EP1426436B1 - Liquid bleaching component comprising amphiphilic polymers - Google Patents

Description

The present invention relates to liquid or pasty, homogeneous and heterogeneous bleach components containing hydrophobically modified copolymers based on acryloyldimethyltaurine. As bleaching components are to be understood organic or organometallic substances which form bleaching-active species in combination with a Peroxydquelle, which can be used for bleaching, oxidation, but also disinfection purposes. These include in particular bleach activators and bleach catalysts as well as oxygen transfer agents. The finished bleaches containing the bleach components according to the invention are characterized by a favorable rheological behavior, as well as by a good compatibility with other components. They have a high physical and chemical storage stability, and high hydrolytic stability of the components, in particular the bleach component and the copolymer.

High demands are placed on modern liquid bleach components for use in commerce and households, which are closely linked to the rheology of the products: in combination with a second, peroxide-containing component, they must develop high bleaching and disinfecting capacity, easy to use, safe, very well tolerated by the skin , but also be environmentally friendly. 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. For commercial use in industrial cleaning, paper or textile bleaching, as well as surface disinfection, the liquid components must be pumpable and well dosed to ensure easy industrial processing.

Synthetic or almost synthetic polymers based on crosslinked polyacrylic acids (carbomers, Carbopols), partially hydrolyzed polyacrylamides, cellulose ethers, xanthan or guar gum. The problem of intolerance to low pH values always occurs, which limits the potential applications of many products to the neutral or weakly acidic range. Particularly problematic is the thickening of bleach components, in particular in those bleach activators which hydrolyze in aqueous formulations particularly easily with the formation of acids and thus cause the pH to drop to the acidic range.

Surprisingly, it has been possible to eliminate this disadvantage by the use of hydrophobically modified copolymers based on acryloyldimethyltaurate, the preparation of which is described in EP 10 69 142.

The copolymers described there can be used to adjust bleach formulations as components for washing, cleaning and disinfecting to viscosities greater than 100 cP. In particular embodiments, these are formulations having an acidic to slightly alkaline character (pH <8). Fortunately, these formulations are additionally characterized by a high UV stability. This allows the use of transparent packaging materials.

1. 1) amphiphile Copolymere, die Struktureinheiten umfassen, welche abgeleitet sind aus
   • a) Acryloyldimethyltaurinsäure in freier, teil- oder vollneutralisierter Form mit ein- oder zweiwertigen anorganischen oder organischen Kationen und
   • b) mindestens einem hydrophoben Comonomer auf Basis von ethylenisch ungesättigten Polyalkylenalkoxylaten und gegebenenfalls
   • c) weiteren von a) und b) verschiedenen, mindestens einfach vinylisch ungesättigten Comonomeren, und
2. 2) mindestens einem Bleichaktivator, Bleichkatalysator oder Sauerstofftransfer-Agens.

The invention relates to liquid bleach components containing

1. 1) Amphiphilic copolymers comprising structural units derived from
   • a) Acryloyldimethyltaurinsäure in free, partially or fully neutralized form with monovalent or divalent inorganic or organic cations and
   • b) at least one hydrophobic comonomer based on ethylenically unsaturated polyalkylene and optionally
   • c) other, at least mono-vinylically unsaturated comonomers other than a) and b), and
2. 2) at least one bleach activator, bleach catalyst or oxygen transfer agent.

The polymer component

The amphiphilic copolymers preferably have a molecular weight of 10 ³ g / mol to 10 ⁹ g / mol, particularly preferably from 10 ⁴ to 10 ⁷ g / mol, particularly preferably 5 * 10 ⁴ to 5 * 10 ⁶ g / mol.

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

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

Based on the total mass of the copolymers, the content of acryloyldimethyltaurine or acryloyldimethyltaurates may be from 0.1 to 100% by weight, preferably from 20 to 99.5% by weight, particularly preferably from 50 to 98% by weight.

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

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

Preferred as macromonomers b) are compounds of the formula (I)

R ¹ -Y - [(A) _v - (B) _w - (C) _x - (D) _z ] -R ² (I)

wherein R ^{1 represents} a polymerizable function from the group of vinylically unsaturated compounds which are suitable for the construction of polymeric structures by free radicals. Preferably, R ^{1 represents} a vinyl, allyl, methallyl, methylvinyl, acrylic, methacrylic, crotonyl, senecionyl, itaconyl, maleinyl, fumaryl or styryl radical.
To attach the polymer chain to the reactive end group, a suitable bridging group Y is required. Preferred bridges Y are -O-, -C (O) -, -C (O) -O-, -S-, -O-CH ₂ -CH (O -) - CH ₂ OH, -O-CH ₂ - CH (OH) -CH ₂ O-, -O-SO ₂ -O-, -O-SO-O-, -PH-, -P (CH ₃ ) -, -PO ₃ -, -NH- and -N (CH ₃ ) -, more preferably -O-.
The polymeric middle part of the macromonomer is represented by the discrete repeating units A, B, C and D. Preferred repeating units A, B, C and D are derived from acrylamide, methacrylamide, ethylene oxide, propylene oxide, AMPS, acrylic acid, methacrylic acid, methyl methacrylate, acrylonitrile, maleic acid, vinyl acetate, styrene, 1,3-butadiene, isoprene, isobutene, diethylacrylamide and diisopropylacrylamide , in particular of ethylene oxide and propylene oxide.
The indices v, w, x and z in formula (I) represent the stoichiometric coefficients relating to repeating units A, B, C and D. v, w, x and z are independently 0 to 500, preferably 1 to 30, wherein Sum of the four coefficients on average must be ≥1.

The distribution of repeating units across the macromonomer chain may be random, blocky, alternating or gradient-like.
R ^{2 represents} a linear or branched aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C ₁ -C ₅₀ ) -hydrocarbon radical, OH, -NH ₂ , -N (CH ₃ ) ₂ or is identical to the structural unit [-YR ¹ ].

In the case of R ² equal to [-YR ¹ ] are difunctional macromonomers, which are suitable for crosslinking of the copolymers. An example of this is the compound polyethylene glycol (molecular weight 440) diacrylate.

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

R ₃ , R ₄ , R ₅ and R ₆ independently of one another denote hydrogen or n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C ₁ -C ₃₀ ) -hydrocarbon radicals.
Preferably, R ₃ and R ₄ are H or -CH ₃ , more preferably H; R ₅ is H or -CH ₃ ; and R ₆ is an n-aliphatic, iso-aliphatic, olefinic, cycloaliphatic, aryl-aliphatic or aromatic (C ₁ -C ₃₀ ) hydrocarbon radical.
Again, v and w are the stoichiometric coefficients concerning the ethylene oxide units (EO) and propylene oxide units (PO). v and w are independently 0 to 500, preferably 1 to 30, wherein the sum of v and w must be on average ≥1. The distribution of EO and PO units across the macromonomer chain can be random, block, alternating or gradient. Y stands for the bridges mentioned above. Preferably Y = oxygen.

Particularly preferred macromonomers have the following structure according to formula (II), where Y is oxygen in all cases: description R ³ R ⁴ R ⁵ R ⁶ v w LA-030 methacrylate H H -CH ₃ lauryl 3 0 LA-070 methacrylate H H -CH ₃ lauryl 7 0 LA-200 methacrylate H H -CH ₃ lauryl 20 0 LA-250 methacrylate H H -CH ₃ lauryl 25 0 T-080 methacrylate H H -CH ₃ -Tallow 8th 0 T-080 acrylate H H H -Tallow 8th 0 T-250 methacrylate H H -CH ₃ -Tallow 25 0 T-250-crotonate -CH ₃ H -CH ₃ -Tallow 25 0 OC-030 methacrylate H H -CH ₃ octyl 3 0 OC-105 methacrylate H H -CH ₃ octyl 10 5 Behenyl 010 methacrylate H H H -Behenyl 10 0 Behenyl 020 methacrylate H H H -Behenyl 20 0 Behenyl 010-senecionylat -CH ₃ -CH ₃ H -Behenyl 10 0 B-11-50 methacrylate H H -CH ₃ butyl 17 13 MPEG-750 methacrylate H H -CH ₃ -Methyl 18 0 P-010-acrylate H H H phenyl 10 0 O-050-acrylate H H H -Oleyl 5 0

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

As comonomers c) it is possible to use all olefinically unsaturated monomers whose reaction parameters permit copolymerization with acryloyldimethyltaurine acid and / or acryloyldimethyltaurates in the respective reaction media.
Preference is given to using open-chain N-vinylamides, preferably N-vinylformamide (VIFA), N-vinylmethylformamide, N-vinylmethylacetamide (VIMA) and N-vinylacetamide; cyclic N-vinylamides (N-vinyllactams) having a ring size of 3 to 9, preferably N-vinylpyrrolidone (NVP) and N-vinylcaprolactam; Amides of acrylic and methacrylic acid, preferably acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and N, N-diisopropylacrylamide; alkoxylated acrylic and methacrylamides, preferably hydroxyethyl methacrylate, hydroxymethylmethacrylamide, hydroxyethylmethacrylamide, hydroxypropylmethacrylamide and succinic mono [2- (methacryloyloxy) ethyl ester]; N, N-dimethylaminomethacrylate; diethylaminomethyl; Acrylic and methacrylamidoglycolic acid; 2- and 4-vinylpyridine; vinyl acetate; methacrylate; styrene; acrylonitrile; stearyl; lauryl;
In addition, one or more unsaturated carboxylic acids or salts thereof can be copolymerized into the structure. Particularly preferred are acrylic acid, methacrylic acid, styrenesulfonic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and senecionic acid.
Preferred as counterions of the acids are Li ⁺ , Na ⁺ , K ⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Al ⁺⁺⁺ , NH ₄ ⁺ , monoalkylammonium, dialkylammonium, trialkylammonium and / or tetraalkylammonium radicals, it being the case with the Alkyl substituents of the amines independently of one another can be (C ₁ -C ₂₂ ) -alkyl radicals, which may optionally be occupied by up to 3 (C ₂ -C ₁₀ ) -hydroxyalkyl groups. In addition, it is also possible to use one to three times ethoxylated ammonium compounds having a different degree of ethoxylation. The degree of neutralization of the carboxylic acids can be between 0 and 100%.

In a further embodiment, the copolymers according to the invention are crosslinked, ie they contain comonomers (structural unit c) having at least two polymerizable vinyl groups.
Preferred crosslinkers are methylenebisacrylamide; methylenebismethacrylamide; Esters of unsaturated mono- and polycarboxylic acids with polyols, preferably diacrylates and triacrylates or -methacrylates, more preferably butanediol and ethylene glycol diacrylate or methacrylate, trimethylolpropane triacrylate (TMPTA) and allyl compounds, preferably allyl (meth) acrylate, triallyl cyanurate, maleic acid diallyl ester, polyallyl ester, tetraallyloxyethane , Triallylamine, tetraallylethylenediamine; Allyl ester of phosphoric acid; and / or vinylphosphonic acid derivatives.
Particularly preferred crosslinkers are trimethylolpropane triacrylate (TMPTA) and timethylolpropane trimethacrylate (TMPTMA).

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

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

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

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

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

The polymerization reaction can be carried out, for example, as precipitation polymerization,
Emulsion polymerization, bulk polymerization, solution polymerization or gel polymerization led. Particularly advantageous for the property profile of Copolymers of the invention is the precipitation polymerization, preferably in tert-butanol.

The bleaching component

By bleach component is meant bleach activators (peroxide activators), bleach catalysts, and oxygen transfer agents which, in combination with a peroxide, form a bleaching-active species.

Examples of peroxides are hydrogen peroxide, in free form or as adduct (urea adduct, percarbonate), perborates, organic and inorganic peracids, such as peracetic acid and higher organic peracids or Caro's acid or salts thereof.

Peroxide activators are organic compounds containing hydrolyzable O-acyl groups, N-acyl groups or nitrile groups.

Examples of O-acyl compounds are: carboxylic anhydrides such as acetic anhydride, nonanoic anhydride, decanoic anhydride, (substituted) succinic anhydrides, phthalic anhydrides or adipic anhydride, lactones such as valerolactone and caprolactone, acylated polyols such as triacetin, ethylene glycol diacetate, acetyl triethyl citrate (ATEC), 2,5-diacetoxy 2,5-dihydrofuran, acetylated sorbitol and mannitol, and their mixtures (SORMAN), as described in EP 525,239, acylated sugars, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose.
Further, in consideration acylated phenols such as Acetylphenolsulfonate, Octanoyloxybenzolsulfonate, nonanoyloxybenzenesulfonates (NOBS), isononanoyloxybenzenesulfonates (ISONOBS), Decanoyloxybenzolsulfonate, Lauroyloxybenzolsulfonate (LOBS), benzoyl (BOBS), Octanoyloxybenzolcarbonsäuren and nonanoyloxybenzenesulfonic, Decanoyloxybenzolsulfonsäuren (DOBA) and their salts, as well as the higher homologues come with C9-C12 alkyl radicals. Furthermore, it is possible to use amido-carboxylic acid-substituted phenol derivatives as described in EP 170 386.

Another important group of bleach activators are the N-acyl compounds. Examples which may be mentioned are acylated lactam derivatives such as acetylcaprolactam, octanoylcaprolactam, nonanoylcaprolactam, benzoylcaprolactam, octanoylvalerolactam, nonanoylvalerolactam, acylated imides such as N-acetylphthalimide or N-nonanoylsuccinimide (NOSI). Of particular interest are acylated amides such as tetraacetylethylenediamine (TAED), tetraacetylglucoluril (TAGU), 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT).

Examples of nitrile derivatives include i.a. in Surf Surf Surf. Det. 34 (1997), 404-409. These include aliphatic or aromatic nitriles, such as acetonitrile, benzonitrile, 2-cyanopyridine, 3-cyanopyridine, 4-cyanopyridine, N-methyl-4-cyanopyridinium chloride, N-methyl-4-cyanopyridinium methosulfate, N-methyl-4-cyanopyridinium tosylat and N-methyl-2-cyanopyridinium chloride, cyanamide derivatives as described in EP 0 008 475 or US 5,478,536, such as n-cyanomorpholine, N-cyanopiperidine, N-cyanopyrrolidine or cyanamide. As nitrile derivatives further Nitrilquats come into consideration, as they u.a. in EP 303 520 A, EP 458 396, EP 484 880, WO 96 40661 and EP 790 244.

The group of bleach catalysts includes both preformed transition metal complexes and their free ligands, which are capable of absorbing corresponding metal atoms during use from the water or the dirt to be bleached and generating the complex in situ. Corresponding complexes or their ligands are i.a. described in EP 458 379, EP 765 381, EP 902 083, EP 909 908, EP 12 25 215, WO 96/37593, WO 97/48787, WO 98/39098, WO 98/39406, WO 00/27975, WO 01 / 64697, WO 01/85717, WO 02/48301, WO 02/50229, WO 02/064721, WO 02/066592, US 6,306,812,

Among the oxygen transfer agents include special ketones that form in situ in the presence of peroxide-containing compounds bleach-active dioxiranes.
Examples of this can be found inter alia in US Pat. No. 3,822,144, US Pat. No. 5,785,887, WO 95/31527 and EP 12 03 576 or EP 12 09 221.
Furthermore, the group of oxygen transfer agents belong to precursors for oxaziridines or oxaziridinium salts, as described, for example, in US Pat. Nos. 5,041,232, 5,047,163, 5,045,233, 5,360,569, 5,710,116, WO 01/016273.

Of these, derivatives of dihydroisoquinolinium salts are used in particular in the formulations according to the invention.

Mixtures of different activators or activators with catalysts can lead to synergistic effects in the bleaching and disinfecting process. Combinations of a hydrophilic activator with a hydrophobic activator are preferred here. Examples are mixtures of TAED with NOBS, NOBS with nitrile quat or acetylcaprolactam with a cyanamide derivative. Particularly preferred are mixtures of an activator with a sulfonimine or an iminium derivative, such as TAED and N-methyl-dihydroisoquinolinium quat.

It does not matter whether the activators, catalysts or oxygen transfer agents per se are solid or liquid, water-soluble, water-miscible or solid. These compounds, when used in solid form, may be in either powdered form, wherein a coating of the individual powder particles may be by microencapsulation or a coating layer, or in granulated form with other components. Aqueous solutions of these compounds may contain from 0.01% to amounts of the solubility limit of the substance.

The bleaching components according to the invention can be used in washing, cleaning, disinfecting and bleaching processes of any kind, in the household or in the industrial sector. They are preferably used in the household sector as a booster component for separate addition to the washing process, as a component of a two-chamber bleaching system in which the peroxide source and bleach activator are initially present separately in two different chambers and mixed or sprayed shortly before the bleaching agent is used via appropriate devices as described, for example, in US Pat. No. 3,760,986, WO 95/16023 or WO 97/31087,
as one of the bleach components in multi-component detergent or as a physically separate bleach component in Liquitabs (individually packaged liquid detergents).

In the industrial sector, the bleaching component is used eg as Separately metered component for commercial textile cleaning, as a separately metered component for the disinfection of hard surfaces or as a separately metered component for wood and paper bleach.

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

In a preferred embodiment, the bleach components of the present invention contain complexing agents to bind traces of heavy metals. The salts of polyphosphoric acids, such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepentamethylenephosphonic acid (DTPMP), preferably in amounts by weight of 0.1 to 1.0 wt% can be used. Furthermore, acidic or alkaline additives are advantageous for adjusting the pH of the liquid component; In order to keep it constant during storage, the use of buffer mixtures makes sense.

The bleach components according to the invention may contain activators, catalysts or oxygen transfer agents in amounts of from 0.01 to 30% by weight, more preferably from 0.5 to 18% by weight, in particular from 1.5 to 9% by weight. In the case of using bleach catalysts, amounts of 0.001 to 5 wt .-% may be included.

Depending on the desired viscosity of the formulation according to the invention, the concentration of the polymer component is between 0.01 and 5% by weight, preferably between 0.05 and 2% by weight. Depending on the amount of polymer used, the viscosity of the resulting gels can be between 100 and 100,000 mPas. Even at elevated storage temperatures, a stable viscosity over months is found. The thickening of the bleaching component makes it easier for the user to set the optimal dosage. The solution does not splash and the handling is safer.

The desired viscosity of the bleaching component 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. The amount of water or organic solvent is generally 70 to 99 wt .-%.

The bleach components according to the invention are customarily adjusted to a pH in the range from 2 to 8, preferably from pH 2.1 to 7.5, more preferably from 2.2 to 6.5.

The bleach components according to the invention may contain in small amounts in each case specific auxiliaries and additives, for example acidic components, surfactants, builders, salts, optical brighteners, grayness inhibitors, solubilizers, enzymes, preservatives, fragrances and dyes, pearlescers, foam inhibitors, sequestering agents. However, these auxiliaries and additives are preferably constituents of detergents and cleaners which contain the liquid bleach components according to the invention.

Suitable acidic components are organic or inorganic acids, preferably organic acids, particularly preferably alpha-hydroxy acids and acids selected from glycolic acid, lactic acid, citric acid, tartaric acid, mandelic acid, salicylic acid, ascorbic acid, pyruvic acid, oligooxa mono- and dicarboxylic acids, fumaric acid, retinoic acid, aliphatic and organic Sulfonic acids, benzoic acid, kojic acid, fruit acid, malic acid, gluconic acid, galacturonic acid.

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

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

eingesetzt werden, worin R⁸ eine Alkyl-, Hydroxyalkyl- oder Alkylphenolgruppe oder Mischungen hiervon darstellt mit einer Kettenlänge von 8 bis 22 Kohlenstoffatome; R⁹ ist eine Alkylen- oder Hydroxyalkylengruppe mit 2 bis 3 Kohlenstoffatomen oder Mischungen hiervon; R¹⁰ ist eine Alkyl- oder Hydroxyalkylgruppe mit. 1 bis 3 Kohlenstoffatomen oder eine Polyethylenoxidgruppe mit 1 bis 3 Ethylenoxideinheiten. Die R¹⁰/R⁹-Gruppen können miteinander über ein Sauerstoff- oder Stickstoffatom verbunden sein und somit einen Ring bilden.
Diese Aminoxide umfassen besonders C₁₀-C₁₈-Alkyldimethylaminoxide und C₈-C_12-Alkoxyethyl-Dihydroxyethylaminoxide.Furthermore, semipolar nonionic surfactants, for example amine oxides of the formula III

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

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

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

Alkyl

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

alkyl sulfates

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

alkyl ether

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

Other anionic surfactants useful in laundry detergents and cleaners are C ₈ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonation of pyrolysis products of alkaline earth metal citrates such as described in British Patent GB 1,082,179, alkyl glycerol sulfates, fatty acyl glycerol sulfates, oleyl glycerol sulfates, Alkylphenol 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 C ₈ -C ₂₂ alkyl, k is a number of 0 to 10 and M is a soluble salt-forming cation. Resin acids or hydrogenated resin acids such as rosin or hydrogenated rosin or tall oil resins and tall oil rosin acids are also useful. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II, Schwartz, Perry and Berch). A variety of such surfactants are also claimed in U.S. Patent 3,929,678.

Examples of amphoteric surfactants are, above all, 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 substituents between. Contains 8 to 18 carbon atoms and an anionic, water-soluble group, such as e.g. Carboxy, sulfonate, sulfate, phosphate or phosphonate contains.

Further preferred amphoteric surfactants are alkyl dimethyl betaines,
Alkylamidobetaines and Alkyldipolyethoxybetaine 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 marketed, for example, by Clariant GmbH under the trade name Genagen® CAB.

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 Layered silicates may be present in an amount of up to 20% by weight 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 the search 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.

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

The formulations 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.

Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases, oxidases and peroxidases 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.

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

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

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

Examples

In the following examples the following copolymers according to the invention were used:

Copolymer A composition

• 48 g AMPS
• 50 g of acrylamide
• 2 g of PLEX 6935-O
• 1.8 g TMPTA
• 1.2 g DLP

Copolymer B composition

• 48 g AMPS
• 50 g of acrylamide
• 2 g of Genapol® LAA70 methacrylate
• 1.8 g TMPTA
• 1.2 g DLP

Copolymer C composition

• 30 g AMPS
• 50 g of acrylamide
• 20 g MPG 750 methacrylate
• 1.8 g TMPTA
• 1.2 g DLP

Copolymer D composition

• 30 g AMPS
• 50 g of acrylamide
• 20 g MPG 1500 methacrylate
• 1.8 g TMPTA
• 1.2 g DLP

• 600 g tert.-Butanol wurden vorgelegt und dazu AMPS, neutralisiert mit NH₄IG, zugegeben. Anschließend wurden die restlichen Monomeren zugegeben, mit Stickstoff inertisiert und dann DLPals Starter zugegeben. Es setzte eine exotherme Reaktion ein, nach deren Abklingen noch 4 Stunden unter Rückfluss erhitzt wurde.
• Das Reaktionsgemisch wurde dann unter Vakuum eingedampft. Die jeweiligen Polymere fielen dabei als weiße Pulver an.

The preparation of the copolymers A, B, C and D was carried out according to the following general procedure:

• 600 g of tert-butanol were initially charged and to it AMPS, neutralized with NH ₄ IG added. Subsequently, the remaining monomers were added, rendered inert with nitrogen and then DLP added as a starter. It began an exothermic reaction, after its decay was heated under reflux for 4 hours.
• The reaction mixture was then evaporated under vacuum. The respective polymers were obtained as white powders.

Abbreviations:

AMPS: Acryloyldimethyltaurinsäure PLEX 6935-O: Behenyl alcohol polyglycol ether (25 EO) methacrylate Genapol LA070- C ₁₂ / C ₁₆ fatty alcohol polyglycol ether methacrylate (7 EO) methacrylate MPG 750 methacrylate: Methanol polyglycol ether (750 EO) methacrylate MPG 1500 methacrylate: Methanol polyglycol ether (1500 EO) methacrylate TMPTA: Trimethylolpropane triacrylate DLP: Di-lauroyl peroxide

Example 1: TAED-containing bleach components

formulation 1 2 3 TAED powder (20-100 μm) 5 10 20 Dequest 0.5 0.4 0.5 Copolymer A 0.07 0.1 0.3 water ad 100 Viscosity (CPS) 1x10 ³ 6x10 ³ 8x10 ³ pH value (1%) 4.6 4.7 4.7

All three formulations are characterized by excellent physical and chemical storage stability. The active oxygen loss on TAED is less than 2% at 4 weeks storage at 25 ° C. The formulations 1 to 3 can be used, for example, in commercial laundries in order to improve the bleaching result of hydrogen peroxide-containing formulations and to significantly increase the disinfecting action. Furthermore, such components are used in wood and paper bleaching where they can replace hard-to-handle powdered bleach activators.

Formulations 4 to 6

formulation 4 5 6 TAED powder (<10 μm) 3 8th 16 Dequest 2066® 0.3 0.3 0.3 Copolymer B 0.05 0.07 0.1 N-methyldihydroisoquinolinium tosylate (US 5,360,569) 0.3 0.1 - water ad 100

Conventional TAED powder was first ground down in a ball mill to the desired particle size, then stirred into the solution of dequest and copolymer in water. The three formulations are characterized by excellent physical and chemical storage stability. The active oxygen loss is <1% at 4 weeks of storage at 25 ° C. Formulations 4 to 6 may e.g. be used as a component of multi-chamber liquid detergents in which hydrogen peroxide and activator are spatially separated during storage and it is combined shortly before use. As a result, the bleaching result of the hydrogen peroxide-containing formulations is significantly improved and the disinfecting effect is significantly increased.

Formulations 7 to 9

formulation 7 8th 9 TAED powder (<10 μm) 3 6 8th Hostapur SAS® 2 - - Genapol OA080 - 5 3 Genapol UD 030 - - 2 Dequest 2066® 0.3 0.3 0.5 Copolymer C 0.05 0.07 0.1 water ad 100

Conventional TAED powder was first ground down in a ball mill to the desired particle size, then stirred into the solution of dequest and copolymer in water. The three formulations are characterized by excellent physical and chemical storage stability. The active oxygen loss on TAED is <3% at 4 weeks storage at 25 ° C. Formulations 7 to 9 may be e.g. be used as a component of multi-chamber liquid detergents in which hydrogen peroxide and activator are spatially separated during storage and it is combined shortly before use. As a result, the bleaching result of hydrogen peroxide-containing formulations is significantly improved and the disinfecting effect significantly increased.

Example 2: Formulation with cyano compounds as bleach activators

formulation 10 11 12 cyanopiperidine 2 - - cyanopyrrolidine - - 3 cyanomorpholine - 4 - Copolymer A 0.05 0.07 - Copolymer D - - 0.1 water ad 100

The three formulations are characterized by excellent physical and chemical storage stability. The active oxygen loss is <2% at 4 weeks storage at 40 ° C. The formulations 10 to 12 can be used, for example, as a component of multi-chamber liquid detergents in which hydrogen peroxide and activator are spatially separated during storage and are combined shortly before use, for example via a spray nozzle. As a result, the bleaching result of hydrogen peroxide-containing formulations is significantly improved and the disinfecting effect significantly increased. The high viscosity of the formulation prevents rapid blistering of the combined bleach from smooth surfaces, thereby allowing for longer exposure time. In a particular embodiment, the hydrogen peroxide solution is also through Addition of 0.03 to 0.5% of the copolymer thickened to adjust an approximately equal viscosity in both chambers of the two-chamber container.

Abbreviations:

Hostapur SAS: sec. alkanesulfonate Genapol OA080: C ₁₄ / C ₁₅ oxo alcohol polyglycol ether (8 EO) Genapol UD030: C ₁₁ -oxalohol polyglycol ether (3 EO) TAED: Tetraacetyl ethylene diamine

Formulations 13 and 14

formulation 13 14 Trimethylammonium acetonitrile methosulfate 2 5 Dequest 2041® 0.1 0.2 Copolymer B 0.07 0.1 water ad 100 Formulations 15 to 17 15 16 17 Lauroyloxybenzenesulfonate-Na 4 - - decanoyloxybenzoic - 2 - Nonanoyloxybenzenesulfonate Na - - 5 Dequest 2041® 0.3 0.3 0.3 Copolymer A 0.1 0.1 0.07 Genapol OA 080® 2 - - water ad 100

Claims (8)

1. A liquid bleaching composition component comprising

   1) amphiphilic copolymers which include structural units which are derived from

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

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

   c) further at least monovinylically unsaturated comonomers different from a) and b), and

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