EP0853655B1 - Builder combinations containing acrolein-vinyl acetate copolymers, detergents and cleaners containing these and their preparation - Google Patents

Abstract

Disclosed is a builder combination of at least one builder and/or complexing agent, containing at least one copolymer based on acrolein and vinyl acetate, having a ratio of acrolein to vinyl acetate ranging from 1:1 to less than 5.7:1 and a mean molecular mass in the range of 3,000 to 5,000, and/or its salt. Disclosed also are detergents and cleaners containing these builders and a method for preparing this builder combination and these detergents.

Description

The present invention relates to acrolein-vinyl acetate copolymer-containing Builders combinations, detergents and cleaning agents containing them and their manufacture.

Y für

und Z für -(F)q^-. steht, worin

A = H, OH, C_1-6 Alkyl, CH₂CO (DECO)_r-1OM;

B = H, OH, C_1-6 Alkyl, COOM;

D = O, NH;

E = C_1-6 Alkyl, linear bzw. verzweigt;

F = ein copolymerisiertes Monomer;

M = H, Alkali- bzw. Erdalkalimetall, Ammonium, substituiertes Ammonium; bei X auch - (CH₂-CH₂-O)_2-4 M;

r = 1 - 5;

ist und

m = 0 - 99,5 mol %

n = 0,5 - 100 mol %

q = 0 - 99,5 mol %

wobei m + n + q = 100 mol %
bedeutet.The pre-filed patent application DE 44 17 734 (EP-A-0684 265) describes polycarboxylates of the general structure (X, Y, Z), in which
X for

Y for

and Z for - (F) q ^- . stands in what

A = H, OH, C _1-6 alkyl, CH ₂ CO (DECO) _r-1 OM;

B = H, OH, C _1-6 alkyl, COOM;

D = O, NH;

E = C _1-6 alkyl, linear or branched;

F = a copolymerized monomer;

M = H, alkali or alkaline earth metal, ammonium, substituted ammonium; with X too - (CH ₂ -CH ₂ -O) _2-4 M;

r = 1-5;

is and

m = 0 - 99.5 mol%

n = 0.5 - 100 mol%

q = 0 - 99.5 mol%

where m + n + q = 100 mol%
means.

These preferred polycarboxylates from the monomers acrolein and Vinyl acetate are produced in such a way that the two monomers in Ratios of 4: 1 to 20: 1 are used. In the Exemplary embodiments of this publication are the characteristic data for acrolein-vinyl acetate copolymers with an acrolein to vinyl acetate ratio of 95: 5, 87:15 and 50:50.

These substrates are lime-binding at room temperature and elevated temperatures and their biodegradability according to Zahn-Wellens characterized. In addition, one finds in the claims of this Registration still indicates the use of these substrates as Cobuilder or builder in detergents or on the use of these substrates in Detergents and cleaning agents.

The present invention is a selection invention from this pre-filed Patent application for partially neutralized acrolein-vinyl acetate copolymers as effective components of builders combinations as well as washing and Detergents are provided.

The present invention therefore relates to a combination of builders at least one builder and / or complexing agent, containing at least a copolymer based on acrolein and vinyl acetate and / or its salt, characterized by a quantitative ratio of these two substances from 1: 1 to less than 5.7: 1 and an average molecular mass in the range from 3,000 to 5,000. The ratio of acrolein to vinyl acetate is preferably 1: 1 to 5.5: 1.

These copolymers based on acrolein and vinyl acetate have Suitability criteria based on what is mandatory for modern detergent builders are, so an elimination of alkaline earth ions, good Primary washing properties, good secondary properties with the Properties of commercial acrylic acid-maleic acid copolymers are comparable as well as good technical properties. Was special found that the copolymers according to the invention based on acrolein and Vinyl acetate an excellent graying inhibition as part of the Have secondary washing performance. In particular, it was found that the copolymers according to the invention based on acrolein and vinyl acetate Comparison to commercially available complexing agents such as polyacrylic acid or Maleic acid has good biodegradability. Compared to usual nitrogen-containing complexing agents, such as EDTA, amino (tri) methylenephosphonic acid, Nitrilotriacetic acid or N- (2) -hydroxyethyliminodiacetic acid, have the copolymers of the invention based of acrolein and vinyl acetate and their salts have the advantage that it is not too eutrophication or other negative effects on biological Systems is coming.

A further embodiment of the invention provides that the builder combination 1 to 50 wt .-%, preferably 2 to 30 wt .-% of at least one of the aforementioned copolymers based on acrolein and vinyl acetate and / or its salt, 50 to 99 wt .-% , preferably 70 to 98 wt .-% zeolite and / or amorphous silicates and / or crystalline sheet silicates of the formula NaMSi _x O _{2x + 1} yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, and optionally contains further builders or cobuilders.

According to a preferred embodiment of the present invention, the Combination of builders with liquid to waxy components, preferably nonionic surfactants, sprayed.

A method for producing this combination of builders is used for this purpose which the builders combination by mixing, granulating and / or Spray drying is produced.

The zeolites come in the usual hydrated, fine crystalline form Commitment. Their water content is preferably between 19 and 22% by weight. she have practically no particles larger than 30 microns and exist preferably at least 80% of particles smaller than 10 Micrometer. Your calcium binding capacity, which according to the German Patent application 24 12 837 is determined, is in the range of 100 to 200 mg Calcium oxide per gram. Zeolite A and Zeolite P are particularly suitable, also zeolite X and mixtures of A and X and / or P. Quantities and weight ratios that relate to the builders are within the scope of this invention - unless otherwise stated - on anhydrous active substance related.

Suitable substitutes or partial substitutes for phosphates and zeolite are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, and preferred values for x are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application 0 164 514. Preferred crystalline layered silicates of this formula are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ x yH ₂ O are preferred. Other silicates are amorphous silicates with secondary washing power, for example those according to DE-A 44 00 024, DE-A 44 19 745 and DE-P 44 46 363.4, especially sodium silicate with a molar ratio Na ₂ O: SiO ₂ of 1: 1 to 1: 4.5, preferably 1: 2 to 1: 3.5.

The agents or builders combinations according to the invention can also Mixtures of zeolite and the crystalline layered silicates of the above Contain formula, the mixing ratio is arbitrary. Preferably however, zeolite either alone or in a zeolite weight ratio crystalline layered silicate from 10: 1 to 1: 3 and in particular 3: 1 to 1: 1 used.

According to a further embodiment, the present invention relates to a Containing detergents and cleaning agents, in particular textile detergents phosphate-free builders and complexing agents, which thereby is characterized in that it contains builders in total from 10 to 60 Contains wt .-%, the builders 0.5 to 20 wt .-% of a copolymer based on acrolein and vinyl acetate or its salt and 80 to 99.5% by weight contains other builders.

The present invention further relates to a detergent and cleaning agent that characterized in that it is 0.5 to 20% by weight, preferably 1 to 15 % By weight of the copolymer based on acrolein and vinyl acetate and / or of its salts, 0 to 50% by weight, preferably 10 to 35% by weight of zeolite and 0 to 40% by weight, preferably 10 to 30% by weight, of at least one amorphous silicate with secondary washing power or a crystalline layered silicate, this agent but at least one other besides the copolymer Contains builders based on zeolite or silicate.

The agent generally has a bulk density between 300 and 1200 g / l, preferably between 500 and 1100 g / l.

Another object of the present invention is a method for Preparation of a granular washing and cleaning agent of the above Composition in which the granules are produced by spray drying becomes. Alternatively, the granular detergent and cleaning agent by a Granulation or extrusion processes can be produced. A is preferred Process for the production of a granular washing and cleaning agent, at which the builders combination described above in the form of a spray-dried or granulated compounds as admixing components other granular components of detergents and cleaning agents becomes.

The detergents and cleaning agents according to the invention can still be used usual builders and complexing agents, for example phosphonates, the polycarboxylic acids preferably used in the form of their sodium salts, such as Citric acid, adipic acid, succinic acid, glutaric acid, aminocarboxylic acid, Nitrilotriacetic acid (NTA), provided that such use from ecological There is no reason for complaint, as well as mixtures of these and (co) polymers Polycarboxylic acids or polycarboxylates, such as the sodium salts of Polyacrylic acids or polymethacrylic acid, for example those with a relative molecular mass of 800 to 150,000 (based on acid), where in particular those of acrylic acid with methacrylic acid and acrylic acid or Methacrylic acid with maleic acid are preferred, additionally contained. But do not wear these additional builders and complexing agents further to significant improvement, especially lower ones Ash values at. According to a preferred embodiment, this contains agents therefore no conventional copolymeric polycarboxylic acids or Polycarboxylates of the type mentioned.

It is also preferred that it contains sodium carbonate and / or potassium carbonate Contains amounts of 0 to 20, preferably 5 to 15 wt .-%. Bicarbonates can also be present.

Phosphonates, preferably the neutral sodium salts for example 1-hydroxyethane-1,1-diphosphonate and Diethylene triamine pentamethylene phosphonate are often used as enzyme or Bleach stabilizers used in amounts of 0.1 to 1.5 wt .-%. It has however, showed that the primary wash performance as well as the bleach and Enzyme stability of the washing and cleaning agents according to the invention by the Use of phosphonates cannot be increased. Surprisingly found that the agents according to the invention, which act as complexing agents acrolein-vinyl acetate copolymers or mixtures of these, in comparison to an agent that instead of the complexing agent according to the invention Usual (co-) polymeric polycarboxylates contains less in textiles Have ash value.

The builder combinations according to the invention can also be used for further combinations Contain components, for example inorganic, alkaline or in water neutral reacting salts. However, it is particularly preferred that the Framework combination with liquid to waxy components, for example Silicone oils and paraffin oils, but preferably with nonionic surfactants are sprayed.

In addition to the ingredients mentioned, the washing agents according to the invention and detergents, other known ones in detergents and cleaning agents Additives usually used, for example surfactants, bleaches and Bleach activators, alkaline salts in water, Solubility improvers such as conventional hydrotropes or polyalkylene glycols, for example polyethylene glycols, foam inhibitors, optical brighteners, Enzymes, enzyme stabilizers, small amounts of neutral filling salts or Adjusting agents as well as colors and fragrances, opacifiers or pearlescent agents contain.

The content of these detergents and cleaning agents in anionic and nonionic surfactants including soap is preferably 10 to 40 % By weight, advantageously 12 to 35% by weight and in particular 15 to 30% by weight.

Suitable anionic surfactants of the sulfonate type include, for example, C ₉ to C ₁₃ alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C12-C18 monoolefins having a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates) are also suitable. In particular, esters of α-sulfo fatty acids which are prepared by α-sulfonation of the alkyl esters of fatty acids of plant and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono salts are suitable. These are preferably the α-sulfonated esters of hydrogenated coconut, palm kernel or tallow fatty acids, and sulfonation products of unsaturated fatty acids, for example oleic acid, are also present in small amounts, preferably in amounts not above about 2 to 3% by weight could be. In particular, a-sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters. The methyl esters of α-sulfofatty acids (MES) are used with particular advantage. Further suitable anionic surfactants are the α-sulfofatty acids obtainable by ester cleavage of the α-sulfofatty acid alkyl esters or their disalts. The mono-salts of the α-sulfofatty acid alkyl esters are obtained as aqueous mixtures in limited amounts even in their large-scale production. Mixtures of monosalts and disalts with other surfactants, for example with alkylbenzenesulfonate, are also preferred.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under Fatty acid glycerol esters are the mono-, di- and triesters and their mixtures to understand how they are made by esterification through a Monoglycerin with 1 to 3 moles of fatty acid or in the esterification of Triglycerides with 0.3 to 2 moles of glycerin are kept. Preferred sulfated Fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Capric acid, myristic acid, lauric acid, palmitic acid, stearic acid and Behenic acid. If you start from fats and oils, i.e. natural mixtures different fatty acid glycerol esters, it is necessary that Products used before sulfonation with oxygen in a manner known per se largely saturate, d. i.e. to harden to iodine numbers <5, preferably <2. Typical examples of suitable feedstocks are palm oil, palm kernel oil, Palm stearin, olive oil, rape oil, coriander oil, sunflower oil, cottonseed oil, Peanut oil, linseed oil, lard oil or lard. Because of their high natural proportion of saturated fatty acids, however, it has turned out to be special proven advantageous to start from coconut oil, palm kernel oil or beef tallow. The Sulfation of saturated fatty acids with 6 to 22 carbon atoms or the Mixtures of fatty acid glycerol esters with iodine numbers <5, the fatty acids with 6 contain up to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous Bases as specified in international patent application WO 91/9009 is.

The sulfonation products are a complex mixture that essentially Mono-, di- and triglyceride sulfonates with α and / or internal Contains sulfonic acid grouping. Sulfonated form as by-products Fatty acid salts, glyceride sulfates, glycerin sulfates, glycerin and soaps. You go in the sulfonation of saturated or hardened fatty acids Fatty acid glycerol ester mixtures, so the proportion of α-sulfonated Depending on the procedure, fatty acid disalts can be up to about 60% by weight.

Anionic surfactants based on alkanesulfonates, which are obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, are also suitable. The sulfonate group is statistically distributed over the entire carbon chain, with the secondary alkanesulfonates predominating.

Suitable anionic surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural or synthetic origin, in particular from fatty alcohols, e.g. B. from tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols, and those secondary alcohols of this chain length. The sulfuric acid monoesters with 1 to 6 moles of ethylene oxide ethoxylated alcohols, such as 2-methyl-branched C ₉ -C ₁₁ alcohols with an average of 3.5 moles of ethylene oxide, are also suitable. Preferred fatty alkyl sulfates are derived from fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil, which additionally contain proportions of unsaturated alcohols, e.g. B. oleyl alcohol, may contain. Mixtures in which the proportion of the alkyl radicals are 50 to 70% by weight on C ₁₂ , 18 to 30% by weight on C ₁₄ , 5 to 15% by weight on C ₁₆ , below 3 find a preferred use % By weight on C ₁₀ and less than 10% by weight on C _{18 are} distributed.

Likewise preferred anionic surfactants are the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which are nonionic surfactants in themselves. Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred.

Soaps, in particular, are particularly suitable as further anionic surfactants Amounts of 0.5 to 5 wt .-% into consideration. Saturated ones are suitable Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. B. coconut, Palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in Form of their sodium or potassium salts.

The nonionic surfactants used are preferably liquid ethoxylated and / or propoxylated alcohols which are derived from primary alcohols preferably having 8 to 18 carbon atoms and an average of 1 to 12 mol of alkylene oxide, in which the alcohol radical can be linear or methyl-branched in the 2-position, or linear or may contain methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, linear residues of alcohols of native origin with 12 to 18 carbon atoms are preferred, such as. B. from coconut, tallow or oleyl alcohol. In particular, C ₁₂ -C ₁₄ alcohols with three moles of ethylene oxide or four moles of ethylene oxide, C ₉ -C ₁₁ alcohol with 7 moles of ethylene oxide, C ₁₃ -C ₁₅ alcohols with three moles of ethylene oxide, five moles of ethylene oxide, seven moles of ethylene oxide or eight moles of ethylene oxide, C ₁₂ -C ₁₈ alcohols with three moles of ethylene oxide, five moles of ethylene oxide or seven moles of ethylene oxide or mixtures thereof, such as mixtures of C ₁₂ to C ₁₄ alcohol with three moles of ethylene oxide and C ₁₂ to C ₁₈ -Alcohol used with five moles of ethylene oxide.

The degrees of ethoxylation given represent statistical averages that can be an integer and a fractional number for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (Narrow Range Ethoxylates, NRE). In particular, alcohol ethoxylates preferred, which have an average of 2 to 8 ethylene oxide groups.

In addition, alkyl polyglycosides of the general formula RO (G) _x can also be used as further nonionic surfactants, in which R denotes a primary, straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, C-atoms branched methyl and G denotes Is symbol which stands for a glucose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides or oligoglycosides, is any number between 1 and 10.

in der R₂ - CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R₃ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Vorzugsweise werden als Polyhydroxyfettsäureamide Fettsäure - N - alkylglucamide eingesetzt, in der R₃ für Wasserstoff oder eine Alkylgruppe, R₂ - CO für den Acylrest einer gesättigten oder ungesättigten Fettsäure und [Z] für einen Glucoserest steht.Other suitable surfactants are polyhydroxy fatty acid amides of the general formula

in which R ₂ - CO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ₃ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 Hydroxyl groups. The polyhydroxy fatty acid amides used are preferably fatty acid-N-alkylglucamides in which R _{3 is} hydrogen or an alkyl group, R ₂ -CO is the acyl radical of a saturated or unsaturated fatty acid and [Z] is a glucose radical.

Among those which serve as bleaching agents and which supply hydrogen peroxide in water Compounds have the sodium perborate tetrahydrate and Sodium perborate monohydrate of particular importance. More usable Bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, Citrate perhydrates and peracid salts or hydrogen peroxide Peracids, the perbenzoates, peroxaphthalates, diperazelaic acid or Diperdodecanedioic acid. The bleach content of the agents is preferably 5 to 25 wt .-% and in particular 10 to 20 wt .-%, advantageously Perborate monohydrate is used.

To when washing at a temperature of 60 ° C and below one To achieve improved bleaching effects, bleach activators can be used in the Preparations are incorporated. Examples include hydrogen peroxide organic peracids forming N-acyl or O-acyl compounds, preferably N, N'-tetraacylated diamines, also carboxylic anhydrides and Esters of polyols such as glucose pentaacetate. The content of bleach Agents of bleach activators are in the usual range, preferably between 1 and 10% by weight and in particular between 2 and 8% by weight. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylene diamine and 1,4-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.

Graying inhibitors have the task of detaching from the fiber Keeping dirt suspended in the fleet and thus turning gray prevent. For this purpose, water-soluble colloids are mostly organic in nature suitable, for example the water-soluble salts of polymeric carboxylic acids, Glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch and the cellulose or salts of acidic sulfuric acid esters of the cellulose or strength. Also water-soluble polyamides containing acidic groups are suitable for this purpose. Soluble starch preparations can also be used and use starch products other than the above, e.g. B. dismantled Starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. Prefers However, carboxymethyl cellulose (sodium salt), methyl cellulose, Methylhydroxyethyl cellulose and mixtures thereof and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition, used.

The foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants; a reduction can also be achieved by adding non-surfactant-like substances. A reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, e.g. B. of sulfates and / or sulfonates with nonionic surfactants and / or with soaps. In the case of soaps, the foam-suppressing effect increases with the degree of saturation and the C number of the fatty acid salt. Soaps of natural or synthetic origin which contain a high proportion of C ₁₈ -C ₂₄ fatty acids are therefore suitable as foam-inhibiting soaps. Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica. Mixtures of different foam inhibitors are also advantageously used, e.g. B. from silicone, paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.

Enzymes in particular come from the class of hydrolases, such as the proteases, esterases, lipases or lipolytically active enzymes, Amylases, cellulases or other glycosyl hydrolases and mixtures of mentioned enzymes in question. All of these hydrolases contribute to the laundry Removal of stains such as those containing protein, fat or starch Stains, and graying. Cellulases and others Glycosyl hydrolases can be removed by removing pilling and microfibrils Color preservation and increase the softness of the textile. For Bleaching or to inhibit color transfer can also be oxidoreductases be used.

Bacterial strains or fungi such as Bacillus are particularly suitable subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens obtained enzymatic active ingredients. Proteases are preferably from Subtilisin type and especially proteases derived from Bacillus lentus be used. There are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic acting enzymes or from protease, amylase and lipase or lipolytic acting enzymes or protease, lipase or lipolytically acting enzymes and cellulase, but especially protease and / or lipase-containing Mixtures or mixtures with lipolytically active enzymes of of special interest. Examples of such lipolytic enzymes are the well-known cutinases. Peroxidases or oxidases have also become proved suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As Cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cello bias, or mixtures of used this. Because the different types of cellulase are characterized by their CMCase and Avicelase activities can be differentiated by targeted Mixtures of cellulases to set the desired activities.

The enzymes can be adsorbed on carrier substances and / or in coating substances embedded to protect them against premature decomposition. The share of Enzymes, enzyme mixtures or enzyme granules can, for example, be about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.

In addition, the agents can contain enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H ₃ BO ₃ ), metaboric acid (HBO ₂ ) and pyrobic acid (tetraboric acid H ₂ B ₄ O ₇ ), is particularly advantageous. .

The agents can be used as optical brighteners Contain diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are z. B. Salts of 4,4'- bis (2-anilino-4-morpholino-1,3,5-triacin-6-ylamino) stilbene-2,2'-disulfonic acid or similarly constructed connections that instead of the morpholino group, a diethanolamino group, one Methylamino group, an anilino group or a 2-methoxyethylamino group wear. Brighteners of the substituted 4,4'-distyryldiphenyl type can also be used be present, e.g. B. the compound 4,4'- bis (4-chloro-3-sulfostyry) diphenyl. Mixtures of the aforementioned brighteners can also be used become.

Both the builder according to the invention and those according to the invention Detergents and cleaning agents can be used in a conventional manner, for example by mixing, granulating, extruding and / or spray drying one aqueous slurry and optionally subsequent admixture of temperature-sensitive components are manufactured. In the case of washing and cleaning agents can separately manufactured builders / builders combinations in the form of a spray dried or granulated Compounds as an admixture to other granular components of the Detergents and cleaning agents are used. It is also possible that Builders and complexing agents individually and in the usual way and incorporate into the funds in any order.

The invention is explained in more detail below by means of exemplary embodiments. The average molecular weight was determined by means of gel permeation chromatography determined on Lichrosphor Diol columns (Merck AG) and with phosphate buffer (pH 7) as an eluent solution. As a standard and calibration medium was distributed narrowly Polyacrylic acid used, as in DE-A-44 17 734 (EP-A-0684 265) in individual explained.

Examples Manufacturing example

The production of the copolymer based on acrolein and vinyl acetate a ratio of 3: 1 was carried out in aqueous media in the presence of Hydrogen peroxide according to the teaching of DE-A-44 17 734 (EP-A-0684 265), in particular the exemplary embodiments to which express reference is made here is taken. This became sample A (solids content 53%) and the sample B (43% solids content).

Application example

The inventive, used in detergents and cleaning agents Acrolein-vinyl acetate copolymers, all of which are better Calcium binding capacity as polyacrylate, i.e. more than 200 mg Calcium carbonate per gram have been with regard to their application properties in a compact detergent on your Primary and secondary washing properties examined.

As a comparison, a compact detergent was used, which is a contained commercially available acrylic acid-maleic acid copolymer selected.

A. Ein nach Beispiel 1 hergestelltes Produkt mit einem Feststoffanteil von 53 %, einer Verseifungszahl von 5,8 cm³/g (VZ 2%, 0,1 M NaBr, Oa, 25 °C), einem Calciumbindevermögen von 1600 (mg CaCO₃ pro Gramm Probe bei Raumtemperatur), einer gemäß Zahn-Wellens-Test über 14 Tage ermittelten biologischen Abbaubarkeit von 30 % und einer Essigsäurezahl von 4,0 %.

B. Ein nach Beispiel 2 erhaltenes Produkt mit einem Feststoffanteil von 43 %, einer VZ von 4,8, einem Calciumbindevermögen von 1450, einer biologischen Abbaubarkeit von 39% und einer Essigsäurezahl von 4,5%

und als Vergleich
C. Acrylsäure-Maleinsäure-Copolymerisat (Natriumsalz)
5,5 Gew.-% der Verbindungen A, B oder C wurden 94,5 Gew.-% einer Kompaktwaschmittelzusammensetzung beigegeben, so daß sich folgende Zusammensetzungen aus Kompaktwaschmittel und Cobuilder ergaben: Zusammensetzung in Gew.-% C₉-C₁₃-Alkylbenzolsulfonat-natriumsalz 9 Talgfettalkoholsulfat 4 C₁₂-C₁₈-Fettalkohol mit 5 EO 4,3 Talgfettalkohol mit 5 EO 1,8 C₁₂-C₁₈-Fettsäureseife-natriumsalz 0,8 Zeolith (wasserfreie Aktivsubstanz) 23,5 Natriumcarbonat 12,6 Natriumsilikat (Na₂O : SiO₂ 1 : 2) 3 Perboratmonohydrat 16 TAED 5,5 Carboxymethylcellulose/Methylcellulose 0,25 Enzymgranulat 1 Entschäumergranulat 0,2 optischer Aufheller 0,2 Wasser 11 Salze aus Rohstoffen Rest Cobuilder A, B oder C 5,5 The following products were chosen:

A. A product prepared according to Example 1 with a solids content of 53%, a saponification number of 5.8 cm ³ / g (VZ 2%, 0.1 M NaBr, Oa, 25 ° C), a calcium binding capacity of 1600 (mg CaCO ₃ per gram of sample at room temperature), a biodegradability of 30% determined according to the Zahn-Wellens test over 14 days and an acetic acid number of 4.0%.

B. A product obtained according to Example 2 with a solids content of 43%, a VZ of 4.8, a calcium binding capacity of 1450, a biodegradability of 39% and an acetic acid number of 4.5%

and as a comparison
C. Acrylic acid-maleic acid copolymer (sodium salt)
5.5% by weight of compounds A, B or C were added to 94.5% by weight of a compact detergent composition, so that the following compositions of compact detergent and cobuilder resulted: Composition in% by weight C ₉ -C ₁₃ alkylbenzenesulfonate sodium salt 9 Tallow fatty alcohol sulfate 4th C ₁₂ -C ₁₈ fatty alcohol with 5 EO 4.3 Tallow fatty alcohol with 5 EO 1.8 C ₁₂ -C ₁₈ fatty acid soap sodium salt 0.8 Zeolite (anhydrous active substance) 23.5 sodium 12.6 Sodium silicate (Na ₂ O: SiO ₂ 1: 2) 3rd Perborate monohydrate 16 TAED 5.5 Carboxymethyl cellulose / methyl cellulose 0.25 Enzyme granules 1 Defoamer granules 0.2 optical brightener 0.2 water 11 Salts from raw materials rest Cobuilder A, B or C 5.5

Übliche Trommel-Haushaltswaschmaschine

Temperatur in der Flotte: 90 °C

Waschmitteldosierung: 5,0 g pro Liter

Wasserhärte: 23° d

Beladung: 3,5 kg weiße Ballastwäsche einschließlich Testgewebe und Testanschmutzung

Anzahl der Wäschen: 25

Hierbei ergaben sich für die Sekundärwaschwirkung, ausgedrückt als Vergrauung in Prozent Remission, gemittelt über die 4 Gewebe: Krefelder Standardgewebe, Bleichnessel, Frottee, Gewirke (jeweils zu 100 % aus Baumwolle) folgende Werte: Anfangswert 84,6 Waschmittel mit Probe A 88,3 Waschmittel mit Probe B 88,6 Waschmittel mit Vergleichssubstanz C 86,6 The test conditions themselves were as follows:

Usual drum household washing machine

Fleet temperature: 90 ° C

Detergent dosage: 5.0 g per liter

Water hardness: 23 ° d

Load: 3.5 kg white ballast laundry including test fabric and test soiling

Number of washes: 25

The secondary washing effect, expressed as graying in percent remission, averaged over the 4 fabrics: Krefeld standard fabrics, bleaching nettle, terry cloth, knitted fabrics (each 100% cotton) resulted in the following values: Initial value 84.6 Detergent with sample A 88.3 Detergent with sample B 88.6 Detergent with comparative substance C 86.6

The detergent with samples A and B shows a significant improvement compared to the comparative substance C. Further clear advantages exist in Environmental behavior of this builder and a biodegradability of 30 or 39%.

Claims (14)

1. A builder combination of at least one builder and/or complexing agent additionally containing at least one copolymer based on acrolein and vinyl acetate and/or a salt thereof, characterized by a quantity ratio of acrolein to vinyl acetate of 1:1 to less than 5.7:1 and an average molecular weight of 3,000 to 5,000.
2. A builder combination as claimed in claim 1 containing 1 to 50% by weight and preferably 2 to 30% by weight of at least one copolymer based on acrolein and vinyl acetate and/or a salt thereof, 50 to 99% by weight and preferably 70 to 98% by weight of zeolite and/or amorphous silicates and/or crystalline layer silicates with the formula NaMSi_xO_2x+1 · yH₂O, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20.
3. A builder combination as claimed in claim 1 or 2, characterized in that the builder combination is sprayed with liquid to wax-like components, preferably nonionic surfactants.
4. A process for the production of the builder combination claimed in claims 1 to 3, characterized in that the builder combination is produced by mixing, granulation and/or by spray drying.
5. A detergent, more particularly a laundry detergent, containing phosphate-free builders and complexing agents, characterized in that it contains builders in quantities of 10 to 60% by weight and the builders contain a copolymer based on acrolein and vinyl acetate and/or a salt thereof according to claim 1.
6. A detergent, more particularly a laundry detergent, containing phosphate-free builders and complexing agents, characterized in that it contains 0.5 to 20% by weight and preferably 1 to 15% by weight of the copolymer based on acrolein and vinyl acetate and/or salts thereof according to claims 1 to 4, 0 to 50% by weight and preferably 10 to 35% by weight of zeolite and 0 to 40% by weight and preferably 10 to 30% by weight of at least one amorphous silicate with multiple wash cycle performance or a crystalline layered silicate, the detergent containing at least one other zeolite- or silicate-based builder besides the copolymer.
7. A detergent as claimed in claim 5 or 6, characterized in that it contains 10 to 40% by weight and preferably 12 to 35% by weight of anionic and nonionic surfactants, including soap.
8. A detergent as claimed in any of claims 5 to 7, characterized in that it contains 1 to 15% by weight of copolymer based on acrolein and vinyl acetate in the form of its alkali metal salts.
9. A detergent as claimed in any of claims 5 to 8, characterized in that it does not contain any (co)polymeric polycarboxylic acids or polycarboxylates.
10. A detergent as claimed in any of claims 5 to 9, characterized in that it contains sodium carbonate and/or potassium carbonate in quantities of 0 to 20% by weight and preferably 5 to 15% by weight.
11. A detergent as claimed in any of claims 5 to 10, characterized in that it has a bulk density of 300 to 1,200 g/l and preferably in the range from 500 to 1,100 g/l.
12. A process for the production of the granular detergent claimed in any of claims 5 to 11, characterized in that the granules are produced by spray drying.
13. A process for the production of the granular detergent claimed in any of claims 5 to 11, characterized in that the granules are produced by a granulation or extrusion process.
14. A process for the production of the granular detergent claimed in any of claims 5 to 11, characterized in that the builder combination claimed in claims 1 to 3 is used in the form of a spray-dried or granulated compound for addition to other granular components of detergents.