EP1477553B1 - Liquid washing and cleaning agents with viscosity modifying polymers - Google Patents

Liquid washing and cleaning agents with viscosity modifying polymers Download PDF

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Publication number
EP1477553B1
EP1477553B1 EP04011034A EP04011034A EP1477553B1 EP 1477553 B1 EP1477553 B1 EP 1477553B1 EP 04011034 A EP04011034 A EP 04011034A EP 04011034 A EP04011034 A EP 04011034A EP 1477553 B1 EP1477553 B1 EP 1477553B1
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Prior art keywords
alkyl
weight
acid
cleaning
structural unit
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EP04011034A
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German (de)
French (fr)
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EP1477553A1 (en
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Johannes Dr. Himmrich
Christoph Dr. Kayser
Roman Dr. Morschhäuser
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Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate

Definitions

  • the present invention relates to liquid washing, cleaning, disinfecting and bleaching agents containing copolymers based on acryloyldimethyltaurine.
  • the finished formulations are characterized by a favorable rheological behavior, as well as good compatibility with other components. They have a high storage stability, in particular a high stability of hydrolysis-sensitive components, for example in the case of oxidizing agents in the formulations, preferably in acidic formulations and are UV stable.
  • 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.
  • these polymeric structures 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.
  • 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.
  • pH-sensitive oxidizing agents such as hydrogen peroxide
  • the mixing ratio concerning structural unit a2) can vary within any limits.
  • Preferred copolymers contain From 2 to 30% by weight, particularly preferably from 3 to 15% by weight, of the structural units a1) or a2), preferably of the structural unit a2), 69.5 to 97.5 wt .-%, particularly preferably 84.5 to 96.5 wt .-%, of the structural unit b) and 0.01 to 5 wt .-%, particularly preferably 0.2 to 3 wt .-%, particularly preferably 0.5 to 2 wt .-%, of the structural unit c).
  • Particularly preferred structural units of the formula (1) are derived from N-vinylpyrrolidone.
  • Suitable structural units according to formula (3) are preferably alkali metal / alkaline earth metal, preferably ammonium salts of 2-acrylamido-2-methylpropanesulfonic acid, particularly preferably the NH 4 + salt.
  • the crosslinking structural units c) are preferably derived from allyl acrylate or methacrylate, trimethylolpropane triacrylate, trimethylolpropane methacrylate, dipropylene glycol diallyl ether, polyglycol diallyl ether, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane or other allyl or vinyl ethers of polyfunctional alcohols, tetraethylene glycol diacrylate, triallylamine, trimethylolpropane diallyl ether, methylenebisacrylamide and / or divinylbenzene.
  • the crosslinking structures are derived from monomers of the general formula (4) where R is hydrogen, methyl or ethyl.
  • the preparation of the copolymers is carried out by polymerization reaction, for example by Precipitation polymerization, emulsion polymerization, bulk polymerization, solution polymerization or gel polymerization, wherein the precipitation polymerization is particularly advantageous for the property profile of the copolymers used according to the invention.
  • polymerization reaction for example by Precipitation polymerization, emulsion polymerization, bulk polymerization, solution polymerization or gel polymerization, wherein the precipitation polymerization is particularly advantageous for the property profile of the copolymers used according to the invention.
  • a protic solvent preferably tert-butanol.
  • one or more crosslinkers c) are added to this solution or dispersion and the polymerization is started in a known manner by addition of a radical-forming compound.
  • the polymerization reaction is preferably carried out in a water-soluble alcohol or a mixture of several alcohols having 1 to 6 C atoms, preferably in tert-butanol.
  • the water content of the alcohol or alcohol mixture should not exceed 10% by weight, since otherwise lumping may occur in the course of the polymerization.
  • the choice of the type and the amount of the solvent should be such that the salt of the acrylamidoalkylsulfonic according to formula (3), in particular the 2-acrylamido-2-methyl-propane-sulfonic acid, is substantially soluble or dispersible therein. Under largely soluble or dispersible is to be understood that even after stopping the agitator no solid material from the solution or dispersion settles.
  • the polymer formed in the course of the reaction should be substantially insoluble in the chosen solvent or solvent mixture. It is to be understood here to be largely insoluble that a readily stirrable, pasty polymer paste is formed in the course of the polymerization in which no lumps or adhesions form.
  • the filtrate obtainable by suction of the paste should have a solids content of at most 5% by weight. If the copolymers are more soluble in the chosen solvent or solvent mixture, clumping may occur during drying of the polymer paste.
  • the polymerization reaction itself is in a conventional manner by radical-forming compounds such as azo initiators (eg azobisisobutyronitrile), peroxides (eg dilauryl peroxide) or persulfates in the temperature range of 20 to 120 ° C, preferably between 40 and 80 ° C, started and over a period of 30 Minutes to several hours continued.
  • azo initiators eg azobisisobutyronitrile
  • peroxides eg dilauryl peroxide
  • persulfates in the temperature range of 20 to 120 ° C, preferably between 40 and 80 ° C, started and over a period of 30 Minutes to several hours continued.
  • the property profile of the copolymers can be varied by varying the above mixing ratio of the monomers and the crosslinker. So can eg the thickening effect of the polymers can be improved by the increased incorporation of acrylamidosulfonic acid / salt.
  • the alkali metal, alkaline earth metal, particularly preferably NH 4 + salts are particularly preferably polymerized in.
  • ammonium salts it is also possible to use the free acrylamidopropylsulfonic acids and to produce the ammonium salts by introducing ammonia before adding the remaining monomers.
  • the copolymers used according to the invention in detergents and cleaners 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 agents according to the invention preferably contain from 0.01 to 10% by weight, more preferably from 0.1 to 5% by weight, particularly preferably from 0.5 to 3% by weight, of copolymers.
  • the 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 are present.
  • Other embodiments may be: emulsions, dispersions, gels and suspensions.
  • 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.
  • preferred embodiments may contain bleaching and disinfecting agents, for example chlorine or bromine-releasing substances, or organic or inorganic peroxides.
  • Suitable chlorine or bromine releasing materials include, for example, heterocyclic N-bromo and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • Anhydrous, water-soluble inorganic salts are also useful as bleaching agents, such as lithium, sodium, or calcium hypochlorite and hypobromite. Chlorinated trisodium phosphate is also considered.
  • Organic peracids and diacyl peroxides for example peroxybenzoic acid and its benzene-substituted analogs, aliphatic and substituted aliphatic monoperoxy acids, for example peroxylauric acid or peroxystearic acid, alkyldiperoxyacids and aryldiperoxyacids such as 1,12-diperoxydodecanoic acid, 1,9-diperoxybrassidic acid, diperoxysebacylic acid, diperoxyisophthalic acid and dibenzoyl peroxide.
  • monopersulfates, perborates and percarbonates may be used.
  • the inorganic peroxy compounds are generally used as alkali metal salts, preferably as lithium, sodium and potassium salts.
  • the preparations according to the invention may contain bleaches and disinfectants 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.
  • 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").
  • nonionic surfactants of this type are Tergitol TM 15-S-9 (condensation product of a C 11 -C 15 linear secondary alcohol with 9 moles of ethylene oxide), Tergitol TM 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 TM brands from Clariant GmbH.
  • 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.
  • 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.
  • 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.
  • 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.
  • Alkyl ester sulfonates are linear esters of C 8 -C 20 carboxylic acids (ie, fatty acids) which are sulfonated by SO 3 as described in U.S. Pat. The Journal of the American Oil Chemists Society, 52 (1975), pp. 323-329 described.
  • Suitable starting materials are natural fatty derivatives, such as tallow or palm oil fatty acid.
  • Alkyl sulfates are water-soluble salts or acids of the formula ROSO 3 M, wherein R preferably has 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 Represents hydroxyalkyl.
  • 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).
  • 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
  • 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.
  • 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.
  • 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.
  • 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 the pyrolysis products of alkaline earth metal citrates, as described, for example, in US Pat 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 die
  • 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 in U.S. Patent 3,929,678 claimed.
  • 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.
  • 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.
  • the washing and cleaning agents contain, depending on the application, in addition to the surfactants mentioned nor the specific auxiliaries and additives
  • auxiliaries and additives For example, builders, salts, 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.
  • 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.
  • NTA nitriloacetate
  • polymeric carboxylates and their salts 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.
  • compositions according to the invention can be used as foam inhibitors fatty acid alkyl ester alkoxylates, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, Microcrystalline waxes and their mixtures with silanized silica. It is also advantageous to use mixtures of different foam inhibitors, for example those of silicone oil, paraffin oil or waxes.
  • 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.
  • 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.
  • organic solvents 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.
  • 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.
  • 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 the behenic acid, as well as polysaccharides, especially xanthan gum, guar guar, agar, alginates and Tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone used.
  • 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.
  • the salts of polyphosphoric acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepentamethylenephosphonic acid (DTPMP), are preferably used in amounts by weight of 0.1 to 1.0 wt .-%.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DTPMP diethylenetriaminepentamethylenephosphonic acid
  • 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.
  • salts or adjusting agents for example, sodium sulfate, sodium carbonate or sodium silicate (water glass) are used.
  • 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 1 to 12, preferably from pH 2.1 to 7.8, more preferably from 2.2 to 6.5.
  • 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.
  • 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 copolymers containing acryloyldimethyltaurate.
  • organic solvents especially alcohols
  • anionic and nonionic surfactants and other formulation ingredients are easily possible through the use of copolymers containing acryloyldimethyltaurate.
  • 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 .-%.
  • copolymers containing 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.
  • cleaning "fat-crusted" hard Surfaces such as tiles, glass or ceramic or metal are called.
  • Possible fields of use according to the invention are, for example, bathroom cleaners, glass cleaners, and floor cleaners.
  • 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.
  • 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.
  • Formulations according to the invention may contain organic or inorganic peroxides, in particular hydrogen peroxide or a mixture thereof. at In various applications, it is desirable that the peroxide solutions adhere to the substrate rather than draining, so that the effect can be fully exploited.
  • 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.
  • Bleaching solutions e.g. for cleaning laundry (liquid stain remover) 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 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 may e.g. be used in the field of cleaning hard surfaces in the hygiene or sanitary sector.
  • 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 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.
  • acryloyldimethyltaurate polymers according to the invention clear formulations are available which correspond to the current trend towards clear formulations and transparent packaging.

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Description

Die vorliegende Erfindung betrifft flüssige Wasch-, Reinigungs-, Desinfektions- und Bleichmittel, enthaltend Copolymere auf Basis von Acryloyldimethyltaurinsäure. Die fertigen Formulierungen zeichnen sich durch ein
günstiges rheologisches Verhalten, sowie durch eine gute Kompatibilität mit anderen Komponenten aus. Sie weisen eine hohe Lagerstabilität auf, insbesondere eine hohe Stabilität von hydrolyseempfindlichen Komponenten, beispielsweise bei Oxidationsmitteln in den Formulierungen, bevorzugt in sauren Formulierungen und sind UV stabil.The present invention relates to liquid washing, cleaning, disinfecting and bleaching agents containing copolymers based on acryloyldimethyltaurine. The finished formulations are characterized by a
favorable rheological behavior, as well as good compatibility with other components. They have a high storage stability, in particular a high stability of hydrolysis-sensitive components, for example in the case of oxidizing agents in the formulations, preferably in acidic formulations and are UV stable.

An moderne flüssige Wasch- Reinigungs- und Desinfektionsmittel werden hohe Ansprüche gestellt, die eng mit der Rheologie der Produkte verknüpft sind: Sie müssen neben einem guten und raschen Reinigungsvermögen gegenüber Schmutz und Fett bzw. Desinfektionsvermögen anwendungsfreundlich, sicher, sehr gut hautverträglich, aber auch umweltverträglich sein. Zur Verbesserung der Handhabung für den Verbraucher und des Erscheinungsbildes kommen zunehmend flüssige Produkte mit höheren Viskositäten in den Handel, so dass Verdickern und Gelbildnern eine tragende Rolle zukommt.High demands are placed on modern liquid detergents and disinfectants, which are closely linked to the rheology of the products: in addition to good and rapid cleaning power, they must be easy to use, dirt-friendly, well tolerated by the environment, 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.

Als Konsistenzgeber werden bisher fast ausschließlich synthetische oder teilsynthetische Polymere auf Basis von vernetzten Polyacrylsäuren (Carbomere, Carbopole), teilhydrolysierten Polyacrylamide, Celluloseethern, Xanthan oder Guar-Gum verwandt. Dabei tritt immer das Problem der Intoleranz gegenüber niedrigen pH-Werten auf, was die Anwendungsmöglichkeiten vieler Produkte auf den Neutral- bzw. schwach sauren Bereich einschränkt.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 levels, which limits the potential applications of many products to the neutral or weakly acidic range.

Aufgabe vorliegender Erfindung war es demzufolge, einen Verdicker für Wasch- und Reinigungsmittelformulierungen zu finden, der auch im sauren Milieu unter pH 5 seine Wirksamkeit nicht verliert.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.

Überraschenderweise wurde nun gefunden, dass dieser gravierende Nachteil durch den Einsatz von Copolymeren auf Basis von Acryloyldimethyltaurat, deren Herstellung in EP-1 116 733 beschrieben ist, beseitigt werden kann.Surprisingly, it has now been found that this serious disadvantage is due to the use of copolymers based on acryloyldimethyltaurate, their preparation in EP-1 116 733 described can be eliminated.

Es ist gelungen mit Hilfe dieser polymeren Strukturen Formulierungen zum Waschen, Reinigen und Desinfizieren auf Viskositäten größer 100 cP einzustellen. In besonderen Ausführungsformen handelt es sich um Formulierungen mit saurem Charakter (pH < 5). Aufgrund des sauren Milieus gelingt es zudem pH-empfindliche Oxidationsmittel wie beispielsweise Wasserstoffperoxid dauerhaft zu stabilisieren und dadurch neuen Anwendungen im Reinigungs- und Hygienebereich zugänglich zu machen. Erfreulicherweise zeichnen sich diese Formulierungen zusätzlich durch eine hohe UV-Stabilität aus. Dies ermöglicht die Verwendung von transparenten Verpackungsmaterialien, die derzeit auf dem Markt sehr gefragt sind.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.

Gegenstand der Erfindung sind flüssige Wasch-, Reinigungs-, Desinfektions- und Bleichmittel, enthaltend Copolymere, erhalten durch Copolymerisation von

  1. a1) 1 bis 50 Gew.-% der wiederkehrenden Struktureinheit der Formel (1)
    Figure imgb0001
     wobei n eine ganze Zahl von 2 bis 9 bedeutet oder
  2. a2) 1 bis 50 Gew.-% einer Mischung der wiederkehrenden Struktureinheit der Formel (1) und der wiederkehrenden Struktureinheit der Formel (2)
    Figure imgb0002
     wobei R, R1 und R2 gleich oder verschieden sein können und Wasserstoff oder eine lineare oder verzweigte Alkyl- oder Alkenylgruppe mit jeweils 1 bis 30, bevorzugt 1 bis 20, insbesondere 1 bis 12 C-Atomen, bedeuten
    und
  3. b) 49,99 bis 98,99 Gew.-% der wiederkehrenden Struktureinheit der Formel (3)
    Figure imgb0003
     worin R3 Wasserstoff, Methyl oder Ethyl, Z (C1-C8)-Alkylen, n eine ganze Zahl von 2 bis 9 und X bevorzugt Li+, Na+, K+, Mg++, Ca++, Al+++, NH4 +, Monoalkyl-ammonium-, Dialkylammonium-, Trialkylammonium- und/oder Tetraalkyl-ammoniumreste, wobei es sich bei den Alkylsubstituenten der Amine unabhängig voneinander um (C1-C22)-Alkylreste oder (C2-C10)-Hydroxyalkylreste handeln kann, bedeuten
    und
  4. c) 0,01 bis 8 Gew.-% vernetzenden Strukturen, die aus Monomeren mit mindestens zwei olefinischen Doppelbindungen hervorgegangen sind.
The invention relates to liquid washing, cleaning, disinfecting and bleaching agents containing copolymers obtained by copolymerization of
  1. a1) from 1 to 50% by weight of the repeating structural unit of the formula (1)
    Figure imgb0001
     where n is an integer from 2 to 9 or
  2. a2) 1 to 50% by weight of a mixture of the repeating structural unit of the formula (1) and the repeating structural unit of the formula (2)
    Figure imgb0002
     wherein R, R 1 and R 2 may be the same or different and are hydrogen or a linear or branched alkyl or alkenyl group having in each case 1 to 30, preferably 1 to 20, in particular 1 to 12 C-atoms
    and
  3. b) from 49.99 to 98.99% by weight of the repeating structural unit of the formula (3)
    Figure imgb0003
     wherein R 3 is hydrogen, methyl or ethyl, Z is (C 1 -C 8 ) -alkylene, n is an integer from 2 to 9 and X is preferably Li + , Na + , K + , Mg ++ , Ca ++ , Al + ++ , NH 4 + , monoalkylammonium, dialkylammonium, trialkylammonium and / or tetraalkylammonium radicals, wherein the alkyl substituents of the amines independently of one another are (C 1 -C 22 ) -alkyl radicals or (C 2 -C 10 ) -Hydroxyalkylreste can act mean
    and
  4. c) 0.01 to 8 wt .-% crosslinking structures, which have emerged from monomers having at least two olefinic double bonds.

Das Mischungsverhältnis betreffend Struktureinheit a2) kann innerhalb beliebiger Grenzen variieren.The mixing ratio concerning structural unit a2) can vary within any limits.

Bevorzugte Copolymere enthalten 2 bis 30 Gew.-%, besonders bevorzugt 3 bis 15 Gew.-%, der Struktureinheiten a1) oder a2), bevorzugt der Struktureinheit a2),
69,5 bis 97,5 Gew.-%, besonders bevorzugt 84,5 bis 96,5 Gew.-%, der Struktureinheit b) und
0,01 bis 5 Gew.-%, besonders bevorzugt 0,2 bis 3 Gew.-%, insbesondere bevorzugt 0,5 bis 2 Gew.-%, der Struktureinheit c).Preferred copolymers contain From 2 to 30% by weight, particularly preferably from 3 to 15% by weight, of the structural units a1) or a2), preferably of the structural unit a2),
69.5 to 97.5 wt .-%, particularly preferably 84.5 to 96.5 wt .-%, of the structural unit b) and
0.01 to 5 wt .-%, particularly preferably 0.2 to 3 wt .-%, particularly preferably 0.5 to 2 wt .-%, of the structural unit c).

Besonders bevorzugte Struktureinheiten gemäß Formel (1) leiten sich vom N-Vinylpyrrolidon ab.Particularly preferred structural units of the formula (1) are derived from N-vinylpyrrolidone.

Als Struktureinheit gemäß Formel (3) eignen sich bevorzugt Alkali-/Erdalkali, bevorzugt Ammoniumsalze der 2-Acrylamido-2-methyl-propan-sulfonsäure, besonders bevorzugt das NH4 +-Salz. Zusätzlich können auch ein bis dreifach ethoxylierte Ammoniumverbindungen mit unterschiedlichem Ethoxylierungsgrad als Gegenion eingesetzt werden.
Die vernetzenden Struktureinheiten c) leiten sich bevorzugt ab von Acryl- oder Methacrylsäureallylester, Trimethylolpropantriacrylat, Trimethylolpropanmethacrylat, Dipropylenglykoldiallylether, Polyglykoldiallylether, Triethylenglykoldivinylether, Hydrochinondiallylether, Tetraallyloxyethan oder anderen Allyl- oder Vinylethern multifunktioneller Alkohole, Tetraethylenglykoldiacrylat, Triallylamin, Trimethylolpropandiallylether, Methylenbisacrylamid und/oder Divinylbenzol.
Besonders bevorzugt sind Acrylsäureallylester, Methacrylsäureallylester, Trimethylolpropantriacrylat und/oder Trimethylolpropanmethacrylat.
Insbesondere bevorzugt leiten sich die vernetzenden Strukturen ab von Monomeren der allgemeinen Formel (4)

Figure imgb0004
worin R Wasserstoff, Methyl oder Ethyl bedeutet.Suitable structural units according to formula (3) are preferably alkali metal / alkaline earth metal, preferably ammonium salts of 2-acrylamido-2-methylpropanesulfonic acid, particularly preferably the NH 4 + salt. In addition, it is also possible to use one to three times ethoxylated ammonium compounds having a different degree of ethoxylation as the counterion.
The crosslinking structural units c) are preferably derived from allyl acrylate or methacrylate, trimethylolpropane triacrylate, trimethylolpropane methacrylate, dipropylene glycol diallyl ether, polyglycol diallyl ether, triethylene glycol divinyl ether, hydroquinone diallyl ether, tetraallyloxyethane or other allyl or vinyl ethers of polyfunctional alcohols, tetraethylene glycol diacrylate, triallylamine, trimethylolpropane diallyl ether, methylenebisacrylamide and / or divinylbenzene.
Particularly preferred are allyl acrylate, allyl methacrylate, trimethylolpropane triacrylate and / or trimethylolpropane methacrylate.
Particularly preferably, the crosslinking structures are derived from monomers of the general formula (4)
Figure imgb0004
 where R is hydrogen, methyl or ethyl.

Die Herstellung der Copolymere erfolgt durch Polymerisationsreaktion, z.B. durch Fällungspolymerisation, Emulsionspolymerisation, Substanzpolymerisation, Lösungspolymerisation oder Gelpolymerisation, wobei besonders vorteilhaft für das Eigenschaftsprofil der erfindungsgemäß eingesetzten Copolymere die Fällungspolymerisation ist.
Wie in EP-1 116 733 beschrieben, werden dabei die Monomeren entsprechend den Formeln (1), (2) und (3) in einem protischen Lösungsmittel, bevorzugt tert.-Butanol gelöst oder dispergiert. Anschließend werden zu dieser Lösung oder Dispersion ein oder mehrere Vernetzer c) gegeben und die Polymerisation in bekannter Weise durch Zugabe einer radikalbildenden Verbindung gestartet.
Die Polymerisationsreaktion erfolgt vorzugsweise in einem wasserlöslichen Alkohol oder einem Gemisch mehrerer Alkohole mit 1 bis 6 C-Atomen, vorzugsweise in tert.-Butanol. Der Wassergehalt des Alkohols oder Alkoholgemisches sollte 10 Gew.-% nicht überschreiten, da sonst im Verlauf der Polymerisation eine Klumpenbildung auftreten kann. Die Wahl der Art und der Menge des Lösungsmittels sollte so erfolgen, dass das Salz der Acrylamidoalkylsulfonsäure entsprechend Formel (3), insbesondere der 2-Acrylamido-2-methyl-propan-sulfonsäure, darin weitgehend löslich oder dispergierbar ist. Unter weitgehend löslich oder dispergierbar ist zu verstehen, dass sich auch nach Abstellen des Rührwerks kein festes Material aus der Lösung oder Dispersion absetzt. Das im Verlaufe der Reaktion entstehende Polymerisat soll hingegen in dem gewählten Lösungsmittel bzw. Lösungsmittelgemisch weitgehend unlöslich sein. Unter weitgehend unlöslich ist hierbei zu verstehen, dass im Verlauf der Polymerisation eine gut rührbare, breiige Polymerpaste entsteht, in der sich keine Klumpen oder Verklebungen bilden. Das durch Absaugen der Paste erhältliche Filtrat sollte einen Feststoffgehalt von maximal 5 Gew.-% aufweisen. Sind die Copolymere in stärkerem Ausmaß im gewählten Lösungsmittel oder Lösungsmittelgemisch löslich, kann es beim Trocknen der Polymerisatpaste zu Verklumpungen kommen.
Die Polymerisationsreaktion selbst wird in an sich bekannter Weise durch radikalbildende Verbindungen wie Azoinitiatoren (z.B. Azobisisobutyronitril), Peroxide (z.B. Dilaurylperoxid) oder Persulfate im Temperaturintervall von 20 bis 120°C, vorzugsweise zwischen 40 und 80°C, gestartet und über einen Zeitraum von 30 Minuten bis mehrere Stunden fortgeführt.
Das Eigenschaftsprofil der Copolymere lässt sich durch Variation des oben Mischungsverhältnisses der Monomere sowie der Vernetzer variieren. So kann z.B. durch den verstärkten Einbau von Acrylamidosulfonsäure/-salz die verdickende Wirkung der Polymerisate verbessert werden. Durch Einbau von mehr cyclischem N-Vinylcarbonsäureamid wird dagegen die Elektrolytverträglichkeit der Polymerisate und deren Löslichkeit in nicht-wässrigen Systemen verbessert.The preparation of the copolymers is carried out by polymerization reaction, for example by Precipitation polymerization, emulsion polymerization, bulk polymerization, solution polymerization or gel polymerization, wherein the precipitation polymerization is particularly advantageous for the property profile of the copolymers used according to the invention.
As in EP-1 116 733 described, while the monomers according to the formulas (1), (2) and (3) are dissolved or dispersed in a protic solvent, preferably tert-butanol. Subsequently, one or more crosslinkers c) are added to this solution or dispersion and the polymerization is started in a known manner by addition of a radical-forming compound.
The polymerization reaction is preferably carried out in a water-soluble alcohol or a mixture of several alcohols having 1 to 6 C atoms, preferably in tert-butanol. The water content of the alcohol or alcohol mixture should not exceed 10% by weight, since otherwise lumping may occur in the course of the polymerization. The choice of the type and the amount of the solvent should be such that the salt of the acrylamidoalkylsulfonic according to formula (3), in particular the 2-acrylamido-2-methyl-propane-sulfonic acid, is substantially soluble or dispersible therein. Under largely soluble or dispersible is to be understood that even after stopping the agitator no solid material from the solution or dispersion settles. By contrast, the polymer formed in the course of the reaction should be substantially insoluble in the chosen solvent or solvent mixture. It is to be understood here to be largely insoluble that a readily stirrable, pasty polymer paste is formed in the course of the polymerization in which no lumps or adhesions form. The filtrate obtainable by suction of the paste should have a solids content of at most 5% by weight. If the copolymers are more soluble in the chosen solvent or solvent mixture, clumping may occur during drying of the polymer paste.
The polymerization reaction itself is in a conventional manner by radical-forming compounds such as azo initiators (eg azobisisobutyronitrile), peroxides (eg dilauryl peroxide) or persulfates in the temperature range of 20 to 120 ° C, preferably between 40 and 80 ° C, started and over a period of 30 Minutes to several hours continued.
The property profile of the copolymers can be varied by varying the above mixing ratio of the monomers and the crosslinker. So can eg the thickening effect of the polymers can be improved by the increased incorporation of acrylamidosulfonic acid / salt. By incorporating more cyclic N-vinylcarboxamide, however, the electrolyte compatibility of the polymers and their solubility in non-aqueous systems is improved.

Besonders bevorzugt werden als Acrylamidopropylsulfonsäure-Salze die Alkali-, Erdalkali, besonders bevorzugt NH4 +-Salze einpolymerisiert. Anstelle der Ammoniumsalze kann man auch die freien Acrylamidopropylsulfonsäuren einsetzen und vor der Zugabe der restlichen Monomere durch Einleiten von Ammoniak die Ammoniumsalze erzeugen.As acrylamidopropylsulfonic acid salts, the alkali metal, alkaline earth metal, particularly preferably NH 4 + salts are particularly preferably polymerized in. Instead of the ammonium salts, it is also possible to use the free acrylamidopropylsulfonic acids and to produce the ammonium salts by introducing ammonia before adding the remaining monomers.

Die erfindungsgemäß in Wasch- und Reinigungsmittel eingesetzten Copolymere besitzen bevorzugt ein Molekulargewicht Mw von 103 g/mol bis 109 g/mol, besonders bevorzugt von 104 bis 107 g/mol, insbesondere bevorzugt 5·104 bis 5·106 g/mol. Mw ist für die Zwecke dieser Erfindung generell durch GPC gegen Polystyrolsulfonsäure zu bestimmen.
Die erfindungsgemäßen Mittel enthalten bevorzugt 0,01 bis 10 Gew.-%, besonders bevorzugt 0,1 bis 5 Gew.-%, insbesondere bevorzugt 0,5 bis 3 Gew.-%, an Copolymeren.The copolymers used according to the invention in detergents and cleaners 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 agents according to the invention preferably contain from 0.01 to 10% by weight, more preferably from 0.1 to 5% by weight, particularly preferably from 0.5 to 3% by weight, of copolymers.

Es sollte angemerkt werden, dass auch Mischungen von zwei oder mehreren der oben genannten Verbindungen erfindungsgemäß sind.It should be noted that mixtures of two or more of the above compounds are also within the scope of the invention.

Erfindungsgemäß können die oben beschriebenen Copolymere auf Basis von Acryloyldimethyltaurat generell in allen Wasch-, Reinigungs-, Desinfektions- und Bleichmitteln jeder Art eingesetzt werden. Bevorzugt werden sie eingesetzt als Verdicker in sauren Reinigungsmittelformulierungen für harte Oberflächen aus Keramik, Metall, Glas oder Kunststoff, beispielsweise in flüssigen Allzweckreinigern, im Sanitärbereich, beispielsweise Flüssigtoilettenstein, kalklösender Badreinigern, aber auch Geschirrspülmitteln. Des weiteren sind sie geeignet für den Einsatz in Fleckensalzmittel, Flüssigwaschmitteln und Wäschebleichmittel.According to the invention, the 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.

Die erfindungsgemäßen Wasch- Reinigungs-, Desinfektions- und Bleichmittel können in Form von wässrigen, wässrig/organischen, insbesondere wässrig/alkoholischen und organischen Formulierungen vorliegen. Weitere Ausführungsformen können sein: Emulsionen, Dispersionen, Gele und Suspensionen.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 are present. Other embodiments may be: emulsions, dispersions, gels and suspensions.

In einer bevorzugten Ausführungsform enthalten die erfindungsgemäßen Wasch-, Reinigungs-, Desinfektions- und Bleichmittel eine saure Komponente.
In Betracht kommen organische oder anorganische Säuren, bevorzugt organische Säuren, insbesondere bevorzugt alpha-Hydroxysäuren und Säuren ausgewählt aus Glykolsäure, Milchsäure, Zitronensäure, Weinsäure, Mandelsäure, Salicylsäure, Ascorbinsäure, Brenztraubensäure, Oligooxa Mono- und Dicarbonsäuren, Fumarsäure, Retinoesäure, aliphatische und organische Sulfonsäuren, Benzoesäure, Kojisäure, Fruchtsäure, Äpfelsäure, Gluconsäure, Galacturonsäure, saure Pflanzen- und/oder Fruchtextrakte und deren Derivate.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.

Des weiteren können bevorzugte Ausführungsformen Bleich- und Desinfektionsmittel, beispielsweise Chlor oder Brom freisetzende Substanzen oder organische oder anorganische Peroxide enthalten.Furthermore, preferred embodiments may contain bleaching and disinfecting agents, for example chlorine or bromine-releasing substances, or organic or inorganic peroxides.

Unter den geeigneten Chlor oder Brom freisetzenden Materialien kommen beispielsweise heterocyclische N-Brom und N-Chloramide, beispielsweise Trichlorisocyanursäure, Tribromisocyanursäure, Dibromisocyanursäure und/oder Dichlorisocyanursäure (DICA) und/oder deren Salze mit Kationen wie Kalium und Natrium in Betracht. Hydanthoinverbindungen, wie 1,3-Dichlor-5,5-dimethylhydanthoin sind ebenfalls geeignet.
Wasserfreie, wasserlösliche anorganische Salze sind ebenfalls als Bleichmittel geeignet, so z.B. Lithium-, Natrium-, oder Calciumhypochlorit und -hypobromit. Chloriertes Trinatriumphosphat kommt ebenfalls in Betracht.
Organische Persäuren und Diacylperoxide, beispielsweise Peroxybenzoesäure und deren am Benzolring substituierte Analoga, aliphatische und substituierte aliphatische Monoperoxysäuren, beispielsweise Peroxylaurinsäure oder Peroxystearinsäure, Alkyldiperoxysäuren und Aryldiperoxysäuren wie 1,12-Diperoxydodecansäure, 1,9-Diperoxybrassidylsäure, Diperoxysebacylsäure, Diperoxyisophthalsäure, sowie Dibenzoylperoxid.
Zu den anorganischen Peroxyverbindungen, die im Rahmen der vorliegenden Erfindung einsetzbar sind, zählen beispielsweise Monopersulfate, Perborate und Percarbonate. Die anorganischen Peroxyverbindungen werden in der Regel als Alkalisalze eingesetzt, vorzugsweise als Lithium-, Natrium- und Kaliumsalze.Suitable chlorine or bromine releasing materials include, for example, heterocyclic N-bromo and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
Anhydrous, water-soluble inorganic salts are also useful as bleaching agents, such as lithium, sodium, or calcium hypochlorite and hypobromite. Chlorinated trisodium phosphate is also considered.
Organic peracids and diacyl peroxides, for example peroxybenzoic acid and its benzene-substituted analogs, aliphatic and substituted aliphatic monoperoxy acids, for example peroxylauric acid or peroxystearic acid, alkyldiperoxyacids and aryldiperoxyacids such as 1,12-diperoxydodecanoic acid, 1,9-diperoxybrassidic acid, diperoxysebacylic acid, diperoxyisophthalic acid and dibenzoyl peroxide.
To the inorganic peroxy compounds, in the context of the present For example, monopersulfates, perborates and percarbonates may be used. The inorganic peroxy compounds are generally used as alkali metal salts, preferably as lithium, sodium and potassium salts.

Die erfindungsgemäßen Zubereitungen können Bleich- und Desinfektionsmittel in Mengen von 0,1 bis 30 Gew.-%, besonders bevorzugt 0,5 bis 18 Gew.-%, insbesondere 1,5 bis 9 Gew.-% enthalten.The preparations according to the invention may contain bleaches and disinfectants 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.

Die erfindungsgemäßen Wasch-, Reinigungs-, Desinfektions- und Bleichmittel können Tenside nichtionischer, anionischer, kationischer oder amphoterer Natur sowie übliche Hilfs- und Zusatzstoffe in unterschiedlichen Mengen enthalten.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.

Bevorzugte nichtionische Tenside sind Fettalkoholoxethylate mit ca. 1 bis ca. 25 mol Ethylenoxid. Die Alkylkette der aliphatischen Alkohole kann linear oder verzweigt, primär oder sekundär sein, und enthält im allgemeinen von 8 bis 22 Kohlenstoffatome. Besonders bevorzugt sind die Kondensationsprodukte von Alkoholen, die eine Alkylkette von 10 bis 20 Kohlenstoffen enthalten, mit 2 bis 18 mol Ethylenoxid pro mol Alkohol. Die Alkylkette kann gesättigt oder auch ungesättigt sein. Ebenso können die Alkoholethoxylate eine enge Homologenverteilung des Ethylenoxides ("Narrow Range Ethoxylates") oder eine breite Homologenverteilung des Ethylenoxides ("Broad Range Ethoxylates") aufweisen. Beispiele von kommerziell erhältlichen nichtionischen Tensiden dieses Types sind Tergitol™ 15-S-9 (Kondensationsprodukt eines C11-C15 linearen sekundären Alkohols mit 9 mol Ethylenoxid), Tergitol™ 24-L-NMW (Kondensationsprodukt eines C12-C14- linearen primären Alkohols mit 6 mol Ethylenoxid mit enger Molgewichtsverteilung). Ebenfalls unter diese Produktklasse fallen die Genapol™-Marken der Clariant GmbH.
Darüber hinaus kommen erfindungsgemäß auch andere bekannte Typen von nichtionischen Tensiden in Frage, wie Polyethylen-, Polypropylen- und Polybutylenoxidaddukte von Alkylphenolen mit 6 bis 12 C-Atomen in der Alkylkette, Additionsprodukte von Ethylenoxid mit einer hydrophoben Base, gebildet aus der Kondensation von Propylenoxid mit Propylenglykol oder Additionsprodukte von Ethylenoxid mit einem Reaktionsprodukt von Propylenoxid und Ethylendiamin.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.

Des weiteren können semipolare nichtionische Tenside, beispielsweise Aminoxide der Formel III

Figure imgb0005
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 Sauerstoff- oder 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
Figure imgb0005
 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.

Anstelle oder zusätzlich zu den nichtionischen Tensiden können die erfindungsgemäßen Mischungen auch anionische Tenside enthalten.Instead of or in addition to the nonionic surfactants, the mixtures according to the invention may also contain anionic surfactants.

Als anionische Tenside kommen in Betracht vor allem geradkettige und verzweigte Alkylsulfate, -sulfonate, -carboxylate, -phosphate, Alkylestersulfonate, Arylalkylsulfonate, Alkylethersulfate und Mischungen aus den genannten Verbindungen. Im folgenden sollen einige der in Frage kommenden Typen von anionischen Tensiden näher beschrieben werden.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.

AlkylestersulfonateAlkyl

Alkylestersulfonate stellen lineare Ester von C8-C20-Carboxylsäuren (d.h. Fettsäuren) dar, die durch SO3 sulfoniert werden, wie in " The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329 beschrieben. Geeignete Ausgangsmaterialien sind natürliche Fettderivate, wie z.B. Talg- oder Palmölfettsäure.Alkyl ester sulfonates are linear esters of C 8 -C 20 carboxylic acids (ie, fatty acids) which are sulfonated by SO 3 as described in U.S. Pat. The Journal of the American Oil Chemists Society, 52 (1975), pp. 323-329 described. Suitable starting materials are natural fatty derivatives, such as tallow or palm oil fatty acid.

Alkylsulfatealkyl sulfates

Alkylsulfate sind wasserlösliche Salze oder Säuren der Formel ROSO3M, worin R bevorzugt einen C10-C24-Kohlenwasserstoffrest, bevorzugt einen Alkyl- oder Hydroxyalkylrest mit 10 bis 20 C-Atomen, besonders bevorzugt einen C12-C18-Alkyl- oder Hydroxyalkylrest darstellt. M ist Wasserstoff oder ein Kation, z.B. ein Alkalimetallkation (z.B. Natrium, Kalium, Lithium) oder Ammonium oder substituiertes Ammonium, z.B. ein Methyl-, Dimethyl- und Trimethylammoniumkation oder ein quaternäres Ammoniumkation, wie Tetramethylammonium- und Dimethylpiperidiniumkation und quartäre Ammoniumkationen, abgeleitet von Alkylaminen wie Ethylamin, Diethylamin, Triethylamin und deren Mischungen. Alkylketten mit C12-C16 sind dabei bevorzugt für niedrige Waschtemperaturen (z.B. unter ca. 50°C) und Alkylketten mit C16-C18 bevorzugt für höhere Waschtemperaturen (z.B. oberhalb ca. 50°C).Alkyl sulfates are water-soluble salts or acids of the formula ROSO 3 M, wherein R preferably has 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 Represents hydroxyalkyl. 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).

Alkylethersulfatealkyl ether

Die Alkylethersulfate sind wasserlösliche Salze oder Säuren der Formel RO(A)mSO3M, worin R einen unsubstituierten C10-C24-Alkyl- oder Hydroxyalkylrest mit 10 bis 24 C-Atomen, bevorzugt einen C12-C20-Alkyl- oder Hydroxyalkylrest, besonders bevorzugt einen C12-C18-Alkyl- oder Hydroxyalkylrest darstellt. A ist eine Ethoxy- oder Propoxyeinheit, m ist eine Zahl von größer als 0, typischerweise zwischen ca. 0,5 und ca. 6, besonders bevorzugt zwischen ca. 0,5 und ca. 3 und M ist ein Wasserstoffatom oder ein Kation wie z.B. ein Metallkation (z.B. Natrium, Kalium, Lithium, Calcium, Magnesium, etc.), Ammonium oder ein substituiertes Ammoniumkation. Beispiele für substituierte Ammoniumkationen sind Methyl-, Dimethyl-, Trimethylammonium- und quaternäre Ammoniumkationen wie Tetramethylammonium und Dimethylpiperidiniumkationen, sowie solche, die von Alkylaminen, wie Ethylamin, Diethylamin, Triethylamin, Mischungen davon und ähnliche, abgeleitet sind. Als Beispiele seien genannt C12-C18-Alkyl-polyethoxylat- (1,0)-sulfat, C12-C18-Alkyl-polyethoxylat (2,25)sulfat, C12-C18-Alkyl-polyethoxylat (3,0)sulfat, C12-C18-Alkyl-polyethoxylat (4,0)sulfat, wobei das Kation Natrium oder Kalium ist.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.

Andere anionische Tenside die nützlich für den Einsatz in Wasch- und Reinigungsmitteln sind, sind C8-C24-Olefinsulfonate, sulfonierte Polycarboxylsäuren, hergestellt durch Sulfonierung der Pyrolyseprodukte von Erdalkalimetallcitraten, wie z.B. beschrieben im britischen Patent GB 1,082,179 , Alkylglycerinsulfate, Fettacylglycerinsulfate, Oleylglycerinsulfate, Alkylphenolethersulfate, primäre Paraffinsulfonate, Alkylphosphate, Alkyletherphosphate, Isethionate, wie Acylisethionate, N-Acyltauride, Alkylsuccinamate, Sulfosuccinate, Monoester der Sulfosuccinate (besonders gesättigte und ungesättigte C12-C18-Monoester) und Diester der Sulfosuccinate (besonders gesättigte und ungesättigte C12-C18-Diester), Acylsarcosinate, Sulfate von Alkylpolysacchariden wie Sulfate von Alkyloylglycosiden, verzweigte primäre Alkylsulfate und Alkylpolyethoxycarboxylate wie die der Formel RO(CH2CH2)kCH2COO-M+ worin R ein C8-C22-Alkyl, k eine Zahl von 0 bis 10 und M ein lösliches Salz bildendes Kation ist. Harzsäuren oder hydrierte Harzsäuren, wie Rosin oder hydriertes Rosin oder Tallölharze und Tallölharzsäuren sind ebenfalls einsetzbar. Weitere Beispiele sind in "Surface Active Agents and Detergents" (Vol. I und II, Schwartz, Perry und Berch) beschrieben. Eine Vielzahl solcher Tenside sind auch im US-Patent 3,929,678 beansprucht.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 the pyrolysis products of alkaline earth metal citrates, as described, for example, in US Pat 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 (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 in U.S. Patent 3,929,678 claimed.

Beispiele für amphotere Tenside, die in den Formulierungen der vorliegenden Erfindung Einsatz finden können, sind vor allem solche, die breit als Derivate von aliphatischen sekundären and tertiären Aminen beschrieben werden, in denen der aliphatische Rest linear oder verzweigt sein kann und in denen einer der aliphatischen Substituenten zwischen. 8 bis 18 Kohlenstoffatome enthält und eine anionische, wasserlösliche Gruppe, wie z.B. Carboxy, Sulfonat, Sulfat, Phosphat oder Phosphonat enthält.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.

Weitere bevorzugte amphotere Tenside sind Alkyldimethylbetaine, Alkylamidobetaine und Alkyldipolyethoxybetaine mit einem Alkylrest, der linear oder verzweigt sein, mit. 8 bis 22 Kohlenstoffatomen, bevorzugt mit 8 bis 18 Kohlenstoffatomen und besonders bevorzugt mit. 12 bis. 18 Kohlenstoffatomen. Diese Verbindungen werden z.B. von der Clariant GmbH unter dem Handelnamen Genagen® CAB vermarktet.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.

Hilfs- und ZusatzstoffeAuxiliaries and additives

Die Wasch- und Reinigungsmittel enthalten, je nach Anwendungszweck, neben den genannten Tensiden noch die jeweils spezifischen Hilfs- und Zusatzstoffe beispielsweise Builder, Salze, Bleichmittel, Bleichaktivatoren, optische Aufheller, Komplexbildner, Vergrauungsinhibitoren, Lösungsvermittler, Enzyme, Verdickungsmittel, Konservierungsmittel, Duft- und Farbstoffe, Perlglanzmittel, Schauminhibitoren, Sequestriermittel.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, bleaches, bleach activators, optical brighteners, complexing agents, grayness inhibitors, solubilizers, enzymes, thickeners, preservatives, fragrances and dyes, pearlescing agents, foam inhibitors, sequestering agents.

Als organische und anorganische Gerüststoffe eignen sich neutral oder insbesondere alkalisch reagierende Salze, die Calciumionen auszufällen oder komplex zu binden vermögen. Geeignete und insbesondere ökologisch unbedenkliche Buildersubstanzen, wie feinkristalline, synthetische wasserhaltige Zeolithe von Typ NaA, die ein Calciumbindevermögen im Bereich von 100 bis 200 mg CaO/g aufweisen, finden eine bevorzugte Verwendung. In nichtwässrigen Systemen werden bevorzugt Schichtsilikate eingesetzt. Zeolith und die Schichtsilikate können in einer Menge bis zu 20 Gew.-% im Mittel enthalten sein. Brauchbare organische Gerüstsubstanzen sind beispielsweise die bevorzugt in Form ihrer Natriumsalze eingesetzten Percarbonsäuren, wie Citronensäure und Nitriloacetat (NTA), Ethylendiamintetraessigsäure, sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist. Analog hierzu können auch polymere Carboxylate und deren Salze eingesetzt werden. Hierzu gehören beispielsweise die Salze homopolymerer oder copolymerer Polyacrylate, Polymethyacrylate und insbesondere Copolymere der Acrylsäure mit Maleinsäure, vorzugsweise solche aus 50 % bis 10 % Maleinsäure und auch Polyvinylpyrrolidon und Urethane. Die relative Molekülmasse der Homopolymeren liegt im allgemeinen zwischen 1000 und 100 000, die der Copolymeren zwischen 2000 und 200 000, vorzugsweise 50 000 bis 120 000, bezogen auf die freie Säure, insbesondere sind auch wasserlösliche Polyacrylate geeignet, die beispielsweise mit etwa 1 % eines Polyallylethers der Sucrose quervernetzt sind und die eine relative Molekülmasse oberhalb einer Million besitzen. Beispiele hierfür sind die unter dem Namen Carbopol 940 und 941 erhältlichen Polymere. Die quervernetzen Polyacrylate werden in Mengen nicht über 1 Gew.-%, vorzugsweise in Mengen von 0,2 bis 0,7 Gew.-% eingesetzt.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.

Die erfindungsgemäßen Mittel können als Schauminhibitoren Fettsäurealkylesteralkoxylate, Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure, enthalten. Mit Vorteil können auch Gemische verschiedener Schauminhibitoren verwendet werden, z.B. solche aus Silikonöl, Paraffinöl oder Wachsen. Vorzugsweise sind Schauminhibitoren an eine granulare, in Wasser lösliche oder dispergierbare Trägersubstanz gebunden.The compositions according to the invention can be used as foam inhibitors fatty acid alkyl ester alkoxylates, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, Microcrystalline waxes and their mixtures with silanized silica. It is also advantageous to use mixtures of different foam inhibitors, for example those of silicone oil, paraffin oil or waxes. Preferably, foam inhibitors are bound to a granular, water-soluble or dispersible carrier substance.

Die Flüssigwaschmittel können optische Aufheller beispielsweise Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten, die sich gut in die Dispersion einarbeiten lassen. Der maximale Gehalt an Aufhellern in den erfindungsgemäßen Mitteln beträgt 0,5 Gew.-%, vorzugsweise werden Mengen von 0,02 bis 0,25 Gew.-% eingesetzt.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.

Die gewünschte Viskosität der Mittel kann durch Zugabe von Wasser und/oder organischen Lösungsmitteln oder durch Zugabe einer Kombination aus organischen Lösungsmitteln und weitere Verdickungsmitteln eingestellt werden.
Prinzipiell kommen als organische Lösungsmittel alle ein- oder mehrwertigen Alkohole in Betracht. Bevorzugt werden Alkohole mit 1 bis 4 Kohlenstoffatomen wie Methanol, Ethanol, Propanol, Isopropanol, geradkettige und verzweigtes Butanol, Glycerin und Mischungen aus den genannten Alkoholen eingesetzt. Weitere bevorzugte Alkohole sind Polyethylenglykole mit einer relativen Molekülmasse unter 2000. Insbesondere ist ein Einsatz von Polyethylenglykol mit einer relativen Molekülmasse zwischen 200 und 600 und in Mengen bis zu 45 Gew.-% und von Polyethylenglykol mit einer relativen Molekülmasse zwischen 400 und 600 in Mengen von 5 bis 25 Gew.-% bevorzugt. Eine vorteilhafte Mischung aus Lösungsmitteln besteht aus monomerem Alkohol, beispielsweise Ethanol und Polyethylenglykol im Verhältnis 0,5 : 1 bis 1,2 : 1, wobei die erfindungsgemäßen Flüssigwaschmittel 8 bis 12 Gew.-% einer solchen Mischung enthalten können. Weitere geeignete Lösungsmittel sind beispielsweise Triacetin (Glycerintriacetat) und 1-Methoxy-2-propanol.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.

Als Verdickungsmittel werden bevorzugt gehärtetes Rizinusöl, Salze von langkettigen Fettsäuren, vorzugsweise in Mengen von 0 bis 5 Gew.-% und insbesondere in Mengen von 0,5 bis 2 Gew.-%, beispielsweise Natrium-. Kalium-, Aluminium-, Magnesium- und Titan-Stearate oder die Natrium und/oder Kalium-Salze der Behensäure, sowie Polysaccharide, insbesondere Xanthan-Gum, Guar-Guar, Agar-Agar, Alginate und Tylosen, Carboxymethylcellulose und Hydroxyethylcellulose, ferner höhermolekulare Polyethylenglycolmono- und -diester von Fettsäuren, Polyacrylate, Polyvinylalkohol und Polyvinylpyrrolidon eingesetzt.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 the behenic acid, as well as polysaccharides, especially xanthan gum, guar guar, agar, alginates and Tyloses, carboxymethyl cellulose and hydroxyethyl cellulose, also higher molecular weight polyethylene glycol mono- and diesters of fatty acids, polyacrylates, polyvinyl alcohol and polyvinylpyrrolidone used.

Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen bzw. deren Gemische in Frage. Ihr Anteil kann 0,2 bis 1 Gew.-% betragen. Die Enzyme können an Trägersubstanzen adsorbiert werden und/oder in Hüllsubstanzen eingebettet sein.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.

Um Spuren von Schwermetallen zu binden, können die Salze von Polyphosphorsäuren, wie 1-Hydroxyethan-1,1-diphosphonsäure (HEDP) und Diethylentriaminpentamethylenphosphonsäure (DTPMP), bevorzugt in Gewichtsmengen von 0,1 bis 1,0 Gew.-% eingesetzt werden.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), are preferably used in amounts by weight of 0.1 to 1.0 wt .-%.

Als Konservierungsmittel eignen sich beispielsweise Phenoxyethanol, Formaldehydlösung, Parabene, Pentandiol oder Sorbinsäure.Suitable preservatives are, for example, phenoxyethanol, formaldehyde solution, parabens, pentanediol or sorbic acid.

Als Perlglanzmittel kommen beispielsweise Glycoldistearinsäureester wie Ethylenglycoldistearat, aber auch Fettsäuremonoglycolester in Betracht.Suitable pearlescing agents are, for example, glycol distearate esters, such as ethylene glycol distearate, but also fatty acid monoglycol esters.

Als Salze bzw. Stellmittel kommen beispielsweise Natriumsulfat, Natriumcarbonat oder Natriumsilikat (Wasserglas) zum Einsatz.
Als typische Einzelbeispiele für weitere Zusatzstoffe sind Natriumborat, Stärke, Saccharose, Polydextrose, Stilbenverbindungen, Methylcellulose, Toluolsulfonat, Cumolsulfonat, Seifen und Silicone zu nennen.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.

Die erfindungsgemäßen Mittel sind üblicherweise auf einen pH Wert im Bereich 1 bis 12, bevorzugt pH 2,1 bis 7,8, besonders bevorzugt 2,2 bis 6,5 eingestellt.The agents according to the invention are customarily adjusted to a pH in the range from 1 to 12, preferably from pH 2.1 to 7.8, more preferably from 2.2 to 6.5.

Durch Einsatz von Acryloyldimethyltaurat enthaltenden Copolymeren gelang es, Formulierungen mit einem pH Wert von < 5 auf Viskositäten oberhalb von 100 mPas zu verdicken. Diese Formulierungen bringen einerseits den Vorteil, dass die Viskosifizierung ein "Verspritzen" des Reinigungsmittels verhindert und dadurch eine sicherere Verwendung gewährleistet. Zudem sorgt die erhöhte Viskosität für ein langsameres Ablaufen des Reinigers von den Oberflächen und garantiert damit eine längere Einwirkzeit. Durch die breite pH-Toleranz der eingesetzten Polymere ist es erstmals möglich stärkere organische Säuren wie beispielsweise Zitronensäure, Äpfelsäure, alpha-Hydroxycarbonsäuren und Oxalsäure in freier Form zu verwenden. Eine verbesserte Wirksamkeit speziell gegen Kalkbeläge kann damit erzielt werden.By using copolymers containing acryloyldimethyltaurate, it was possible to thicken formulations having a pH of <5 to viscosities above 100 mPas. On the one hand, these formulations have the advantage that the viscosification prevents a "splattering" of the cleaning agent and thus a 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 den besagten Formulierungen werden Acryloyldimethyltaurat enthaltenden Copolymere in einer Menge von 0,01 bis 10 Gew.-% eingesetzt. Bevorzugt wird mit einer Menge von 0,1 bis 5 Gew.-% gearbeitet. Besonders bevorzugt ist der Bereich von 0,2 bis 2 Gew.-%. Je nach eingesetzter Polymermenge kann die Viskosität der resultierenden Gele zwischen 100 und 100.000 mPas liegen.In said formulations, 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.

Flüssige Reinigungsgele enthaltend Wasser/organische Lösungsmittel-GemischeLiquid cleansing gels containing water / organic solvent mixtures

Die Verdickung von organischen Lösungsmitteln, speziell Alkoholen, in Kombination mit anionischen und nichtionischen Tensiden und anderen Formulierungsbestandteilen ist durch den Einsatz von Acryloyldimethyltaurat enthaltenden Copolymeren leicht möglich. Einschränkend muss angemerkt werden, dass lediglich wasserkompatible organische Lösungsmittel im Sinne der Erfindung sind. Als nicht limitierende Beispiele können Ethanol, Propanol, Isopropanol, DMSO, NMP, Aceton, Methanol und Butanol genannt werden. Die resultierenden Gele können zwischen 0,1 und 90 Gew.-% organischen Lösungsmittelanteil enthalten. Bevorzugt wird ein Anteil von 5 bis 80 Gew.-%. Besonders bevorzugt sind Gele mit einem Gehalt an organischen Lösungsmitteln von 20 bis 60 Gew.-%. Allgemein werden Acryloyldimethyltaurat enthaltende Copolymere in diesen Formulierungen in einer Menge von 0,01 bis 10 Gew.-% eingesetzt. Bevorzugt wird mit einer Menge von 0,1 bis 5 Gew.-% gearbeitet. Besonders bevorzugt ist der Bereich von 0,2 bis 2 Gew.-%. Dabei können die Viskositäten der resultierenden Reinigergele enthaltend organische Lösungsmittel zwischen 100 und 100.000 mPas variieren, je nach eingesetzter Polymermenge.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 copolymers containing acryloyldimethyltaurate. 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 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.

Als Einsatzgebiet können auch hier die Reinigung "fettverkrusteter" harter Oberflächen wie Kacheln, Glas oder Keramik oder Metall genannt werden. Mögliche erfindungsgemäße Einsatzgebiete sind beispielsweise Badreiniger, Glasreiniger, und Bodenreiniger.As a field of application can also be here the cleaning "fat-crusted" hard Surfaces such as tiles, glass or ceramic or metal are called. Possible fields of use according to the invention are, for example, bathroom cleaners, glass cleaners, and floor cleaners.

Flüssige, Desinfektionsmittel enthaltende ReinigungsgeleLiquid cleaning gels containing disinfectants

Desinfektionsgele spielen im Hygienebereich eine große Rolle und erfreuen sich am Markt seit einigen Jahren steigender Beleibtheit. Speziell Gele in der Verwendung als "flüssige Toilettensteine" sind im sanitären Bereich seit Jahren auf dem Vormarsch.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.

Die Verdickung von wässrigen Desinfektionslösungen durch herkömmliche Verdicker auf Basis von Celluloseethern oder Polyacrylsäuren erfordert teilweise eine hohe Einsatzkonzentration dieser Polymere und ist zudem auf den neutralen bis schwach sauren pH-Bereich beschränkt.
Durch Einsatz von Acryloyldimethyltaurat enthaltenden Copolymere kann diese Limitierung beseitigt werden. Es ist erstmals möglich, flüssige Desinfektionsmittel enthaltende Reinigungsgele mit sauren Formulierungsbestandteilen wie Fruchtsäure oder alpha-Hydroxycarbonsäuren zu kombinieren und damit neben der antiseptischen auch noch eine "kalklösende" Wirkung zu erzielen.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 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 den besagten Formulierungen werden Acryloyldimethyltaurat enthaltende Copolymere in einer Menge von 0,01 bis 10 Gew.-% eingesetzt. Bevorzugt wird mit einer Menge von 0,1 bis 5 Gew.-% gearbeitet. Besonders bevorzugt ist der Bereich von 0,2 bis 2 Gew.-%. Je nach eingesetzter Polymermenge kann die Viskosität der resultierenden Gele zwischen 100 und 100.000 mPas liegen.In the said formulations 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.

Verdickung saurer Peroxid enthaltender Lösungen mit AcryloyldimethytauratpolymerenThickening of acid peroxide-containing solutions with acryloyldimethytaurate polymers

Für flüssige Formulierungen von Peroxidlösungen ist es wünschenswert diese zu verdicken. Dadurch wird die Handhabung vereinfacht und sicherer gestaltet.
Erfindungsgemäße Formulierungen können organische oder anorganische Peroxide, insbesondere Wasserstoffperoxid oder eine Mischung dieser enthalten. Bei verschiedenen Anwendungen ist es wünschenswert, dass die Peroxidlösungen auf dem Untergrund haften und nicht Ablaufen, damit die Wirkung zur vollen Entfaltung kommen kann. Jedoch lassen sich Lösungen von Peroxid mit herkömmlichen Verdickern nur schwer über einen längeren Zeitraum verdicken bzw. stabilisieren. Der Grund ist darin zu suchen, dass eine Wasserstoffperoxidlösung bei neutralen bzw. nur schwach sauren pH-Werten bereits vergleichsweise instabil ist. Bei dem Zerfall werden auch die Verdicker angegriffen und die Viskosität baut über die Zeit stark ab. Dadurch kommt es zusätzlich zu einem erheblichen Verlust der Wasserstoffperoxidaktivität Bei sauren pH-Werten ist der Zerfall von Wasserstoffperoxid stark retardiert, jedoch bricht die Verdickungsleistung von Verdickern auf Acrylsäurebasis bei pH-Werten < 5,5 zusammen.
Der Einsatz von Acryloyldimethytauratpolymeren in Bleichlösungen verdickt die Formulierung auch bei pH-Werten deutlich unterhalb des Schwellenwertes von pH 5. Die Verdickungsleistung der erfindungsgemäßen Polymere bleibt in einem pH-Wert-Intervall von 1 bis 9 nahezu konstant. Es sind mit den erfindungsgemäßen Verdickern daher sogar Formulierungen mit pH-Werten um pH 1 zugänglich. In diesem pH-Bereich findet über normale Lagerzeiträume kein merklicher Zerfall von H2O2 statt, was zu Folge hat, dass die erfindungsgemäßen Acryloyldimethytauratpolymere nicht angegriffen und zerstört werden und somit die Viskosität der erfindungsgemäßen Formulierung nahezu konstant bleibt. Im folgenden werden zur Illustration der Erfindung einige nicht beschränkende Einsatzmöglichkeiten von solchen sauren verdickten Wasserstoffperoxidlösungen dargestellt: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. at In various applications, it is desirable that the peroxide solutions adhere to the substrate rather than draining, so that the effect can be fully exploited. 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 acryloyldimethytaurate polymers in bleaching solutions thickens the formulation even at pH values well below the threshold value of pH 5. The thickening performance of the polymers according to the invention remains virtually constant at a pH value interval of 1 to 9. Therefore, with the thickeners according to the invention, even formulations with pH values around pH 1 are accessible. In this pH range, no appreciable decomposition of H 2 O 2 takes place over normal storage periods, which has the consequence that the Acryloyldimethytauratpolymere invention are not attacked and destroyed and thus the viscosity of the formulation according to the invention remains almost constant. In the following, to illustrate the invention, some non-limiting applications of such acidic thickened hydrogen peroxide solutions are shown:

Bleichlösungen z.B. für die Reinigung von Wäsche (flüssiges Fleckensalz) oder Geschirr:Bleaching solutions e.g. for cleaning laundry (liquid stain remover) or dishes:

Eine Lösung von 0,1 bis 30 %ww H2O2, bevorzugt von 1 bis 15 %ww, besonders bevorzugt von 3 bis 10 %ww lässt sich mittels erfindungsgemäßer Acryloyldimethytauratpolymere bei pH-Werten < 5 verdicken. Auch bei erhöhten Lagertemperaturen wird eine über Monate stabile Viskosität gefunden. Durch die Verdickung der Bleichlösung wird es dem Anwender erleichtert, die optimale Dosierung einzustellen. Die Lösung verspritzt nicht und die Handhabung wird dadurch sicherer.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 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.

Peroxidhaltige Reiniger können z.B. im Bereich der Reinigung harter Oberflächen im Hygiene- oder Sanitärbereich eingesetzt werden. In diesem Fall können Formulierungen hergestellt werden, die auch anionische und nichtionische Tenside enthalten. Sehr nützlich sind solche Mittel, beispielsweise für die Reinigung von Toiletten. Der peroxidhaltige Reiniger haftet an der Keramik und kann so seine reinigende und desinfizierende Wirkung optimal entfalten.Peroxide-containing cleaners may e.g. be used in the field of cleaning hard surfaces in the hygiene or sanitary sector. 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 bzw. Flüssigkeit gefüllte Dauerreiniger (Flüssigtoilettensteine) zum Einhängen in den Spülkasten oder das WC-Becken können mit einer ähnlichen Formulierung realisiert werden. Ein Teil der gelartig verdickten Lösung wird bei jedem Spülvorgang mit dem Wasserstrom im Becken verteilt und sorgt so für eine reinigende und desinfizierende Wirkung. Mit den erfindungsgemäßen Acryloyldimethyltaurat Polymeren sind klare Formulierungen zugänglich, die dem heutigen Trend nach klaren Formulierungen und transparenten Verpackungen entsprechen.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 acryloyldimethyltaurate polymers according to the invention, clear formulations are available which correspond to the current trend towards clear formulations and transparent packaging.

Claims (3)

  1. A liquid washing, cleaning, disinfecting or bleaching composition comprising copolymers obtained by copolymerization of
    a1) 1 to 50% by weight of those monomers which produce a repeating structural unit of the formula (1)
    Figure imgb0009
     where n is an integer from 2 to 9
    or
    a2) 1 to 50% by weight of a mixture of those monomers which produce a repeating structural unit of the formula (1) and the repeating structural unit of the formula (2)
    Figure imgb0010
     where R, R1 and R2 can be identical or different and are hydrogen or a linear or branched alkyl or alkenyl group having in each case 1 to 30, preferably 1 to 20, in particular 1 to 12 carbon atoms
    and
    b) 49.99 to 98.99% by weight of those monomers which produce a repeating structural unit of the formula (3)
    Figure imgb0011
     in which R3 is hydrogen, methyl or ethyl, Z is (C1-C8)-alkylene and X is preferably Li+, Na+, K+, Mg++, Ca++, Al+++, NH4 +, monoalkylammonium, dialkylammonium, trialkylammonium and/or tetraalkylammonium radicals, it being possible for the alkyl substituents of the amines independently of one another to be (C1-C22)-alkyl radicals or (C2-C10)-hydroxyalkyl radicals,
    and
    c) 0.01 to 8% by weight of crosslinking structures originating from monomers having at least two olefinic double bonds.
  2. The liquid washing, cleaning, disinfecting or bleaching composition as claimed in claim 1, in which the copolymers have a molecular weight Mw 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 b) are Li+, Na+, K+, Mg++, Ca++, AI+++, 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.
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Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0716228D0 (en) * 2007-08-20 2007-09-26 Reckitt Benckiser Nv Detergent composition
FR2931687B1 (en) * 2008-05-27 2017-11-24 Commissariat A L'energie Atomique AQUEOUS DECONTAMINANT AND FOAMING SOLUTION.
EP2322594A1 (en) 2009-10-13 2011-05-18 Clariant S.A., Brazil Discrete or single dose detergent formulation
US7939484B1 (en) * 2009-10-27 2011-05-10 Clariant International, Ltd. Method for reducing the adhesion forces between hard surfaces and subsequently occurring soil
US20110207648A1 (en) * 2010-02-24 2011-08-25 Clariant International Ltd. Use Of N,N-Bis(2-Hydroxyethyl)Cocoamine Oxide For The Cleaning Of Hard Surfaces
US9523006B2 (en) * 2011-06-03 2016-12-20 Hewlett-Packard Development Company, L.P. Erasure fluid
WO2012166160A1 (en) 2011-06-03 2012-12-06 Hewlett-Packard Development Company, L.P. Method of erasing an ink from a medium
US9315042B2 (en) 2011-06-03 2016-04-19 Hewlett-Packard Development Company, L.P. Systems for erasing an ink from a medium
EP3310736B1 (en) 2015-06-17 2019-01-30 Clariant International Ltd Water-soluble or water-swellable polymers as fluid loss additives for cement slurries
ES2759984T3 (en) 2015-06-17 2020-05-12 Clariant Int Ltd Process for the production of polymers based on acryloyldimethyl laurate, neutral monomers, monomers with carbonic acids and special crosslinkers
EP3106470A1 (en) 2015-06-17 2016-12-21 Clariant International Ltd Method for producing polymers on the basis of acryloyldimethyl taurate and special crosslinking agents
EP3106471A1 (en) 2015-06-17 2016-12-21 Clariant International Ltd Method for producing polymers on the basis of acryloyldimethyl taurate, neutral monomers and special crosslinking agents
EP3239120A1 (en) 2016-04-27 2017-11-01 Clariant International Ltd Water resistance additive for ammonium nitrate - fuel oil (anfo) explosives
JP7089487B2 (en) 2016-06-20 2022-06-22 クラリアント・インターナシヨナル・リミテツド Compounds containing certain levels of biobase carbon
KR200485769Y1 (en) 2016-08-10 2018-03-29 주식회사 코비스 스포츠 Ball Pick Up Device
WO2018108609A1 (en) * 2016-12-12 2018-06-21 Clariant International Ltd Polymer comprising certain level of bio-based carbon
EP3551681A1 (en) * 2016-12-12 2019-10-16 Clariant International Ltd Polymer comprising certain level of bio-based carbon
CN110300573B (en) 2016-12-12 2023-07-25 科莱恩国际有限公司 Use of biobased polymers in cosmetic, dermatological or pharmaceutical compositions
WO2018108608A1 (en) * 2016-12-12 2018-06-21 Clariant International Ltd Polymer comprising certain level of bio-based carbon
US11401362B2 (en) 2016-12-15 2022-08-02 Clariant International Ltd Water-soluble and/or water-swellable hybrid polymer
EP3554646A1 (en) 2016-12-15 2019-10-23 Clariant International Ltd Water-soluble and/or water-swellable hybrid polymer
US11542343B2 (en) 2016-12-15 2023-01-03 Clariant International Ltd Water-soluble and/or water-swellable hybrid polymer
WO2018108664A1 (en) 2016-12-15 2018-06-21 Clariant International Ltd Water-soluble and/or water-swellable hybrid polymer
KR20180081994A (en) 2017-01-09 2018-07-18 엘지전자 주식회사 Partial Laundry Detergent Composition
CN112876596B (en) * 2021-01-06 2022-12-13 广州市东雄化工有限公司 Solution type alcohol disinfection gel thickening agent and preparation method thereof

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1082179A (en) * 1965-07-19 1967-09-06 Citrique Belge Nv Unsaturated carboxylic salt materials and derivatives thereof
DE2437090A1 (en) * 1974-08-01 1976-02-19 Hoechst Ag CLEANING SUPPLIES
JP3042546B2 (en) * 1991-04-23 2000-05-15 昭和電工株式会社 Fine-particle crosslinked N-vinylamide resin and microgel, production method and use thereof
ES2123601T3 (en) * 1992-08-22 1999-01-16 Clariant Gmbh USE OF WATER-SOLUBLE COPOLYMERS BASED ON ACRYLAMIDALKYLENSULPHONIC ACIDS AS AN ADDITIVE TO DETERGENTS.
US6475501B1 (en) * 1997-06-04 2002-11-05 The Procter & Gamble Company Antiviral compositions for tissue paper
US6617849B1 (en) * 1999-06-15 2003-09-09 Georgsmarienhütte Gmbh Device for the nondestructive testing of especially hot bar shaped rolling material
AU1096101A (en) * 1999-10-19 2001-04-30 Procter & Gamble Company, The Antimicrobial compositions comprising a dicarboxylic acid and a metal salt
US6517849B1 (en) * 1999-10-19 2003-02-11 The Procter & Gamble Company Tissue products containing antiviral agents which are mild to the skin
DE10000648A1 (en) * 2000-01-11 2001-07-12 Clariant Gmbh New crosslinked copolymers containing vinyl lactam and N-(sulfoalkyl)-acrylamide salt repeating units, especially useful as thickeners in cosmetic or pharmaceutical compositions
DE10059818A1 (en) * 2000-12-01 2002-06-13 Clariant Gmbh Decorative cosmetic and dermatological means
JP2002327102A (en) * 2000-12-01 2002-11-15 Clariant Gmbh Composition containing copolymer based on acryloyldimethyltaurine acid and synergistic additive
DE10059833A1 (en) * 2000-12-01 2002-06-13 Clariant Gmbh Fluorine-modified comb polymers based on acryloyldimethylauric acid
DE10059823A1 (en) * 2000-12-01 2002-06-13 Clariant Gmbh Deodorants and antiperspirants
DE10059822A1 (en) * 2000-12-01 2002-06-13 Clariant Gmbh Acid cosmetic, pharmaceutical and dermatological agents
DE10119338A1 (en) * 2001-04-20 2002-10-24 Clariant Gmbh Use of copolymers based on acrylamidoalkylsulfonic acids as thickeners in preparations containing organic solvents
US6437088B1 (en) * 2001-08-14 2002-08-20 E. I. Du Pont De Nemours And Company Process for producing polyester with coated titanium dioxide
DE10243661A1 (en) * 2002-09-19 2004-04-01 Clariant Gmbh Liquid washing and cleaning agents with consistency-giving polymers
JP4075557B2 (en) * 2002-10-02 2008-04-16 株式会社デンソー Compressor and vehicle air conditioner
DE10250755B4 (en) * 2002-10-31 2007-02-08 Merz Pharma Gmbh & Co. Kgaa A foamable composition based on an O / W emulsion comprising a combination of a silicone-based emulsifier and an anionic surfactant having improved skin action, their preparation and their use

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