EP0345587A1 - Use of cationic non-silicate layer compounds in detergents - Google Patents

Abstract

Cationic non-silicate layer compounds of the general formula (I) Mgx Al (OH) y Az. nH2O (I) where A is an equivalent of a non-silicate anion, x is a value between 1 and 5, y is greater than z and (y + z) = 2x + 3 and n is a number between 0 and 10, in Reduced phosphate detergents used to reduce incrustation.

Description

The invention relates to the use of cationic non-silicate layer compounds in detergent compositions and in particular in reduced phosphate detergents based on zeolite.

In the course of the complete substitution of the ecologically undesirable sodium tripolyphosphate in detergent compositions, combinations of zeolite A and so-called co-builders, such as polycarboxylates, have proven themselves in practice. However, the polycarboxylates known and used today for detergent compositions are almost exclusively difficult to biodegrade. Inorganic, layer-like compounds have been proposed as alternative builder components which, from an ecological point of view, have no effect on the environment. For example, synthetic, finely divided, water-insoluble layered silicates with smectite-like crystal phase in EP-A 0 209 840 or crystalline, layered sodium silicates in DE-OS 34 13 571. These layered compounds are, without exception, layered silicates.

The use of non-silicate layer compounds as a builder component in detergent compositions is not known. Only EP-A 0 206 799 describes the use of mixed metal hydroxides to prevent dye transfer in washing processes.

In the context of the present invention, "reduced phosphate" means that detergent compositions contain at most 30% by weight sodium tripolyphosphate, but can also be completely phosphate-free.

The object of the present invention was to provide new phosphate-reduced detergent compositions and to bring about a reduction in the deposition of tissue in conventional washing processes.

The above-mentioned objects are achieved by using cationic non-silicate layer compounds as a separate additive to zeolite-containing, phosphate-reduced and in particular phosphate-free detergent compositions or as an integrated detergent component. It was found that the incrustations on fabrics were significantly reduced and thus made a significant contribution to the formulation of environmentally friendly builder systems.

The invention relates to the use of cationic non-silicate layer compounds of the general formula (I)
Mg _x Al (OH) _y A _z . nH₂O (I)
in which
A stands for an equivalent of a non-silicate anion and the conditions 1 less than x less than 5, y greater than z, (y + z) = 2x + 3, 0 less than n less than 10 apply, in phosphate-reduced detergent compositions, the cationic layer compounds belong to the structure type of hydrotalcite, with a grating distance for the most intense line in the X-ray diffraction diagram from 7.4 to Å for the product dried at 110 ° C.

Cationic layer connections are understood here to mean solids, the structure of which is derived from the layered magnesium hydroxide brucite in that some of the divalent metal ions are replaced by trivalent metal ions. The resulting positive excess charge of the metal hydroxide layers is compensated for by exchangeable anions between the layers. Hydrotalcite can be used as a model substance for this class of solids.

Hydrotalcite is a naturally occurring mineral with an approximate composition
Mg₆Al₂ (OH) ₁₆CO₃. 4H₂O
the ratio of Mg to Al and thus also the carbonate content can fluctuate within relatively wide limits. Instead of the carbonate, other anions can also be present. In contrast, the layer structure with the ABAB ... layer sequence is characteristic of the substance, if A stands for a positively charged triple layer consisting of hydroxyl ions, metal cations and again hydroxyl ions. B means an intermediate layer of anions and water of crystallization. This layer structure becomes clear in the X-ray powder diagram, which can be used for characterization: ASTM card no. 30, 1.96, 1.53 and 1.50 Å. The distance is 7.69 Å basic repetition period of the layers (= layer spacing) of the substance usually containing water of crystallization. Sharper drying at elevated temperatures (120 to 200 ° C at normal pressure) leads to reduced layer spacing due to the release of the water of crystallization.

The crystal structure of natural hydrotalcite was determined by X-ray analysis by Allmann and Jepsen. (N. Jahrb. Mineral. Monthly 1969, pp. 544 - 551). The range of variation of the Mg to Al ratio and the influence on the repetition period of the layers were investigated, for example, by Gastuche, Brown and Mortland (Clay Miner. 7 (1967), pp 177-192). Possible processes for the industrial production of synthetic hydrotalcite and its use as gastric acid binding agent were described in 1967 by Kyowa Chemical Industry Co., Tokyo (DE-OS 15 92 126). In addition to neutralizing gastric acid, hydrotalcite can generally be used to bind acidic components, for example impurities from catalytic processes (DE-OS 27 19 024) or undesirable dyes (DE-OS 29 29 991). Other possible uses are in the field of corrosion protection (DE-OS 31 28 716), the stabilization of plastics, in particular PVC (DE-PS 30 19 632), waste water treatment (JP-PS 79 24 993, JP-PS 58 214 388 ) and the production of color pigments (JP-PS 81 98 265).

The incorporation of carbonate ions as interlayer anions is particularly preferred. Hydrotalcite-like solids with other anions can be obtained by using a soluble salt of another acid instead of sodium carbonate in the production or by driving off the carbonate as CO₂ from the carbonate-containing product by reaction with weak acids. The anions are exchanged Noticeable in the X-ray diffraction diagram by a change in the layer spacings (T. Reichle, Chemtech. Jan. 1986, pp. 58-63).

A further embodiment of the present invention consists in the use of cationic non-silicate layer compounds, wherein A in the general formula (I) stands for one equivalent of a carbonate ion.

Another preferred embodiment of the present invention consists in the use of cationic non-silicate layer compounds of the general formula (I) in an amount of 1 to 15% by weight, based on the detergent composition. The use of 2 to 10% by weight of the cationic non-silicate layer compounds, based on the detergent composition, is particularly preferred.

While in principle the phosphate content, based on tripolyphosphate, is not critical in the sense of the present invention, it is preferred according to a further embodiment of the present invention that the phosphate content, calculated as sodium tripolyphosphate, is less than 30% by weight.

Another preferred embodiment of the present invention is that the use of cationic non-silicate layer compounds is carried out in phosphate-free detergent compositions.

In particular, the use of cationic non-silicate layer compounds is preferred if the detergent compositions contain 10 to 30% of zeolite A and 1 to 15% of the contain cationic non-silicate layer compounds.

The layer compounds to be used according to the invention can be incorporated by conventional techniques for the production of detergents, e.g. by hot atomization together with other detergent components, by granulation together with solid and / or liquid detergent components or by subsequent application to solid detergent parts (e.g. spray powder, granules, zeolite, layered silicate).

In addition to cationic layered compounds, detergent compositions according to the invention can contain further builder substances, builder substances, surfactants, soaps, non-surfactant-like foam inhibitors and dirt carriers.

The builder constituents which may be present in the detergents according to the invention are described in more detail below:
Suitable organic and inorganic builder substances are weakly acidic, neutral or alkaline-reacting salts, in particular alkali salts, which are able to precipitate or bind calcium ions in a complex manner. Of the inorganic salts, the water-soluble alkali metal or alkali polyphosphates, in particular pentasodium triphosphate, in addition to the alkali ortho- and alkali pyrophosphates, are of particular importance. All or part of these phosphates can be replaced by organic complexing agents for calcium ions. These include compounds of the aminopolycarboxylic acid type, such as, for example, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and higher homologs. Suitable phosphorus-containing organic complexing agents are the water-soluble salts of alkanephosphonic acids, amino- and hydroxyalkanephosphonic acids and phosphonopolycarboxylic acids such as methane diphosphonic acid, dimethylaminomethane-1,1-diphosphonic acids, aminotrimethylene triphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 1-phosphonicarboxylic acid , 2-phosphonobutane-1,2,4-tricarboxylic acid.

Of the organic framework substances, the nitrogen-free and phosphorus-free polycarboxylic acids which form complex salts with calcium ions, which also include polymers containing carboxyl groups, are of particular importance. Suitable are e.g. Citric acid, tartaric acid, benzene hexacarboxylic acid and tetrahydrofuran tetracarboxylic acid. Polycarboxylic acids containing ether groups are also suitable, such as 2,2'-oxydisuccinic acid and polyhydric alcohols or hydroxycarboxylic acids partially or completely etherified with glycolic acid, e.g. Biscarboxymethylethylengylkol, carboxymethyloxysuccinic acid, carboxymethyltartronic acid and carboxymethylated or oxidized polysaccharides. Polymeric carboxylic acids with a molecular weight between 350 and about 1,500,000 in the form of water-soluble salts are also suitable. Particularly preferred polymeric polycarboxylates have a molecular weight in the range from 500 to 175,000 and in particular in the range from 10,000 to 100,000. These compounds include, for example, polyacrylic acid, polyhydroxyacrylic acid, polymaleic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds such as vinyl methyl ether . The water-soluble salts of polyglyoxylic acid are also suitable.

Suitable water-insoluble inorganic builders are those in DE-OS 24 12 837 as phosphate substitutes for Detergents and cleaning agents described in more detail finely divided, synthetic, bound water-containing sodium aluminosilicates of the zeolite A type.

The cation-exchanging sodium aluminosilicates are used in the usual hydrated, finely crystalline form, that is to say that they have practically no particles larger than 30 μm and preferably consist of at least 80% of particles smaller than 10 μm. Your calcium binding capacity, which is determined according to the details of DE-OS 24 12 837, is in the range of 100 to 200 mg CaO / g. Zeolite NaA is particularly suitable, as is zeolite NaX and mixtures of NaA and NaX.

Suitable inorganic, non-complexing salts are the alkali salts of bicarbonates, carbonates, borates, sulfates and silicates - also referred to as "washing alkalis". Of the alkali silicates, the sodium silicates in which the Na₂O: SiO₂ ratio is between 1: 1 and 1: 3.5 are particularly preferred.

Other builder substances that are mostly used in liquid agents because of their hydrotropic properties are the salts of the non-capillary-active sulfonic acids containing 2 to 9 carbon atoms, carboxylic acids and sulfocarboxylic acids, for example the alkali salts of alkanoic, benzene, toluene, xylene or cumene sulfonic acids Sulfobenzoic acids, sulfophthalic acid, sulfoacetic acid, sulfosuccinic acid and the salts of acetic acid or lactic acid. Acetamide and ureas are also suitable as solubilizers.

Surfactants, which can be contained as additional components in existing washing and cleaning agents, have in Molecule at least one hydrophobic organic residue and a water-solubilizing anionic, zwitterionic or nonionic group. The hydrophobic radical is usually an aliphatic hydrocarbon radical with 8 to 26, preferably 10 to 22 and in particular 12 to 18 C atoms or an alkyl aromatic radical with 6 to 18, preferably 8 to 16 aliphatic C atoms.

As anionic surfactants e.g. Soaps from natural or synthetic, preferably saturated fatty acids, optionally also from resin or naphthenic acids, can be used. Suitable synthetic anionic surfactants are those of the sulfate, sulfonate and synthetic carboxylate type.

The surfactants of the sulfonate type include alkylbenzenesulfonates (C₉₋₁₅ alkyl), olefin sulfonates, i.e. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from C₁₂₋₁₈ monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products, are considered.

Also suitable are the alkanesulfonates which are obtainable from C₁₂₋₁₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the esters of alpha-sulfofatty acids, e.g. the alpha-sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie from fatty alcohols, such as, for example, coconut oil alcohols, tallow oil alcohols, oleyl alcohol, lauryl, myristyl, Palmityl or stearyl alcohol, or the C₁₀₋₂₀ oxo alcohols, and those secondary alcohols of this chain length. The sulfuric acid monoesters of the aliphatic primary alcohols or ethoxylated secondary alcohols or alkylphenols ethoxylated with 1 to 6 mol of ethylene oxide are also suitable. Sulfated fatty acid alcoholamides and sulfated fatty acid monoglycerides are also suitable.

Other suitable anionic surfactants are the fatty acid esters or amides of hydroxy or aminocarboxylic acids or sulfonic acids, e.g. the fatty acid sarcosides, glycolates, lactates, taurides or isethionates.

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

Addition products of 1 to 40, preferably 2 to 20 moles of ethylene oxide with 1 mole of a compound having essentially 10 to 20 carbon atoms from the group of alcohols, alkylphenols and fatty acids can be used as nonionic surfactants. The addition products of 8 to 20 mol of ethylene oxide with primary alcohols, such as, for example, with coconut oil or tallow fatty alcohols, with oleyl alcohol, with oxo alcohols, or with secondary alcohols with 8 to 18, preferably 12 to 18, carbon atoms, and with mono- or dialkylphenols with 6 to 14 carbon atoms in the alkyl radicals. In addition to these water-soluble nonionics, non-fully or not fully water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants.

Furthermore, the non-ionic surfactants which can be used are the water-soluble adducts of ethylene oxide with 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol, alkylenediamine-polypropylene glycol and with alkylpolypropylene glycols having 1 to 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic radical. Nonionic surfactants of the amine oxide or sulfoxide type can also be used, for example the compounds N-cocoalkyl-N, N-dimethylamine oxide, N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) amine oxide, N-tallow alkyl-N, N-dihydroxyethylamine oxide. For the purposes of the present invention, N-alkoxylated fatty acid amides are not to be understood as nonionic surfactants.

The optionally used zwitterionic surfactants are preferably derivatives of aliphatic quaternary ammonium compounds in which one of the aliphatic radicals consists of a C₈-C₁₈ radical and another contains an anionic, water-solubilizing carboxy, sulfo or sulfato group. Typical representatives of such surface-active betaines are, for example, the compounds 3- (N-hexadecyl-N, N-dimethylammonio) propane sulfonate; 3- (N-tallow alkyl-N, N-dimethylammonio) -2-hydroxypropanesulfonate; 3- (N-hexadecyl-N, N-bis (2-hydroxyethyl) ammonium) -2-hydroxypropyl sulfate; 3- (N-cocoalkyl-N, N-bis (2,3-dihydroxypropyl) ammonium) propane sulfonate; N-tetradecyl-N, N-dimethyl-ammonioacetate; N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonioacetate.

A reduced foaming power, which is desirable when working in machines, can be achieved, for example, by using soaps. In the case of soaps, foam attenuation increases with the degree of saturation and the C number of the fatty acid ester; Soaps of saturated and unsaturated C₁₂₋₂₄ fatty acids are therefore particularly suitable as foam suppressants.

The non-surfactant-like foam inhibitors are generally water-insoluble, mostly aliphatic C₈-C₂₂-carbon-containing compounds. Suitable non-surfactant foam inhibitors are e.g. the N-alkylaminotriazines, i.e. Reaction products of 1 mol of cyanuric chloride with 2 to 3 mol of a mono- or dialkylamine with essentially 8 to 18 carbon atoms in the alkyl radical. Propoxylated and / or butoxylated aminotriazines, e.g. the reaction products of 1 mole of melamine with 5 to 10 moles of propylene oxide and additionally 10 to 50 moles of butylene oxide and the aliphatic C₁₈-C₄₀ ketones, e.g. Stearon, the fatty ketones made from hardened trans-fatty acid or tallow fatty acid, as well as the paraffins and halogen paraffins with melting points below 100 ° C and silicone oil emulsions based on polymeric organosilicon compounds.

The detergents according to the invention can additionally contain bleaching agents and bleach activators. Of the compounds used as bleaching agents which supply H₂O₂ in water, sodium perborate tetrahydrate (NaBO₂. H₂O₂. 3H₂O) and monohydrate (NaBO₂. H₂O₂) are of particular importance. However, other borates which supply H₂O₂ are also useful, e.g. the perborax Na₂B₄O₇. 4H₂O₂. These compounds can be partially or completely by other active oxygen carriers, in particular by peroxypyrophosphates, citrate perhydrates, urea / H₂O₂ or melamine / H₂O₂ compounds as well as by H₂O₂ delivering peracid salts such as e.g. Caroate (KHSO₅), perbenzoate or peroxyphthalate can be replaced.

Since the detergents according to the invention are intended in particular for washing at low washing temperatures, ar preferably bleach components containing activator are incorporated into the detergents. Certain organic peracid-forming N-acrylic or O-acyl compounds serve as activators for per compounds which supply H₂O₂ in water. Compounds which can be used include N-diacylated and N, N`-tetraacylated amines, such as N, N, N`, N`-tetraacetyl-methylenediamine or -ethylenediamine or tetraacetylglycoluril.

As a further component, the washing and cleaning agents can contain dirt carriers, which keep the dirt detached from the fibers suspended in the liquor and thus prevent graying. For this purpose, water-soluble colloids, usually of an organic nature, are suitable, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, such as degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.

Examples

The magnesium aluminum hydroxocarbonate (hydrotalcite) used for example 1 with a structure similar to hydrotalcite was prepared in accordance with DE-OS 15 92 126 by adding a solution of 6.4 kg of Mg (NO₃) ₂. 6 H₂O and 4.7 kg Al (NO₃) ₃. 6H₂O in 17.5 kg of deionized water was added within 4 hours with stirring at room temperature to a solution of 7 kg of 50% strength by weight sodium hydroxide solution and 2.5 kg of sodium carbonate in 25 kg of deionized water. The reaction mixture was then stirred at 65 ° C. for a further 18 hours, the white precipitate was centrifuged off and washed with about 60 l of deionized water. The product was then dried at 110 ° C. in vacuo.

The product shows the X-ray diffraction diagram typical of hydrotalcite with the interferences for interplanar distances d = 7.68, 3.82, 2.67 (reflex with shoulder), 2.32 (wide), 1.97 (wide), 1.52 and 1.50 Å. The analytically determined ratio of Mg to Al is 2.08 to 1.

In the following examples, EO stands for ethylene oxide.

Comparative Example 1

Washing trials were carried out in a household drum washing machine. For this purpose, a phosphate-free, zeolite-based basic detergent with the following composition was first produced:

The basic detergent A was dosed in a 90 ° C cooking program with 104 g in the prewash and 144 in the main wash (water hardness approx. 16 ° d). It was washed 19 times with 3.5 kg of normally soiled laundry in the presence of cotton fabrics. After 19 washes, the cotton fabrics were ashed. The result is shown in Table 1.

Comparative Example 2

Washing tests were carried out in a household drum washing machine with a detergent of the following composition:

Detergent B, like basic detergent A, was dosed in a 90 ° C cooking program with 104 g in the prewash and 144 in the main wash (water hardness approx. 16 ° d). It was washed 19 times with 3.5 kg of normally soiled laundry in the presence of cotton fabrics. After 19 washes, the cotton fabrics were ashed. The result is shown in Table 1.

example 1

Washing tests were carried out in a household drum washing machine with a detergent of the following composition:

Detergent C was, as described in the comparative examples, metered in a 90 ° C. hot-washing program with 104 g in the prewash and 144 in the main wash (water hardness approx. 16 ° d). It was washed 19 times with 3.5 kg of normally soiled laundry in the presence of cotton fabrics. After 19 washes, the cotton fabrics were ashed. Table 1 Example (detergent composition) % Ashes See 1 (A) 1.21 See 2 (B) 0.99 1 (C) 0.84

It can be seen from the results in Table 1 that the use according to the invention of cationic non-silicate layered compounds of the hydrotalcite type in the detergent composition according to the invention leads to a reduction in the deposition of tissue (incrustations) with a constant washing performance.

Claims (7)

1. Use of cationic non-silicate layer compounds of the general formula (I)
Mg _x Al (OH) _y A _z . nH₂O (I)
in which
A stands for an equivalent of a non-silicate anion and the conditions 1 less than x less than 5, y greater than z, (y + z) = 2x + 3, 0 less than n less than 10 apply,
in reduced phosphate detergent compositions,
the cationic non-silicate layer compounds belong to the structural type of hydrotalcite, with a grating distance for the most intense line in the X-ray diffraction diagram of 7.4 to 8 Å for the product dried at 110 ° C. 2. Use of layered connections according to claim 1, characterized in that A stands for one equivalent of a carbonate ion. 3. Use of layered compounds according to claim 1 or 2 in an amount of 1 to 15 wt .-%, based on the detergent composition. 4. Use of layered compounds according to claim 1 or 2 in an amount of 2 to 10 wt .-%, based on the detergent composition. 5. Use of layered compounds according to one of claims 1 to 4 in detergent compositions, the phosphate content being less than 30% by weight. 6. Use of layered compounds according to one of claims 1 to 4 in phosphate-free detergent compositions. 7. Use of layered compounds according to one of claims 1 to 6 in detergent compositions which contain 10 to 35% by weight of zeolite A and 1 to 15% by weight of the cationic non-silicate layered compounds.