EP1426436A1 - Liquid bleaching component comprising amphiphilic polymers - Google Patents

Abstract

Liquid bleach activator composition comprises a bleach activator and an amphiphilic copolymer comprising optionally neutralized acryloyldimethyltauric acid, a hydrophobic ethylenically unsaturated polyalkylene oxide and optionally a vinyl comonomer.

Description

The present invention relates to liquid or pasty, homogeneous and heterogeneous Bleaching agent components containing hydrophobically modified copolymers based on of acryloyldimethyltauric acid. Bleaching agent components are to be understood organic or organometallic substances, which in combination with a Peroxide source form bleaching active species that lead to bleaching, oxidation, but also Disinfection purposes can be used. These include in particular Bleach activators and bleach catalysts as well as oxygen transfer agents. The manufacture bleaches containing the bleach components according to the invention are characterized by favorable rheological behavior, as well as good Compatibility with other components. They have a high physical and chemical storage stability, as well as high hydrolysis stability of the components, especially the bleach component and the copolymer.

Of modern liquid bleach components for use in commercial and Household demands are high, closely related to the rheology of the products are linked: They must be combined with a second one containing peroxide Develop high bleach and disinfectant component user-friendly, safe, very well tolerated by the skin, but also environmentally friendly his. To improve handling for the consumer and the consumer Appearance increasingly come liquid products with higher viscosities in the trade, so that thickeners and gel formers play a major role. For commercial use in industrial cleaning, for paper or boring Textile bleaching and surface disinfection require the liquid components to be pumpable and easy to dose in order to make simple industrial processing possible guarantee.

So far, almost exclusively synthetic or semi-synthetic polymers based on cross-linked polyacrylic acids (carbomers, Carbopole), partially hydrolyzed polyacrylamides, cellulose ethers, xanthan or guar gum related. The problem of intolerance to low pH always arises on what the applications of many products are on the neutral or weakly acidic range. This is particularly problematic Thickening of bleach components, especially those Bleach activators that form particularly easily in aqueous formulations hydrolyze of acids and consequently pH in the acidic range let it sink.

Surprisingly, it has been possible to overcome this disadvantage by using Hydrophobically modified copolymers based on acryloyldimethyltaurate, their Production is described in EP 10 69 142 to eliminate.

Due to the copolymers described there, bleaching agent formulations can be used as Component for washing, cleaning and disinfecting to viscosities larger 100 cP can be set. In special embodiments, these are Formulations with an acid to weakly alkaline character (pH <8). Fortunately, these formulations are also characterized by a high UV stability. This enables the use of transparent Packaging materials.

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) mindestens einem Bleichaktivator, Bleichkatalysator oder Sauerstofftransfer-Agens.

The invention relates to liquid bleaching agent components containing

1) amphiphilic copolymers comprising structural units which are derived from

a) Acryloyldimethyltauric acid in free, partially or fully 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 mono vinylically unsaturated comonomers different from a) and b), and

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 10 ⁴ to 10 ⁷ g / mol, particularly preferably 5 * 10 ⁴ to 5 * 10 ⁶ g / mol.

The Acryloyldimethyltauraten (structural unit a) can be the inorganic or organic salts of Acryloyldimethyltaurinsäure. The Li ⁺ , Na ⁺ , K ⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Al ⁺⁺⁺ and / or NH ₄ ⁺ salts are preferred. Also preferred are the monoalkylammonium, dialkylammonium, trialkylammonium and / or tetraalkylammonium salts, where the alkyl substituents of the amines can be (C ₁ -C ₂₂ ) alkyl radicals independently of one another, which may optionally contain up to 3 (C ₂ - C ₁₀ ) hydroxyalkyl groups can 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 representatives are also suitable.

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

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

According to the invention, at least one so-called Macromonomers (structural unit b) are used. It is the Macromonomers with at least simple olefinically functionalized polymers one or more discrete repetition units and a number-average Molecular weight greater than or equal to 200 g / mol. When copolymerizing mixtures of chemically different macromonomers can also be used.

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

Preferred macromonomers b) are compounds of the formula (I) R ¹ - Y - [(A) _v - (B) _w - (C) _x - (D) _z ] - R ² where R ^{1 represents} a polymerizable function from the group of vinylically unsaturated compounds which are suitable for building polymeric structures by radical means. R ¹ preferably represents a vinyl, allyl, methallyl, methylvinyl, acrylic, methacrylic, crotonyl, senecionyl, itaconyl, maleinyl, fumaryl or styryl radical.
A suitable bridging group Y is required to connect the polymer chain to the reactive end group. 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 ) -, particularly preferably -O-.
The polymeric middle part of the macromonomer is represented by the discrete repeat 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 , especially of ethylene oxide and propylene oxide.
The indices v, w, x and z in formula (I) represent the stoichiometric coefficients relating to the repeating units A, B, C and D. v, w, x and z are independently 0 to 500, preferably 1 to 30, the The sum of the four coefficients must be ≥1 on average.

The distribution of the repeating units over the macromonomer chain can be statistical, block-like, 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 ], these are difunctional macromonomers which are suitable for crosslinking the copolymers. An example of this is the compound polyethylene glycol (molecular weight 440) diacrylate.

R₃, R₄, R₅ und R₆ bedeuten hier unabhängig voneinander Wasserstoff oder n-aliphatische, iso-aliphatische, olefinische, cycloaliphatische, arylaliphatische oder aromatische (C₁-C₃₀)-Kohlenwasserstoffreste.
Bevorzugt sind R₃ und R₄ gleich H oder -CH₃, besonders bevorzugt H; R₅ ist gleich H oder -CH₃; und R₆ ist gleich einem n-aliphatischen, iso-aliphatischen, olefinischen, cycloaliphatischen, arylallphatlschen oder aromatischen (C₁-C₃₀)-Kohlenwasserstoffrest.
v und w sind wiederum die stöchiometrischen Koeffizienten betreffend die Ethylenoxideinheiten (EO) und Propylenoxideinheiten (PO). v und w betragen unabhängig voneinander 0 bis 500, bevorzugt 1 bis 30, wobei die Summe aus v und
w im Mittel ≥1 sein muss. Die Verteilung der EO- und PO-Einheiten über die Makromonomerkette kann statistisch, blockartig, alternierend oder gradientenartig sein. Y steht für die obengenannten Brücken. Vorzugsweise ist Y = Sauerstoff.Particularly preferred macromonomers b) are acrylic or methacrylic monofunctionalized alkyl ethoxylates of the formula (II).

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

Particularly preferred macromonomers have the following structure according to formula (II), where Y in all cases means oxygen: description R ³ R ⁴ R ⁵ R ⁶ v w LA-030 methacrylate H H -CH _3rd lauryl 3 0 LA-070 methacrylate H H -CH _3rd lauryl 7 0 LA-200 methacrylate H H -CH _3rd lauryl 20 0 LA-250 methacrylate H H -CH _3rd lauryl 25 0 T-080 methacrylate H H -CH _3rd -Tallow 8th 0 T-080 acrylate H H H -Tallow 8th 0 T-250 methacrylate H H -CH _3rd -Tallow 25 0 description R ³ R ⁴ R ⁵ R ⁶ v w T-250-crotonate -CH _3rd H -CH _3rd -Tallow 25 0 OC-030 methacrylate H H -CH _3rd octyl 3 0 OC-105 methacrylate H H -CH _3rd 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 _3rd -CH ₃ - H -Behenyl 10 0 B-11-50 methacrylate H H -CH _3rd butyl 17 13 MPEG-750 methacrylate H H -CH _3rd -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, particularly preferably 150 to 10 ⁴ g / mol and particularly preferably 200 to 5000 g / mol.

All olefinically unsaturated monomers can be used as comonomers c) are the reaction parameters of a copolymerization with acryloyldimethyltauric acid and / or Acryloyldimethyltauraten in the respective reaction media allow.

Open-chain N-vinylamides are preferably used, preferably N-vinylformamide (VIFA), N-vinylmethylformamide, N-vinylmethylacetamide (VIMA) and N-vinylacetamide; cyclic N-vinylamides (N-vinyllactams) with a ring size of 3 to 9, preferably N-vinylpyrrolidone (NVP) and N-vinylcaprolactam; Amides of acrylic and methacrylic acid, preferably acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and N, N-diisopropylacrylamide; alkoxylated acrylic and methacrylamides, preferably hydroxyethyl methacrylate, hydroxymethyl methacrylamide, hydroxyethyl methacrylamide, hydroxypropyl methacrylamide and succinic acid mono- [2- (methacryloyloxy) ethyl ester]; N, N-dimethylaminomethacrylate; diethylaminomethyl; Acrylic and methacrylamidoglycolic acid; 2- and 4-vinyl pyridine; vinyl acetate; methacrylate; styrene; acrylonitrile; stearyl; lauryl;
In addition, one or more unsaturated carboxylic acids or their salts can be polymerized into the structure. Acrylic acid, methacrylic acid, styrene sulfonic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and senecionic acid are particularly preferred.
Preferred counterions of the acids are Li ⁺ , Na ⁺ , K ⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Al ⁺⁺⁺ , NH ₄ ⁺ , monoalkylammonium, dialkylammonium, trialkylammonium and / or tetraalkylammonium residues, where the Alkyl substituents of the amines can independently of one another be (C ₁ -C ₂₂ ) alkyl radicals which can optionally be occupied by up to 3 (C ₂ -C ₁₀ ) hydroxyalkyl groups. In addition, one to three times ethoxylated ammonium compounds with different degrees of ethoxylation can also be used. 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) with at least two polymerizable vinyl groups.
Preferred crosslinkers are methylene bisacrylamide; methylenebismethacrylamide; Esters of unsaturated mono- and polycarboxylic acids with polyols, preferably diacrylates and triacrylates or methacrylates, particularly preferably butanediol and ethylene glycol diacrylate or methacrylate, trimethylolpropane triacrylate (TMPTA) and allyl compounds, preferably allyl (meth) acrylate, triallyl cyanyl esterylate, maleic acid allyl allyl anilide, maleic acid allyl allyl allyl allyl allyl allyl, , Triallylamine, tetraallylethylenediamine; Allyl esters of phosphoric acid; and / or vinylphosphonic acid derivatives.
Trimethylolpropane triacrylate (TMPTA) and timethylolpropane trimethacrylate (TMPTMA) are particularly preferred as crosslinkers.

Mixtures of mono-vinyl unsaturated comonomers with multiple Unsaturated 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 0.01 to 90% by weight, particularly preferably 0.05 to 50% by weight and particularly preferably 0.1 to 40% by weight.

All organic or inorganic can be used as the polymerization medium Solvents are used that relate to radical polymerization reactions behave largely inert and advantageously the formation of medium or high Allow molecular weights. Water is preferred; lower alcohols; preferably methanol, ethanol, propanols, iso-, sec.- and t-butanol, particularly preferably t-butanol; Hydrocarbons from 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, particularly preferably between 10 and 100 ° C, both at normal pressure and even under increased or reduced pressure. If necessary, the Polymerization also under a protective gas atmosphere, preferably under Nitrogen.

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, for example, azodiisobutyronitrile (AIBN), can be used to trigger the polymerization.
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 (e.g. sodium bisulfite, ascorbic acid, iron (II) sulfate etc.) or redox systems which contain an aliphatic or aromatic sulfonic acid (for example benzenesulfonic acid, toluenesulfonic acid etc.) as reducing component.

The polymerization reaction can e.g. as precipitation polymerization, Emulsion polymerization, bulk polymerization, solution polymerization or Gel polymerization performed. Particularly advantageous for the property profile of Copolymers according to the invention is the precipitation polymerization, preferably in tert-butanol.

The bleach component Bleaching agent components are to be understood as bleach activators (Peroxide activators), bleaching 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 an adduct (Urea adduct, percarbonate), perborates, organic and inorganic Peracids such as peracetic acid and higher organic peracids or Caro's Acid or its salts.

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

Examples of O-acyl compounds are: carboxylic acid 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, acetylacetoxyethyl, acetylene triethyl acetylene triacetate, ethylene glycol triacetate, ethylene glycol triacetate, ethylene glycol triacetate, ethylene glycol triacetate, ethylene glycol triacetate, acetylene triacetate, ethylene glycol triacetate, ethylene glycol triacetate, acetylene diacetyl, -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 residues. It is also possible to use amidocarboxylic acid-substituted phenol derivatives as described in EP 170 386.

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

Examples of nitrile derivatives include in Surfactants Surf. Det. 34: 404-409 (1997) described. 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 tosylate 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. Come as nitrile derivatives continue to consider nitrile quats, such as in EP 303 520 A, EP 458 396, EP 484 880, WO 96 40661 and EP 790 244 are described.

The group of bleach catalysts includes both prefabricated ones Transition metal complexes, as well as their free ligands, which are able to corresponding metal atoms during use from the water or to pick up bleaching dirt and generate the complex in-situ. Corresponding complexes and their ligands include 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,

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

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

Mixtures of different activators or activators with catalysts can lead to synergistic effects in the bleaching and disinfection process. Combinations of a hydrophilic and a hydrophobic are preferred here Activator. Examples are mixtures of TAED with NOBS, NOBS with nitrile quat or Acetylcaprolactam with a cyanamide derivative. Are particularly preferred 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 solid or liquid, water soluble, water miscible or are firm. These compounds can, if used in solid form be either in powder form, with an envelope of each Powder particles can be given by microencapsulation or a coating layer can, or be in granular form with other components. aqueous Solutions of these compounds can range from 0.01% to amounts of Contain the solubility limit of the substance.

The bleaching agent components according to the invention can be used in washing, cleaning, disinfection and bleaching processes of all kinds, in the household or in the industrial field. They are preferably used in the household sector as a booster component for the 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 are mixed or sprayed shortly before use of the bleaching agent using 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 detergents or
as a physically separate bleach component in Liquitabs (individually packaged liquid detergents).

In the industrial sector, the bleach component is e.g. use as separately metered component for commercial textile cleaning, as separately metered component for disinfection of hard surfaces or as separately metered component for wood and paper bleaching.

The washing, cleaning, disinfecting and bleaching agents that the Bleach components according to the invention can contain in the form of aqueous, aqueous / organic, especially aqueous / alcoholic and organic formulations. Other embodiments can be: Emulsions, dispersions, gels and suspensions.

In a preferred embodiment, the inventive Bleaching agent complexing agent to trace traces of heavy metals tie. It can be the salts of polyphosphoric acids, such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and diethylenetriaminepentamethylenephosphonic acid (DTPMP), preferably in quantities of 0.1 to 1.0 wt%. Furthermore, acidic or alkaline additives are advantageous to adjust the pH of the adjust liquid component; to keep it constant during storage hold, the use of buffer mixtures makes sense.

The bleaching agent components according to the invention can be activators, Catalysts or oxygen transfer agents in amounts of 0.01 to 30% by weight, particularly preferably contain 0.5 to 18% by weight, in particular 1.5 to 9% by weight. If bleaching catalysts are used, amounts of 0.001 to 5 can be used % By weight 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 viscosity that is stable 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 becomes safer.

The desired viscosity of the bleach component can be achieved by adding Water and / or organic solvents or by adding a combination from organic solvents and other thickeners. In principle, all mono- or polyvalent come as organic solvents Alcohols into consideration. Alcohols with 1 to 4 carbon atoms such as Methanol, ethanol, propanol, isopropanol, straight-chain and branched butanol, Glycerin and mixtures of the alcohols mentioned. Further preferred alcohols are polyethylene glycols with a relative molecular weight below 2000. In particular, the use of polyethylene glycol with a relative Molecular mass between 200 and 600 and in amounts up to 45 wt .-% and from Polyethylene glycol with a molecular weight between 400 and 600 in Amounts of 5 to 25% by weight are preferred. The amount of water or organic Solvent is generally 70 to 99 wt .-%.

The bleaching agent components according to the invention are usually at a pH Value in the range 2 to 8, preferably pH 2.1 to 7.5, particularly preferably 2.2 to 6.5 set.

The bleach components according to the invention can be used in small amounts still specific auxiliaries and additives, for example acidic Components, surfactants, builders, salts, optical brighteners, graying inhibitors, Solubilizers, enzymes, preservatives, fragrances and dyes, Pearlescent agents, foam inhibitors, sequestering agents. These are preferred Auxiliaries and additives, however, part of detergents and cleaning agents contain the liquid bleaching agent 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.

The surfactants can be nonionic, anionic, cationic or amphoteric in nature.
Preferred nonionic surfactants are fatty alcohol oxyethylates with approx. 1 to approx. 25 mol ethylene oxide. The alkyl chain of the aliphatic alcohols can be linear or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. The condensation products of alcohols which contain an alkyl chain of 10 to 20 carbons with 2 to 18 mol of ethylene oxide per mol of alcohol are particularly preferred. The alkyl chain can be saturated or unsaturated. Likewise, the alcohol ethoxylates can 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 mol of ethylene oxide), Tergitol ™ 24-L-NMW (condensation product of a C ₁₂ -C ₁₄ linear primary Alcohol with 6 mol ethylene oxide with a narrow molecular weight distribution). The Genapol ™ brands from Clariant GmbH also fall under this product class.

In addition, other known types of come according to the invention nonionic surfactants in question, such as polyethylene, polypropylene and Polybutylene oxide adducts of alkylphenols with 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 with propylene glycol or addition products from Ethylene oxide with a reaction product of propylene oxide and ethylenediamine.

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

are used, wherein R ^{8 represents} an alkyl, hydroxyalkyl or alkylphenol group or mixtures thereof with 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 can be connected to one another via an oxygen or nitrogen atom and thus form a ring.
These amine oxides particularly include C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₈ -C ₁₂ alkoxyethyl dihydroxyethylamine oxides.

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

Straight-chain and branched are particularly suitable as anionic surfactants Alkyl sulfates, sulfonates, carboxylates, phosphates, alkyl ester sulfonates, Arylalkyl sulfonates, alkyl ether sulfates and mixtures of the above Links. The following are some of the types of anionic surfactants are described in more detail.

Alkyl

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 "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials are natural fat 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, in which R preferably represents a C ₁₀ -C ₂₄ hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical having 10 to 20 C atoms, particularly preferably a C ₁₂ -C ₁₈ alkyl or hydroxyalkyl radical , M is hydrogen or a cation, for example an alkali metal cation (for example 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 approx. 50 ° C) and alkyl chains with C ₁₆ -C _{18 are} preferred for higher washing temperatures (eg above approx. 50 ° C).

alkyl ether

The alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) _m SO ₃ M, in which 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 or hydroxyalkyl, particularly preferably a C ₁₂ -C ₁₈ alkyl or hydroxyalkyl radical. A is an ethoxy or propoxy unit, m is a number greater than 0, typically between approximately 0.5 and approximately 6, particularly preferably between approximately 0.5 and approximately 3, and M is a hydrogen atom or a cation such as e.g. a metal cation (e.g. 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 include 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, the cation being sodium or potassium.

Other anionic surfactants which are useful for use in detergents and cleaning agents are C ₈ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids, prepared by sulfonating the pyrolysis products of alkaline earth metal citrates, as described, for example, in British Patent GB 1,082,179, alkyl glycerol sulfates, fatty acyl glycerol sulfates, oleyl glycerol sulfates alkylphenol ether sulfates, primary paraffinsulfonates, alkyl phosphates, alkyl ether phosphates, isethionates such as the acyl isethionates, N-acyl taurides, alkyl succinamates, sulfosuccinates, monoester 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 polyethoxy carboxylates such as those of the formula RO (CH ₂ CH ₂ ) _k CH ₂ COO ^- M ⁺ where R is a C ₈ -C ₂₂ alkyl, k a number from 0 to 10 and M is a soluble one Is salt forming cation. Resin acids or hydrogenated resin acids such as rosin or hydrogenated rosin or tall oil resins and tall oil resin acids can also be used. 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, especially those that are widely used as derivatives of aliphatic secondary and tertiary amines are described, 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 one anionic, water-soluble group, e.g. Carboxy, sulfonate, sulfate, phosphate or contains phosphonate.

Further preferred amphoteric surfactants are alkyldimethylbetaines, Alkylamidobetaines and alkyldipolyethoxybetaines with an alkyl radical which is linear or be branched out with. 8 to 22 carbon atoms, preferably 8 to 18 Carbon atoms and particularly preferably with. 12 to. 18 carbon atoms. These connections are e.g. from Clariant GmbH under the trade name Genagen® CAB marketed.

Neutral or are suitable as organic and inorganic builders especially alkaline salts that precipitate calcium ions or able to bind complex. Suitable and especially ecological harmless builder substances, such as finely crystalline, synthetic water-containing Zeolites of type NaA, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g have a preferred use. In non-aqueous Systems preferably use layered silicates. Zeolite and the Layered silicates can be contained in an amount of up to 20% by weight. Useful organic builders are, for example, those in the preferred form their sodium salts used percarboxylic acids, such as citric acid and Nitriloacetate (NTA), ethylenediaminetetraacetic acid, provided such use ecological reasons is not objectionable. Analogous to this, too polymeric carboxylates and their salts are used. This includes for example the salts of homopolymeric or copolymeric polyacrylates, Polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those from 50% to 10% maleic acid and also polyvinylpyrrolidone and urethanes. The relative molecular weight of the homopolymers is generally between 1000 and 100,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid, in particular also water-soluble polyacrylates are suitable, for example with about 1% Polyallylethers of the search rose are cross-linked and have a relative molecular mass own over a million. Examples of this are those under the name Carbopol 940 and 941 available polymers. The cross-linked polyacrylates are in Amounts not exceeding 1% by weight, preferably in amounts of 0.2 to 0.7% by weight used.

Examples of foam inhibitors are fatty acid alkyl ester alkoxylates, Organopolysiloxanes and their mixtures with microfine, optionally silanated Silica as well as paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of different can also be used with advantage Foam inhibitors are used, e.g. those made of silicone oil, paraffin oil or To grow. Foam inhibitors are preferably granular in water soluble or dispersible carrier substance bound.

The formulations can be optical brighteners, for example derivatives of Contain diaminostilbenedisulfonic acid or its alkali metal salts, which are good in let the dispersion work in. The maximum amount of brighteners in the agents according to the invention is 0.5 wt .-%, preferably amounts of 0.02 to 0.25 wt .-% used.

Enzymes come from the class of proteases, lipases, amylases, Cellulases, oxidases and peroxidases or their mixtures in question. Their share can be 0.2 to 1% by weight. The enzymes can be carried on carrier substances be adsorbed and / or be embedded in coating substances.

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

Sodium sulfate, sodium carbonate, for example, come as salts or adjusting agents or sodium silicate (water glass). As typical individual examples for other additives are sodium borate, starch, sucrose, polydextrose, Stilbene compounds, methyl cellulose, toluenesulfonate, cumene sulfonate, soaps and To name silicones.

The following examples and applications are intended to illustrate the invention explain, but without restricting it to (deals with all percentages % by weight).

Examples

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

Copolymer A composition

48 g AMPS

50 g acrylamide

2 g PLEX 6935-O

1.8 g TMPTA

1.2 g DLP

Copolymer B composition

48 g AMPS

50 g acrylamide

2 g Genapol® LA070 methacrylate

1.8 g TMPTA

1.2 g DLP

Copolymer C composition

30 g AMPS

50 g acrylamide

20 g MPG 750 methacrylate

1.8 g TMPTA

1.2 g DLP

Copolymer D composition

30 g AMPS

50 g acrylamide

20 g MPG 1500 methacrylate

1.8 g TMPTA

1.2 g DLP

Copolymers A, B, C and D were prepared according to the following general regulation:

600 g of tert-butanol were introduced and AMPS, neutralized with NH ₄ IG, was added. The remaining monomers were then added, inertized with nitrogen and then DLP as starter added. An exothermic reaction started, after which it had refluxed for 4 hours.

The reaction mixture was then evaporated in vacuo. The respective Polymers were obtained as white powders.

Abbreviations:

AMPS:

acryloyidimethyltaurine

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 bleaching agent 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 at TAED is less than 2% with 4 weeks storage at 25 ° C. Formulations 1 to 3 can e.g. in commercial laundries are used to control the bleaching result of formulations containing hydrogen peroxide and to improve the To significantly increase the disinfectant effect. Such components are also found when using wood and paper bleaching where it is difficult to handle can replace powdery 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-methyl-dihydroisoquinolinium tosylate (US 5,360,569) 0.3 0.1 - water ad 100

Conventional TAED powder was first applied to the in a ball mill Desired grain size, then in the solution from Dequest and copolymer stirred into water. The three formulations stand out excellent physical and chemical storage stability. The Active oxygen loss is <1% when stored for 4 weeks at 25 ° C. The Formulations 4 to 6 can e.g. as a component of Multi-chamber liquid detergents are used in which hydrogen peroxide and activator are physically separate during storage and he is shortly before Use can be combined. This will bleach the Formulations containing hydrogen peroxide significantly improved and the Disinfectant effect increased significantly.

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 applied to the in a ball mill Desired grain size, then in the solution from Dequest and copolymer stirred into water. The three formulations stand out excellent physical and chemical storage stability. The Active oxygen loss at TAED is <3% when stored for 4 weeks at 25 ° C. The Formulations 7 to 9 can e.g. as a component of Multi-chamber liquid detergents are used in which hydrogen peroxide and activator are physically separate during storage and he is shortly before Use can be combined. The bleaching result of Formulations containing hydrogen peroxide significantly improved and the Disinfectant effect increased significantly.

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. Formulations 10 to 12 can e.g. as a component of Multi-chamber liquid detergents are used in which hydrogen peroxide and activator are physically separate during storage and he is shortly before Use e.g. can be combined via a spray nozzle. This will Bleaching result of formulations containing hydrogen peroxide significantly improved and significantly increased the disinfectant effect. The high viscosity of the Formulation prevents the combined bleach from draining away quickly smooth surfaces and thereby enables an extension of the exposure time. In In a special embodiment, the hydrogen peroxide solution is also carried out Addition of 0.03 to 0.5% of the copolymer thickened to approximately the same Adjust the viscosity in both chambers of the two-chamber container.

Abbreviations:

Hostapur SAS:

sec. alkanesulfonate

Genapol OA080:

C ₁₄ / C ₁₅ oxoalcohol polyglycol ether (8 EO)

Genapol UD030:

C ₁₁ oxoalcohol polyglycol ether (3 EO)

TAED:

Tetraacetyl ethylene diamine

Formulations 13 and 14

formulation 13 14 trimethyl 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)

Containing liquid bleach components 1) amphiphilic copolymers comprising structural units which are derived from a) Acryloyldimethyltauric acid in free, partially or fully 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 mono vinylically unsaturated comonomers different from a) and b), and 2) at least one bleach activator, bleach catalyst or oxygen transfer agent. Bleaching agent components according to claim 1, wherein the copolymers have a molecular weight M _w of 10 ³ g / mol to 10 ⁹ g / mol. Bleaching agent components according to claim 1, wherein the acryloyldimethyltaurates (structural unit a) Li ⁺ , Na ⁺ , K ⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Al ⁺⁺⁺ , NH ₄ ⁺ , monoalkylammonium, dialkylammonium , Trialkylammonium and / or tetraalkylammonium salts, the alkyl substituents of the amines independently of one another being (C ₁ -C ₂₂ ) alkyl radicals which can optionally be occupied by up to 3 (C ₂ -C ₁₀ ) hydroxyalkyl groups. Bleach components according to claim 1, wherein based on the Total mass of the copolymers, the content of acryloyldimethyltauric acid or Acryloyldimethyltaurates is 0.1 to 99.9 wt .-%. Bleaching agent components according to Claim 1, in which the copolymer as macromonomers b) compounds of the formula (I) R ¹ - Y - [(A) _v - (B) _w - (C) _x - (D) _z ] - R ² contains what
R ^{1 is} a polymerizable function from the group of the vinylically unsaturated compounds which is suitable for building polymer structures by radical means,
R ^{2 is} a linear or branched aliphatic, olefinic, cycloaliphatic, arylaliphatic or aromatic (C ₁ -C ₅₀ ) hydrocarbon radical, OH, -NH ₂ , -N (CH ₃ ) ₂ or the structural unit [-YR ¹ ],
Y for -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 ) - stands,
A, B, C and D are derived from acrylamide, methacrylamide, ethylene oxide, propylene oxide, AMPS, acrylic acid, methacrylic acid, methyl methacrylate, acrylonitrile, maleic acid, vinyl acetate, styrene, 1,3-butadiene, isoprene, isobutene, diethylacrylamide and diisopropylacrylamide,
v, w, x and z are independently numbers from 0 to 500, with the sum of the four coefficients on average ≥1. Bleaching agent components according to claim 1, wherein the molecular weight of the macromonomers b) is 200 g / mol to 10 ⁶ g / mol. Bleaching agent components according to claim 1, wherein the comonomers c) are olefinic unsaturated monomers are used, selected from N-vinylformamide (VIFA), N-vinylmethylformamide, N-vinylmethylacetamide (VIMA) and N-vinylacetamide; cyclic N-vinyl amides (N-vinyl lactams) with a ring size of 3 to 9, preferably N-vinylpyrrolidone (NVP) and N-vinylcaprolactam; Amides of acrylic and Methacrylic acid, preferably acrylamide, methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and N, N-diisopropylacrylamide; alkoxylated acrylic and Methacrylamides, preferably hydroxyethyl methacrylate, hydroxymethyl methacrylamide, Hydroxyethyl methacrylamide, hydroxypropyl methacrylamide and succinic acid mono- [2- (methacryloyloxy) ethyl ester]; N, N-dimethylaminomethacrylate; diethylaminomethyl; Acrylic and methacrylamidoglycolic acid; 2- and 4-vinyl pyridine; vinyl acetate; methacrylate; styrene; acrylonitrile; stearyl; Lauryl. Bleaching agent component according to Claim 1, containing a bleach activator organic compound with hydrolyzable O-acyl, N-acyl or nitrile groups.