulator so far almost exclusively synthetic or partially synthetic polymers based on crosslinked polyacrylic acids (carbomers, carbopols), partly hydrolyzed polyacrylamides, cellulose ethers, xanthan or guar gum are used. There is always the problem of intolerance to low pH, which limits the potential applications of many technologies to the neutral or weakly acidic range.

Object of the present invention was therefore to find a thickener for washing and cleaning formulations, which does not lose its effectiveness in an acidic environment below pH 5.
Surprisingly, it has now been found that this serious disadvantage the use of hydrophobically modified copolymers based on Acrylolydimethyltaurat, the preparation of which is described in EP-A-1 069 142 and US 6,645,476, can be eliminated.

WO 0 244 230, WO 0 244 270 and WO 0 244 271 disclose compositions with acryloyldimethyltaurine acid.

With the help of these polymeric structures, it has been possible to adjust formulations for washing, cleaning and disinfecting to viscosities greater than 100 cP. In particular embodiments, they are formulations with an acid character (pH <5). Due to the acidic environment, it is also possible to permanently stabilize pH-sensitive oxidizing agents, such as hydrogen peroxide, thereby making them accessible to new applications in the cleaning and hygiene sector. Fortunately, these formulations are additionally characterized by a high UV stability. This allows the use of transparent packaging materials that are currently in great demand in the marketplace.

• a) Acryloyldimethyltaurinsäure in freier, teil- oder vollneutralisierter Form mit ein- oder zweiwertigen anorganischen oder organischen Kationen, und
• b) mindestens einem hydrophoben Comonomer auf Basis von ethylenisch ungesättigten Polyalkylenalkoxylaten, und gegebenenfalls
• c) weiteren, von a) und b) verschiedene, mindestens einfach vinylisch ungesättigten Comonomeren.

The invention relates to liquid washing, cleaning, disinfecting and bleaching agents having a pH of below 5, containing amphiphilic copolymers comprising structural units which are derived from

• a) Acryloyldimethyltaurinsäure in free, partially or fully neutralized form with monovalent or divalent inorganic or organic cations, and
• b) at least one hydrophobic comonomer based on ethylenically unsaturated polyalkylene alkoxylates, and optionally
• c) other comonomers which differ from a) and b) and are at least simply vinylically unsaturated.

Comonomers with more than one polymerizable unit lead to crosslinking of the structures according to the invention.

The copolymers according to the invention preferably have a molecular weight M _{w of} from 10 ³ g / mol to 10 ⁹ g / mol, more preferably from 10 ⁴ to 10 ⁷ g / mol, particularly preferably from 5 × 10 ⁴ to 5 × 10 ⁶ g / mol. M _w for the purposes of this invention is generally to be determined by GPC versus polystyrene sulfonic acid.

The acryloyldimethyltaurates (structural unit a) may be the inorganic or organic salts of acryloyldimethyltaurine acid. Preference is given to the Li ⁺ , Na ⁺ , K ⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Al ⁺⁺⁺ and / or NH ₄ ⁺ salts. Likewise preferred are the monoalkylammonium, dialkylammonium, trialkylammonium and / or tetraalkylammonium salts, where the alkyl substituents of the amines can independently of one another be (C ₁ -C ₂₂ ) -alkyl radicals which are optionally substituted by up to 3 (C ₂ -) C ₁₀ ) hydroxyalkyl groups may be occupied. Furthermore, one to three times ethoxylated ammonium compounds with different degrees of ethoxylation are preferred. It should be noted that mixtures of two or more of the above compounds are also within the scope of the invention.

The degree of neutralization of acryloyldimethyltaurine can be between 0 and 100%, particularly preferred is a degree of neutralization of above 80%.

Based on the total weight of the copolymers, the content of acryloyldimethyltaurine or acryloyldimethyltaurates may be from 0.1 to 99.9% by weight, preferably from 20 to 99.5% by weight, particularly preferably from 50 to 98% by weight.

According to the invention, at least one so-called macromonomer (structural unit b) is used in the copolymerization. The macromonomers are at least monoolefinically functionalized polymers having one or more discrete repeating units and a number average molecular weight greater than or equal to 200 g / mol. In the copolymerization, it is also possible to use mixtures of chemically different macromonomers b).

Based on the total mass of the copolymers, the content of macromonomers (structural unit b) may preferably be 0.1 to 99.9% by weight, in particular 0.5 to 80% by weight, particularly preferably 2 to 50% by weight.

Preferred as macromonomers b) are compounds according to formula (I).
R ¹ - Y - [(A) _v - (B) _w - (C) _x - (D) _z ] - R ² (I)

R ¹ represents a polymerizable function from the group of vinylically unsaturated compounds, which are suitable for the construction of polymeric structures by free radicals. Preferably, R ^{1 represents} a vinyl, allyl, methallyl, methylvinyl, acrylic, methacrylic, crotonyl, senecionyl, itaconyl, maleinyl, fumarylo or styryl radical.

To attach the polymer chain to the reactive end group, a suitable bridging group Y is required. Preferred bridges Y are -O-, -C (O) -, - C (O) -O-, -S-, -O-CH ₂ -CH (O -) - CH ₂ OH, -O-CH ₂ - CH (OH) -CH ₂ O-, -O-SO ₂ -O-, -O-SO-O-, -PH-, -P (CH ₃ ) -, -PO ₃ -, -NH- and -N (CH ₃ ) -, more preferably -O-.

The polymeric middle part of the macromonomer is represented by the discrete repeating units A, B, C and D. Preferred repeating units A, B, C and D are derived from acrylamide, methacrylamide, ethylene oxide, propylene oxide, AMPS, acrylic acid, methacrylic acid, methyl methacrylate, acrylonitrile, maleic acid, vinyl acetate, styrene, 1,3-butadiene, isoprene, isobutene, diethylacrylamide and diisopropylacrylamide , in particular of ethylene oxide and propylene oxide.
The indices v, w, x and z in formula (I) represent the stoichiometric coefficients relating to repeating units A, B, C and D. v, w, x and z are independently 0 to 500, preferably 1 to 30, wherein Sum of the four coefficients on average must be ≥1.

The distribution of repeating units across the macromonomer chain may be random, blocky, alternating or gradient-like.

R ^{2 represents} a linear or branched aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C ₁ -C ₅₀ ) -hydrocarbon radical, OH, -NH ₂ , -N (CH ₃ ) ₂ or is identical to the structural unit [-YR ¹ ]. In the case of R ² equal to [-YR ¹ ] are difunctional macromonomers, which are suitable for crosslinking of the copolymers.

Particularly preferred as macromonomers b) are acrylic or methacrylic monofunctionalized alkyl ethoxylates according to formula (II).

R ₃ , R ₄ , R ₅ and R ₆ independently of one another are hydrogen or n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C ₁ -C ₃₀ ) -hydrocarbon radicals.

R ₃ and R ₄ are preferably H or -CH ₃ , particularly preferably H. R ₅ is H or -CH ₃ , and R ₆ is equal to an n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic ( C ₁ -C ₃₀ ) hydrocarbon radical.

In turn, m and n are the stoichiometric coefficients concerning the ethylene oxide units (EO) and propylene oxide units (PO). m and n are independently 0 to 500, preferably 1 to 30, wherein the sum of m and n must be on average ≥1. The distribution of EO and PO units across the macromonomer chain can be random, block, alternating or gradient. Y stands for the bridges mentioned above.

Particularly preferred macromonomers have the following structure according to formula (II): description R ³ R ⁴ R ⁵ R ⁶ m n ^® LA-030 methacrylate H H -CH ₃ lauryl 3 0 LA-070 methacrylate H H -CH ₃ lauryl 7 0 LA-200 methacrylate H H -CH ₃ lauryl 20 0 LA-250 methacrylate H H -CH ₃ lauryl 25 0 T-080 methacrylate H H -CH ₃ -Tallow 8th 0 T-080 acrylate H H H -Tallow 8th 0 T-250 methacrylate H H -CH ₃ -Tallow 25 0 T-250-crotonate -CH ₃ H -CH ₃ -Tallow 25 0 OC-030 methacrylate H H -CH ₃ octyl 3 0 OC-105 methacrylate H H -CH ₃ octyl 10 5 Behenyl 010-metharyl H H H -Behenyl 10 0 Behenyl 020-metharyl H H H -Behenyl 20 0 Behenyl 010-senecionyl -CH ₃ -CH ₃ H -Behenyl 10 0 PEG-440 diacrylate H H H -Acrylic 10 0 B-11-50 methacrylate H H -CH ₃ butyl 17 13 MPEG-750 methacrylate H H -CH ₃ -Methyl 18 0 P-010-acrylate H H H phenyl 10 0 O-050-acrylate H H H -Oleyl 5 0

The molecular weight of the macromonomers b) is preferably 200 g / mol to 10 ⁶ g / mol, more preferably 150 to 10 ⁴ g / mol and particularly preferably 200 to 5000 g / mol.

As comonomers c) it is possible to use all olefinically unsaturated monomers whose reaction parameters permit copolymerization with acryloyldimethyltaurine acid and / or acryloyldimethyltaurates in the respective reaction media.

Preference is given to using open-chain N-vinylamides, preferably N-vinylformamide (VIFA), N-vinylmethylformamide, N-vinylmethylacetamide (VIMA) and N-vinylacetamide; cyclic N-vinylamides (N-vinyllactams) having a ring size of 3 to 9, preferably N-vinylpyrrolidone (NVP) and N-vinylcaprolactam; Amides of acrylic and methacrylic acid, preferably acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and N, N-diisopropylacrylamide; alkoxylated acrylic and methacrylamides, preferably hydroxyethyl methacrylate, hydroxymethyl methacrylamide, hydroxyethyl methacrylamide, hydroxypropyl methacrylamide and succinic acid mono [2- (methacryloyloxy) ethyl ester]; N, N-dimethylaminomethacrylate; diethylaminomethyl; Acrylic and methacrylamidoglycolic acid; 2- and 4-vinylpyridine; vinyl acetate; methacrylate; styrene; acrylonitrile; stearyl; Lauryl.

In addition, one or more unsaturated carboxylic acids or salts thereof can be copolymerized into the structure. Particularly preferred are acrylic acid, methacrylic acid, styrenesulfonic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and senecioic acid.

Preferred as counterions of the acids are Li ⁺ , Na ⁺ , K ⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Al ⁺⁺⁺ , NH ₄ ⁺ , monoalkylammonium, dialkylammonium, trialkylammonium and / or tetraalkylammonium radicals, it being the case with the Alkyl substituents of the amines independently of one another can be (C ₁ -C ₂₂ ) -alkyl radicals, which may optionally be occupied by up to 3 (C ₂ -C ₁₀ ) -hydroxyalkyl groups. In addition, it is also possible to use one to three times ethoxylated ammonium compounds having a different degree of ethoxylation. The degree of neutralization of the carboxylic acids can be between 0 and 100%.

In a further embodiment, the copolymers of the invention are crosslinked, i. they contain comonomers (structural unit c) with at least two polymerizable vinyl groups.

Preferred crosslinkers are methylenebisacrylamide; methylenebismethacrylamide; Esters of unsaturated mono- and polycarboxylic acids with polyols, preferably diacrylates and triacrylates or -methacrylates, more preferably butanediol and ethylene glycol diacrylate or methacrylate, trimethylolpropane triacrylate (TMPTA) and allyl compounds, preferably allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl ester, polyallylester, tetraallyloxyethane , Triallylamine, tetraallylethylenediamine; Allyl ester of phosphoric acid; and / or vinylphosphonic acid derivatives.
Particularly preferred crosslinkers are trimethylolpropane triacrylate (TMPTA) and timethylolpropane trimethacrylate (TMPTMA).

Mixtures of monounsaturated vinyl comonomers with multiple unsaturated comonomers (crosslinkers) are also according to the invention.

The proportion by weight of the comonomers (structural unit c), based on the total mass of the copolymers according to the invention, is preferably from 0.01 to 90% by weight, more preferably from 0.05 to 50% by weight and especially preferably from 0.1 to 40% by weight. -%.

The polymerization medium can be any organic or inorganic solvent which is largely inert with respect to radical polymerization reactions and advantageously allows the formation of medium or high molecular weights. Preference is given to using water, lower alcohols, preferably methanol, ethanol, propanols, iso-, sec- and t-butanol, particularly preferably t-butanol, hydrocarbons having 1 to 30 carbon atoms and mixtures of the abovementioned compounds.

The polymerization reaction is preferably carried out in the temperature range between 0 and 150 ° C, more preferably between 10 and 100 ° C, both at atmospheric pressure and under elevated or reduced pressure. Optionally, the polymerization can also be carried out under a protective gas atmosphere, preferably under nitrogen.

To initiate the polymerization, high-energy electromagnetic radiation, mechanical energy or the usual chemical polymerization initiators, such as organic peroxides, for example benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dilauroyl peroxide (DLP) or azo initiators, such as azodiisobutyronitrile (AIBN) can be used. Also suitable are inorganic peroxy compounds, such as (NH ₄ ) ₂ S ₂ O ₈ , K ₂ S ₂ O ₈ or H ₂ O ₂ , optionally in combination with reducing agents (eg sodium hydrogen sulfite, ascorbic acid, iron (II) sulfate, etc.) or redox systems containing as reducing component an aliphatic or aromatic sulfonic acid (eg benzenesulfonic acid, toluenesulfonic acid etc.).

The polymerization reaction can be carried out, for example, as precipitation polymerization, emulsion polymerization, bulk polymerization, solution polymerization or Gel polymerization led. Particularly advantageous for the property profile of the copolymers according to the invention is the precipitation polymerization, preferably in tert-butanol.

According to the invention, the hydrophobically modified copolymers based on acryloyldimethyltaurate described above can generally be used in all types of washing, cleaning, disinfecting and bleaching agents. They are preferably used as thickeners in acid detergent formulations for hard surfaces made of ceramic, metal, glass or plastic, for example in liquid all-purpose cleaners, in the sanitary sector, for example liquid toilet block, limesolvents bathroom cleaners, but also dishwashing detergents. Furthermore, they are suitable for use in stain removers, liquid detergents and laundry bleaches.

The washing, cleaning, disinfecting and bleaching agents according to the invention may be in the form of aqueous, aqueous / organic, in particular aqueous / alcoholic and organic formulations. Other embodiments may be: emulsions, dispersions, gels and suspensions.

In a preferred embodiment, the washing, cleaning, disinfecting and bleaching agents according to the invention contain an acidic component.
Suitable organic or inorganic acids, preferably organic acids, more preferably alpha-hydroxy acids and acids selected from glycolic, lactic, citric, tartaric, mandelic, salicylic, ascorbic, pyruvic, oligooxa mono- and dicarboxylic, fumaric, retinoic, aliphatic and organic Sulfonic acids, benzoic acid, kojic acid, fruit acid, malic acid, gluconic acid, galacturonic acid, acidic plant and / or fruit extracts and their derivatives.

Furthermore, preferred embodiments may contain oxidizing agents, in particular hydrogen peroxide or its addition compounds, for example the addition compounds of hydrogen peroxide with urea, melamine or sodium borate, or solutions of perborate or percarbonate optionally also contain caroate.

The preparations according to the invention may contain oxidizing agents in amounts of from 0.1 to 30% by weight, more preferably from 0.5 to 18% by weight, in particular from 1.5 to 9% by weight.

The washing, cleaning, disinfecting and bleaching agents according to the invention may contain surfactants of nonionic, anionic, cationic or amphoteric nature as well as customary auxiliaries and additives in varying amounts.

Preferred nonionic surfactants are fatty alcohol ethoxylates containing from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohols may be linear or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols containing an alkyl chain of 10 to 20 carbons with 2 to 18 moles of ethylene oxide per mole of alcohol. The alkyl chain can be saturated or unsaturated. Likewise, the alcohol ethoxylates may have a narrow homolog distribution of the ethylene oxide ("narrow range ethoxylates") or a broad homolog distribution of the ethylene oxide ("broad range ethoxylates"). Examples of commercially available nonionic surfactants of this type are Tergitol ™ 15-S-9 (condensation product of a C ₁₁ -C ₁₅ linear secondary alcohol with 9 moles of ethylene oxide), Tergitol ™ 24-L NMW (condensation product of a C ₁₂ -C ₁₄ linear primary Alcohol with 6 moles of ethylene oxide with narrow molecular weight distribution). Also included in this product class are the Genapol ™ brands from Clariant GmbH.

In addition, according to the invention, other known types of nonionic surfactants come into question, such as polyethylene, polypropylene and Polybutylenoxidaddukte of alkylphenols having 6 to 12 carbon atoms in the alkyl chain, addition products of ethylene oxide with a hydrophobic base, formed from the condensation of propylene oxide Propylene glycol or addition products of ethylene oxide with a reaction product of propylene oxide and ethylenediamine.

eingesetzt werden, worin R⁸ eine Alkyl-, Hydroxyalkyl- oder Alkylphenolgruppe oder Mischungen hiervon darstellt mit einer Kettenlänge von 8 bis 22 Kohlenstoffatome; R⁹ ist eine Alkylen- oder Hydroxyalkylengruppe mit 2 bis 3 Kohlenstoffatomen oder Mischungen hiervon; R¹⁰ ist eine Alkyl- oder Hydroxyalkylgruppe mit 1 bis 3 Kohlenstoffatomen oder eine Polyethylenoxidgruppe mit 1 bis 3 Ethylenoxideinheiten. Die R¹⁰/R⁹-Gruppen können miteinander über ein Sauerstoffoder Stickstoffatom verbunden sein und somit einen Ring bilden.
Diese Aminoxide umfassen besonders C₁₀-C₁₈-Alkyldimethylaminoxide und C₈-C₁₂-Alkoxyethyl-Dihydroxyethylaminoxide.Furthermore, semipolar nonionic surfactants, for example Amine oxides of the formula III

where R ^{8 is} an alkyl, hydroxyalkyl or alkylphenol group or mixtures thereof having a chain length of 8 to 22 carbon atoms; R ⁹ is an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures thereof; R ¹⁰ is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a polyethylene oxide group having 1 to 3 ethylene oxide units. The R ¹⁰ / R ⁹ groups may be linked together via an oxygen or nitrogen atom and thus form a ring.
These amine oxides particularly include C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₂ alkoxyethyl dihydroxyethyl amine oxides.

Instead of or in addition to the nonionic surfactants, the mixtures according to the invention may also contain anionic surfactants.

Suitable anionic surfactants are, in particular, straight-chain and branched alkyl sulfates, sulfonates, carboxylates, phosphates, alkyl ester sulfonates, arylalkyl sulfonates, alkyl ether sulfates and mixtures of the abovementioned compounds. In the following, some of the candidate types of anionic surfactants will be described in more detail.

Alkyl

Alkyl ester sulfonates are linear esters of C ₈ -C ₂₀ carboxylic acids (ie, fatty acids) that are sulfonated by SO ₃ , as described in The Journal of the American Oil Chemists Society, 52 (1975), pp. 323-329. Suitable starting materials are natural fatty derivatives, such as tallow or palm oil fatty acid.

alkyl sulfates

Alkyl sulfates are water-soluble salts or acids of the formula ROSO ₃ M, wherein R is preferably a C ₁₀ -C ₂₄ -hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical having 10 to 20 C-atoms, particularly preferably a C ₁₂ -C ₁₈ -alkyl or hydroxyalkyl radical , M is hydrogen or a cation, for example an alkali metal cation (eg sodium, potassium, lithium) or ammonium or substituted ammonium, for example a methyl, dimethyl and trimethylammonium cation or a quaternary ammonium cation, such as tetramethylammonium and dimethylpiperidinium cation and quaternary ammonium cations, derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof. Alkyl chains with C ₁₂ -C ₁₆ are preferred for low washing temperatures (eg below about 50 ° C) and alkyl chains with C ₁₆ -C ₁₈ preferably for higher washing temperatures (eg above about 50 ° C).

alkyl ether

The alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) _m SO ₃ M, where R is an unsubstituted C ₁₀ -C ₂₄ -alkyl or hydroxyalkyl radical having 10 to 24 C atoms, preferably a C ₁₂ -C ₂₀ -alkyl radical. or hydroxyalkyl radical, particularly preferably a C ₁₂ -C ₁₈ -alkyl or hydroxyalkyl radical. A is an ethoxy or propoxy moiety, m is a number greater than 0, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is a hydrogen atom or a cation such as for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium, or a substituted ammonium cation. Examples of substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Examples which may be mentioned are C ₁₂ -C ₁₈ -alkyl polyethoxylate (1.0) sulfate, C ₁₂ -C ₁₈ -alkyl polyethoxylate (2,25) sulfate, C ₁₂ -C ₁₈ -alkyl polyethoxylate (3.0 ) sulfate, C ₁₂ -C ₁₈ alkyl polyethoxylate (4.0) sulfate, wherein the cation is sodium or potassium.

Other anionic surfactants which are useful for use in detergents and cleaners are C ₈ -C ₂₄ -olefin sulfonates, sulfonated polycarboxylic acids, prepared by sulfonation of pyrolysis products of alkaline earth metal citrates such as described in British Patent GB 1,082,179, alkyl glycerol sulfates, fatty acyl glycerol sulfates, oleyl glycerol sulfates, alkyl phenol ether sulfates, primary paraffin sulfonates, alkyl phosphates, alkyl ether phosphates, isethionates such as acyl isethionates, N-acyl taurides, alkyl succinamates, sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₁₈ diesters), acyl sarcosinates, sulfates of alkyl polysaccharides such as sulfates of alkyloyl glycosides, branched primary alkyl sulfates and alkyl polyethoxycarboxylates such as those of the formula RO (cf. CH ₂ CH ₂ ) _k CH ₂ COO ^- M ⁺ wherein R is a C ₈ -C ₂₂ alkyl, k is a number from 0 to 10 and M is a soluble salt forming cation. Resin acids or hydrogenated resin acids such as rosin or hydrogenated rosin or tall oil resins and tall oil rosin acids are also useful. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II, Schwartz, Perry and Berch). A variety of such surfactants are also claimed in U.S. Patent 3,929,678.

Examples of amphoteric surfactants which can be used in the formulations of the present invention are, in particular, those which are broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be linear or branched and in which one of the aliphatic radicals Substituents between. Contains 8 to 18 carbon atoms and an anionic, water-soluble group, such as e.g. Carboxy, sulfonate, sulfate, phosphate or phosphonate contains.

Further preferred amphoteric surfactants are alkyl dimethyl betaines, alkyl amidobetaines and alkyl dipolyethoxy betaines having an alkyl radical which may be linear or branched, with. 8 to 22 carbon atoms, preferably having 8 to 18 carbon atoms and more preferably with. 12 to. 18 carbon atoms. These compounds are e.g. marketed by Clariant GmbH under the trade name Genagen® CAB.

Auxiliaries and additives

The washing and cleaning agents contain, depending on the application, in addition to the surfactants mentioned nor the specific auxiliaries and additives For example, builders, salts (electrolytes), bleaches, bleach activators, optical brighteners, complexing agents, grayness inhibitors, solubilizers, enzymes, thickeners, preservatives, fragrances and dyes, pearlescing agents, foam inhibitors, sequestering agents.

Suitable organic and inorganic builders are neutral or, in particular, alkaline salts which are able to precipitate or complex calcium ions. Suitable and in particular ecologically acceptable builder substances, such as fine-crystalline, synthetic hydrous zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g, find a preferred use. In non-aqueous systems, phyllosilicates are preferably used. Zeolite and the phyllosilicates may be present in an amount of up to 20 wt .-% on average. Useful organic builders are, for example, the percarboxylic acids preferably used in the form of their sodium salts, such as citric acid and nitriloacetate (NTA), ethylenediaminetetraacetic acid, if such use is not objectionable for ecological reasons. Analogously, it is also possible to use polymeric carboxylates and their salts. These include, for example, the salts of homopolymeric or copolymeric polyacrylates, polymethyacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those of 50% to 10% of maleic acid and also polyvinylpyrrolidone and urethanes. The molecular weight of the homopolymers is generally between 1000 and 100,000, those of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid, in particular water-soluble polyacrylates are suitable, for example, about 1% of a Polyallylethers of sucrose are cross-linked and have a molecular weight above one million. Examples of these are the polymers available under the name Carbopol 940 and 941. The crosslinked polyacrylates are used in amounts of not more than 1% by weight, preferably in amounts of from 0.2 to 0.7% by weight.

As electrolyte, the agents according to the invention contain salts. The salts are heteropolar compounds whose crystal lattice has at least one cation species other than hydrogen ions and at least one of hydroxide clays different anion species are involved. The agents according to the invention preferably contain inorganic salts, more preferably ammonium or metal salts, preferably halides, oxides, carbonates, bicarbonates, phosphates, sulfates, nitrates, most preferably sodium chloride; and / or organic salts, preferably ammonium or metal salts, preferably glycolic, lactic, citric, tartaric, mandelic, salicylic, ascorbic, pyruvic, fumaric, retinoic, sulfonic, benzoic, kojic, fruit, malic, gluconic, galacturonic.
The salts are preferably derived from mono- or polybasic acids and bases, preferably from monovalent acids and / or monovalent bases. Particularly preferred are sodium, potassium and ammonium salts.
As electrolyte, the agents may also contain mixtures of different salts. The agents usually contain the electrolytes in a concentration of from 0.01 to 50% by weight, preferably from 0.1 to 50% by weight, particularly preferably from 0.5 to 10% by weight.

The compositions according to the invention may contain, as foam inhibitors, fatty acid alkyl ester alkoxylates, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica. Advantageously, mixtures of various foam inhibitors may also be used, e.g. those made of silicone oil, paraffin oil or waxes. Preferably, foam inhibitors are bound to a granular, water-soluble or dispersible carrier substance.

The liquid detergents may contain optical brighteners, for example derivatives of diaminostilbenedisulfonic acid or their alkali metal salts, which can be incorporated well into the dispersion. The maximum content of brighteners in the compositions according to the invention is 0.5% by weight, preferably amounts of 0.02 to 0.25% by weight are used.

The desired viscosity of the agents can be adjusted by adding water and / or organic solvents or by adding a combination of organic solvents and other thickening agents.

In principle, all mono- or polyhydric alcohols are suitable as organic solvents. Alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, propanol, isopropanol, straight-chain and branched butanol, glycerol and mixtures of the alcohols mentioned are preferably used. More preferred alcohols are polyethylene glycols having a molecular weight less than 2,000. In particular, use of polyethylene glycol having a molecular weight of between 200 and 600 and up to 45% by weight and polyethylene glycol having a molecular weight of between 400 and 600 in amounts of 5 to 25 wt .-% preferred. An advantageous mixture of solvents consists of monomeric alcohol, for example ethanol and polyethylene glycol in a ratio of 0.5: 1 to 1.2: 1, wherein the liquid detergent according to the invention may contain 8 to 12 wt .-% of such a mixture. Other suitable solvents include triacetin (glycerol triacetate) and 1-methoxy-2-propanol.
Preferred thickeners are hardened castor oil, salts of long-chain fatty acids, preferably in amounts of from 0 to 5% by weight and in particular in amounts of from 0.5 to 2% by weight, for example sodium. Potassium, aluminum, magnesium and titanium stearates or the sodium and / or potassium salts of behenic acid, as well as polysaccharides, in particular xanthan gum, guar guar, agar agar, alginates and tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, and also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone.

Suitable enzymes are those from the class of proteases, lipases, amylases or mixtures thereof. Their proportion can be 0.2 to 1 wt .-%. The enzymes can be adsorbed to carrier substances and / or embedded in encapsulating substances.

In order to bind traces of heavy metals, the salts of polyphosphoric acids, such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepentamethylenephosphonic acid (DTPMP), preferably in amounts by weight of 0.1 to 1.0 wt% can be used.

Suitable preservatives are, for example, phenoxyethanol, Formaldehyde solution, parabens, pentanediol or sorbic acid.

Suitable pearlescing agents are, for example, glycol distearate esters, such as ethylene glycol distearate, but also fatty acid monoglycol esters.

As salts or adjusting agents, for example, sodium sulfate, sodium carbonate or sodium silicate (water glass) are used.
Typical individual examples of further additives include sodium borate, starch, sucrose, polydextrose, stilbene compounds, methylcellulose, toluenesulfonate, cumene sulfonate, soaps and silicones.

The agents according to the invention are customarily adjusted to a pH in the range from 2 to 12, preferably from pH 2.1 to 7.8, more preferably from 2.2 to 6.5.

By using hydrophobically modified acryloyldimethyltaurate-containing copolymers, it was possible to thicken formulations with a pH of <5 to viscosities above 100 mPas. On the one hand, these formulations have the advantage that the viscosification prevents "spattering" of the cleaning agent and thereby ensures safer use. In addition, the increased viscosity ensures a slower expiration of the cleaner from the surfaces and thus guarantees a longer exposure time. Due to the broad pH tolerance of the polymers used it is now possible to use stronger organic acids such as citric acid, malic acid, alpha-hydroxycarboxylic acids and oxalic acid in free form. An improved effectiveness especially against limescale can be achieved.

In the said formulations hydrophobically modified acryloyldimethyltaurate-containing copolymers are used in an amount of 0.01 to 10 wt .-%. Preference is given to working with an amount of 0.1 to 5 wt .-%. Particularly preferred is the range of 0.2 to 2 wt .-%. Depending on the amount of polymer used, the viscosity of the resulting gels can be between 100 and 100,000 mPas.

Liquid cleansing gels containing water / organic solvent mixtures The thickening of organic solvents, especially alcohols, in combination with anionic and nonionic surfactants and other formulation ingredients is easily possible through the use of hydrophobically modified acryloyldimethyltaurate-containing copolymers. By way of limitation, it should be noted that only water-compatible organic solvents are within the meaning of the invention. Non-limiting examples can be mentioned ethanol, propanol, isopropanol, DMSO, NMP, acetone, methanol and butanol. The resulting gels may contain between 0.1 and 90% by weight of organic solvent. Preference is given to a proportion of 5 to 80 wt .-%. Particularly preferred are gels having a content of organic solvents of 20 to 60 wt .-%. In general, copolymers containing hydrophobically modified acryloyldimethyltaurate are used in these formulations in an amount of from 0.01 to 10% by weight. Preference is given to working with an amount of 0.1 to 5 wt .-%. Particularly preferred is the range of 0.2 to 2 wt .-%. The viscosities of the resulting cleaner gels containing organic solvents may vary between 100 and 100,000 mPas, depending on the amount of polymer used.

The field of application here too can be the cleaning of "hard-encrusted" hard surfaces such as tiles, glass or ceramic or metal. Possible fields of use according to the invention are, for example, bathroom cleaners, glass cleaners, and floor cleaners.

Liquid cleaning gels containing disinfectants

Disinfection gels play a major role in the hygiene sector and have been enjoying increasing obesity on the market for some years now. Especially gels in use as "liquid toilet blocks" have been on the rise in sanitation for years.

The thickening of aqueous disinfectant solutions by conventional thickeners based on cellulose ethers or polyacrylic acids sometimes requires a high use concentration of these polymers and is also limited to the neutral to weakly acidic pH range.

By using hydrophobically modified acryloyldimethyltaurate-containing copolymers, this limitation can be eliminated. For the first time, it is possible to combine cleaning gels containing liquid disinfectants with acidic formulation constituents, such as fruit acid or alpha-hydroxycarboxylic acids, and thus, in addition to the antiseptic, also to achieve a "lime-dissolving" effect.

In the said formulations, hydrophobically modified copolymers containing acryloyldimethyltaurate are used in an amount of from 0.01 to 10% by weight. Preference is given to working with an amount of 0.1 to 5 wt .-%. Particularly preferred is the range of 0.2 to 2 wt .-%. Depending on the amount of polymer used, the viscosity of the resulting gels can be between 100 and 100,000 mPas.
Thickening of acid peroxide-containing solutions with hydrophobically modified acryloyldimethyltaurate polymers

For liquid formulations of peroxide solutions, it is desirable to thicken them. This simplifies handling and makes it safer. Formulations according to the invention may contain organic or inorganic peroxides, in particular hydrogen peroxide or a mixture thereof. In various applications, it is desirable that the peroxide solutions adhere to the substrate rather than draining so that the effect can be fully deployed. However, solutions of peroxide with conventional thickeners are difficult to thicken or stabilize over an extended period of time. The reason lies in the fact that a hydrogen peroxide solution is already comparatively unstable at neutral or only slightly acidic pH values. In the decay, the thickeners are attacked and the viscosity decreases over time greatly. In addition, there is a significant loss of hydrogen peroxide activity. At acidic pH levels, the decomposition of hydrogen peroxide is greatly retarded, but the thickening performance of acrylic acid thickeners breaks down at pH values <5.5.
The use of hydrophobically modified acryloyldimethyltaurate polymers according to the invention in bleaching solutions thickens the formulation, even at pH values well below the threshold value of pH 5. Die Thickening performance of the polymers of the invention remains almost constant at a pH value interval of 1.5 to 9. Therefore, with the thickeners according to the invention, even formulations with pH values around pH 2 are accessible. In this pH range, no appreciable decomposition of H2O2 takes place over normal storage periods, with the result that the hydrophobically modified acryloyldimethyltaurate polymers according to the invention are not attacked and destroyed and thus the viscosity of the formulation according to the invention remains virtually constant.
In the following, to illustrate the invention, some non-limiting applications of such acidic thickened hydrogen peroxide solutions are shown:

Bleaching solutions eg for cleaning laundry (liquid stain salt) or dishes:
A solution of 0.1 to 30% ww H ₂ O ₂ , preferably from 1 to 15% ww, particularly preferably from 3 to 10% ww can be thickened by means of inventive hydrophobically modified acryloyldimethyltaurate polymers at pH values <5. Even at elevated storage temperatures, a stable viscosity over months is found. The thickening of the bleaching solution makes it easier for the user to set the optimal dosage. The solution does not splash and the handling is safer.

Peroxide-containing cleaners can, for. B. in the field of cleaning hard surfaces in the sanitary or sanitary area. In this case, formulations can be prepared which also contain anionic and nonionic surfactants. Very useful are such means, for example for the cleaning of toilets. The peroxide-based cleaner adheres to the ceramic and can thus unfold its cleaning and disinfecting effect optimally.

Gel or liquid filled permanent cleaners (liquid toilet stones) for hanging in the cistern or the toilet bowl can be realized with a similar formulation. Part of the gel-like thickened solution is distributed with each rinse with the flow of water in the basin and thus ensures a cleansing and disinfecting effect. With the hydrophobically modified acryloyldimethytaurate polymers according to the invention, clear formulations are obtainable which are suitable for the Today's trend for clear formulations and transparent packaging.

The following examples and applications are intended to illustrate the invention without, however, limiting it to it (all percentages are by weight).

Polymer A is poly [acryloyldimethyltauric acid ammonium salt-co-Genapol T-250 methacrylate-co-trimethylolpropane trimethacrylate], Mw 570,000 g / mol.

Polymer B is poly [acryloyldimethyltaurate sodium salt co-Genapol 070 acrylate], Mw 1,000,000 g / mol.

Polymer C is poly [acryloyldimethyltauric acid ammonium salt-co-vinylformamide-co-MPEG 750-methacrylate-co-trimethylolpropane triacrylate], Mw 1,500,000 g / mol.

Liquid cleaning gels with pH <5 for hard surfaces

All formulations additionally contain, as needed, preservative, dye and / or perfume.

1. Formulation Liquid Bleach Booster (liquid stain salts)

1.5% Linear alkyl benzene sulphonate 2.5% Genapol OA 070 6.6% H ₂ O ₂ 0.2% phosphonate 88.7% water 0.5% Polymer A pH (1 g / l) 4.3 2.2% lauryl sulfate 4.5% Genapol OA 070 7.0% H ₂ O ₂ 0.5% phosphonate 85.3% water 0.5% Polymer B pH (1g / l) 4.8 viscosity 300 mPas

Typical viscosities of highly concentrated formulations are in the range of 700 to 1000 mPas, typical viscosities of gels are in the range of 2000 to 3000 mPas.

Liquid Bleach Boosters are added to the washing machine in addition to the detergent to improve stain removal. They can also be applied directly to the fabric on the stain for pretreatment. The higher viscosity simulates a higher activity. With direct order, a more targeted application can also be made possible.

2. Formulation Hard Surface Cleaner Gel with Bleach

(not according to the invention) 6.7% Genapol UD 080 0.4% Soap 0.8% soda 6.2% H ₂ O ₂ 0.3% phosphonate 85.2% water 0.4% Polymer A pH (1 g / l) 5.0 viscosity 250 mPas

3. Formulation rinse aid gel for automatic dishwashing

14.0% Genapol 2909 3.0% citric acid 5.0%. Cumolsulphonat 77.5% water 0.5% Polymer C pH (1 g / l) 2.8 viscosity 2000 mPas

4. Formulation Machine Dishwashing Gel

(not according to the invention) 1.0% Genapol 2544 2.1% soda 32.9% Citrate / citric acid 0.3% Monopropylenglykol 0.5% Polymer A 63.2% water pH (1 g / l) 5.9 viscosity 7 mPas

5. Formulation of acid bath cleanser

1.7% Hostapur SAS 60 4.0% Genapol UD 080 2.0% Sokalan CP 45 0.5% propylene glycol 0.3% lactic acid 2% Polymer A 89.6% water pH (1 g / l) 3.3 viscosity 500 mPas 4.4% lauryl sulfate 1.4% Soap 3.9% Genaminox LA 9.8% Citrate / Citonensäure 3.3% propylene glycol 0.45% Polymer C 76.75% water pH (1 g / l) 3.7 viscosity <3000 mPas 2.3% Sandosan LNBA 2.5% Genapol UD 080 2.0% propylene glycol 2% Polymer B 91.2% water pH (1 g / l) 3.3 viscosity > 2000 mPas

6. Formulation acidic cleaner (clear)

6.5% Hostapur SAS 60 1.8% Genapol LA 070 18.0% citric acid 2.4% sodium chloride 1 % Polymer A 71.3% water pH (1 g / l) 2.0 viscosity > 2000 mPas

This formulation would need to be further thickened. The advantage would be a simulation of a higher activity and a longer exposure time / slower expiration time on vertical surfaces.

Examples of applications for liquid cleaning gels with pH values <5 include floor and tile cleaning, tub and faucet cleaning and toilet cleaning.

Claims (7)

1. A liquid washing, cleaning, disinfecting or bleaching composition having a pH of below 5, comprising amphiphilic copolymers which include structural units derived from

   a) acryloyldimethyltauric acid in free form, partially neutralized form or completely neutralized form with monovalent or divalent inorganic or organic cations, and

   b) at least one hydrophobic comonomer based on ethylenically unsaturated polyalkylene alkoxylates, and optionally

   c) further at least monovinylically unsaturated comonomers different from a) and b).
2. The liquid washing, cleaning, disinfecting or bleaching composition as claimed in claim 1, in which the copolymers have a molecular weight M_w of from 10³ g/mol to 10⁹ g/mol.
3. The liquid washing, cleaning, disinfecting or bleaching composition as claimed in claim 1 and/or 2, in which the acryloyldimethyltaurates (structural unit a) are Li⁺, Na⁺, K⁺, Mg⁺⁺, Ca⁺⁺, Al⁺⁺⁺, NH₄ ⁺, monoalkylammonium, dialkylammonium, trialkylammonium and/or tetraalkylammonium salts, where the alkyl substituents of the amines are, independently of one another, (C₁-C₂₂)-alkyl radicals, which may optionally be occupied by up to 3 (C₂-C₁₀)-hydroxyalkyl groups.
4. The liquid washing, cleaning, disinfecting or bleaching composition as claimed in one or more of claims 1 to 3, in which, based on the total mass of the copolymers, the content of acryloyldimethyltauric acid or acryloyldimethyltaurates is 0.1 to 99.9% by weight.
5. The liquid washing, cleaning, disinfecting or bleaching composition as claimed in one or more of claims 1 to 4, in which the macromonomers b) used are compounds according to formula (I)
   
           R¹ - Y - [(A)_v - (B)_w - (C)_x - (D)_z] - R²     (I)
   
   in which
   R¹ is a function capable of polymerization from the group of vinylically unsaturated compounds which is suitable for building up polymeric structures in a free-radical manner,
   R² is a linear or branched aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C₁-C₅₀)-hydrocarbon radical, OH, -NH₂, -N(CH₃)₂ or is the structural unit [-Y-R¹],
   Y is -O-, -C(O)-, -C(O)-O-, -S-, -O-CH₂-CH(O-)-CH₂OH, -O-CH₂-CH(OH)-CH₂O-, -O-SO₂-O-, -O-SO-O-, -PH-, -P(CH₃)-, -PO₃-, -NH- and -N(CH₃)-,
   A, B, C and D are derived from acrylamide, methacrylamide, ethylene oxide, propylene oxide, AMPS, acrylic acid, methacrylic acid, methyl methacrylate, acrylonitrile, maleic acid, vinyl acetate, styrene, 1,3-butadiene, isoprene, isobutene, diethylacrylamide and diisopropylacrylamide,
   v, w, x and z, independently of one another are 0 to 500, where the sum of the four coefficients must on average be ≥ 1.
6. The liquid washing, cleaning, disinfecting or bleaching composition as claimed in one or more of claims 1 to 5, in which the molecular weight of the macromonomers b) is 200 g/mol to 10⁶ g/mol.
7. The liquid washing, cleaning, disinfecting and bleaching composition as claimed in one or more of claims 1 to 6, in which the comonomers c) used are olefinically unsaturated monomers chosen from N-vinylformamide (VIFA), N-vinylmethylformamide, N-vinylmethylacetamide (VIMA) and N-vinylacetamide; cyclic N-vinylamides (N-vinyllactams) with a ring size from 3 to 9, preferably N-vinylpyrrolidone (NVP) and N-vinylcaprolactam; amides of acrylic acid and methacrylic acid, preferably acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide and N,N-diisopropylacrylamide; alkoxylated acrylamides and methacrylamides, preferably hydroxyethyl methacrylate, hydroxymethylmethacrylamide, hydroxyethylmethacrylamide, hydroxypropylmethacrylamide and succinic mono-[2-(methacryloyloxy)ethyl ester]; N,N-dimethylaminomethacrylate; diethylaminomethyl methacrylate; acryl- and methacrylamidoglycolic acid; 2- and 4-vinylpyridine; vinyl acetate; glycidyl methacrylate; styrene; acrylonitrile; stearyl acrylate; lauryl methacrylate.