EP0576479A1

EP0576479A1 - Liquid or paste-like washing product.

Info

Publication number: EP0576479A1
Application number: EP19920906453
Authority: EP
Inventors: Helmut Blum; Johannes Hachgenei; Karl Schwadtke; Siglinde Hemmann
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1991-03-21
Filing date: 1992-03-12
Publication date: 1994-01-05
Anticipated expiration: 2012-03-12
Also published as: JPH06506006A; DE4109247A1; WO1992016608A1; EP0576479B1; DE59203122D1; ES2075688T3; ATE125862T1

Abstract

New washing products form suspensions of crystalline, stratified sodium silicates and other components typical of washing products in liquid non-ionic surface-active agents or in mixtures of such surface-active agents with organic solvents selected from the group composed of glycols, glycolethers and glycerine, whereas these washing products should not contain more than 30 wt. % water. The silicates used are compounds having the general formula: NaMSIx?O2x+1?.yH2?O, in which M stands for sodium or hydrogen, x is a number between 1.9 and 4 and y is a number from 0 to 20.

Description

"Liquid or pasty detergent"

The present invention relates to liquid to pasty detergents which contain silicates and nonionic surfactants.

For a long time, efforts have been made to replace the phosphates previously contained in almost all detergents as builders (builders) with other substances having the same effect, since phosphates can be responsible for the eutrophication of surface waters. Although substitutes were found with the zeolites in the 1970s that met practically all requirements for such substances, so that they have largely displaced the phosphates from detergents, efforts are still being made to find alternative substitutes for phosphates. A recent proposal concerns crystalline, layered sodium silicates of the general formula a Si _x 02χ + l-yH2Ö \ in which M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 interpret (EP 164 514, EP 337217 and EP 337 219). In contrast to amorphous silicates, which have always been used in detergents, in some cases alone or in addition to phosphate, these crystalline, layered silicates presented there have a pronounced binding capacity for calcium and magnesium ions. They were therefore proposed in the above-mentioned patent applications for use in water softening and as components of solid detergents.

Of these crystalline, layered silicates, however, it was also known that they are inconsistent in the presence of polar, protic liquids and convert into amorphous silicates. With the loss of the layer structure, however, there is inevitably a loss of calcium and magnesium binding capacity, so that an essential function that a detergent builder should have no longer exists. For the These crystalline, layered disilicates therefore did not appear to be suitable for use in liquid or pasty detergents.

Surprisingly, it has now been found that this use in liquid and pasty detergents is nevertheless possible if these detergents contain a liquid phase of a certain composition and the crystalline, layered disilicates are predominantly in suspended form in this liquid phase.

The invention relates to liquid to pasty detergents, the crystalline, layered sodium silicate of the general formula NaMSi _x 02 _{x +} ι.yH2θ, in which M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 mean, wherein this silicate is suspended in a liquid phase, the nonionic surfactants, of the formula R- (0-CH2-CH2-) _n OH (-0. In which R is a long-chain primary or secondary alkyl radical with 8 up to 20 carbon atoms and n represent a number between 3 and 20, and optionally organic solvents from the group of glycols and glycol ethers, and not more than 30% by weight, based on the total agent, of water agents in which the liquid phase contains not more than 20% by weight, in particular not more than 10% by weight, of water.

In the new agents, the decomposition of the crystalline, layered sodium late is suppressed to such an extent that it no longer interferes with the storage times customary for detergents. The builder effect remains at the level necessary for the washing process. Another advantage is that inorganic peroxides can be stably incorporated into these detergents.

The crystalline, layered sodium silicates used according to the invention can be naturally occurring minerals, for example anemite. However, preference is given to using synthetically produced, layered silicates which have been described in various forms in the literature. The silicates of the formula Na-MSι ^' 2θ5 * yH2Ü are particularly preferred, of which in turn the beta and delta modification of Na2Sι ^* 2θ5 are particularly preferred. The crystalline, layered Sodium silicates are preferably contained in the liquid to pasty detergents in amounts between 10 and 50% by weight and in particular in amounts between 20 and 40% by weight, based on the total agent. Preferably, the crystalline, layered sodium silicates are used in the form of very small particles, which are preferably less than 100 .mu.m, in particular less than 30 .mu.m.

The liquid phase, in which the crystalline, layered sodium silicates are suspended, contains non-ionic surfactants of the formula (I) as essential constituents, and optionally organic solvents from the group of glycols and glycol ethers and up to 30% by weight, based on that total funds, in water. The water content is preferably between 0.5 and 20% by weight, in particular not more than 10% by weight, based on the total composition. The water which is introduced into the agents in the form of hydrated water solid salts or in a similarly bound form is to be included in the calculation. Otherwise, the composition of the liquid phase is preferably chosen so that the pour point of this phase is below 15 ° C., in particular below 10 ° C. These values can easily be achieved by using appropriately liquid nonionic surfactants and / or sufficient proportions of organic solvents and / or water.

The nonionic surfactants of the formula (I) which can be used according to the invention are the addition products of 3 to 20 mol of ethylene oxide (E0) and long-chain primary and secondary alcohols having 8 to 20 C atoms, preferably 10 to 18 C atoms. These are preferably addition products of 4 to 10 ol E0 and 1 mol saturated or unsaturated fatty alcohols having 12 to 18 carbon atoms or oxo alcohols of this chain length. Examples of such surfactants are coconut alcohol C1 / 14 ⁺ 3 E0, coconut alcohol C12 / I8 ⁺ 5 E0 and oleyl cetyl alcohol + 10 E0, as well as oxo alcohol C11 13 ⁺ - ¹ ^ .0. The nonionic surfactants of the formula (I) are preferably present in the agents according to the invention in amounts between 10 and 60% by weight, in particular in amounts between 10 and 40% by weight.

As organic solvents, which together with the nonionic surfactants of formula (I) and optionally water, the liquid phase of can form agents according to the invention, are primarily water-soluble glycols and glycol ethers and glycerol into consideration; before preferably no other organic solvents are used additionally. The glycols are preferably those having 2 to 6 carbon atoms in the molecule, and also the di and oligomers of propylene glycol and, preferably, ethylene glycol which are liquid at room temperature. The glycol ethers are preferably the monoethers from methanol, ethanol, propanol or butanol and mono-, di- or triglycols. In particular, the ethers contain no more than 10 carbon atoms per molecule. The organic solvent content is preferably no more than 30% by weight, in particular between 0.5 and 10% by weight, based on the detergent as a whole.

Another preferred component of the liquid to pasty detergents according to the invention are inorganic peroxides, which are effective as bleaching agents. In the simplest case, an equal weight of hydrogen peroxide can be used instead of part of the water present in the liquid phase. However, solid inorganic peroxides are preferably used, which on average are then predominantly also in undissolved, i.e. suspended form. Perborate tetrahydrate, perborate monohydrate and the adduct of H2O2 with sodium carbonate, which is also referred to as percarbonate, are very particularly preferred. The solid inorganic peroxides, like the crystalline, layered sodium silicates, are preferably used in the compositions in very finely divided form. Their content in the agents according to the invention can be up to 30% by weight, preferably between 5 and 30% by weight and in particular between 10 and 25% by weight.

In addition to the constituents already mentioned, the detergents according to the invention can contain further active ingredients and auxiliaries, as are customary in liquid and pasty detergents, provided that these further ingredients do not impair the stability of the detergents. The following are primarily mentioned as such constituents: surfactants of other types, in particular ionic and anionic surfactants, further organic or inorganic builders and sequestering agents, foam regulators, graying inhibitors and bleach activators. Further Examples of such auxiliaries and additives are optical brighteners, detergency boosters, enzymes, dyes, perfumes, inorganic salts and preservatives. The total content of the abovementioned active substances and auxiliaries in the agents according to the invention is generally not more than 50% by weight, preferably between 0.5 and 20% by weight, it being possible for the individual components to be present in the agents in dissolved or suspended form .

The other nonionic surfactants are primarily the addition products of ethylene oxide with polypropylene oxide or with fatty acids, fatty acid amides or alkylphenols with 12 to 18 carbon atoms, and the alkylglycosides, for example the alkylglucosides accessible from glucose and long-chain primary alcohols or to name alkyl polyglucosides. These alkyl glucosides preferably contain 10 to 14 carbon atoms in the alcohol part and 1 to 3 glucose units per molecule. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N.N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is generally not more than that of the nonionic surfactants of the formula (I), preferably not more than half of them.

Suitable synthetic anionic surfactants are in particular those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type come alkyl benzene sulphonates with a Cg_i5 alkyl, olefin sulfonates, ie mixtures of alkene and Hydroxialkansulfonaten, and the disulfonates obtained, for example from Ci2-i8-M ° ^no ° l ^e finen with a terminal or internal Dop¬ obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products. Also suitable are the alkanesulfonates that are made from by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the esters of α-sulfofatty acids, such as. B. the α-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 of primary alcohols of natural or synthetic origin, ie of fatty alcohols such as, for example, coconut oil, tallow oil, oleyl, lauryl, myristyl, palmityl or stearyl alcohol or the C 1 -C 2 -oxo alcohols or secondary alcohols of this chain length. The sulfuric acid monoesters of the aliphatic primary alcohols or ethoxylated secondary alcohols ethoxylated with 1 to 6 mol EO are also suitable. Sulfated fatty acid alkanolamides and sulfated fatty acid onoglycer are also suitable. The anionic surfactants based on natural raw materials are, in particular, the wash-active soaps, ie the salts of the Ci2-Cl8 ~ ^{Fe't' acids} . The anionic surfactants are present in the agents according to the invention preferably in the form of their sodium salts or in the form of the soluble salts with organic bases, in particular mono-, di- and triethanola. The amount of anionic surfactants in the agents according to the invention is preferably not greater than the total amount of nonionic surfactants, in particular it is less than half of the nonionic surfactants. A preferred content is between 5 and 20% by weight, based on the total agent.

Cationic surfactants include, in particular, the quaternary ammonium compounds which, in addition to three shorter alkyl radicals, each with no more than 2 C atoms, have a long-chain alkyl radical with 10 to 18 C atoms on nitrogen. Two or three of the shorter alkyl chains can also be closed to form a ring, for example a pyridine ring. Examples of such compounds are N, N, N-trimethyl-N-tetradecylammonium chloride and N, N-dimethyl-N-hydroxyethyl-N-dodecylammonium hydrogen sulfate.

The betaine surfactants are predominantly long-chain quaternary ammonium compounds in which one of the shorter alkyl substituents contains an anionic group, usually a carboxyl group. An example of a betaine surfactant is N, N-dimethyl-N-cocoalkylaminoacetate.

Although the agents according to the invention preferably contain the crystalline, layered sodium silicates alone as builder substances, the agents may also contain further organic and / or inorganic, soluble or insoluble builder substances. The amount of these additional builder substances is generally not more than the amount of layered silicates and is preferably less than half these silicates; in particular the amount is between 0.1 and 5% by weight, based on the total agent.

The alkaline-reacting salts, in particular alkali salts, which not only precipitate or complexly bind calcium ions, but also, if possible, bring about a synergistic increase in washing power and have a dirt-carrying capacity, should be mentioned as an additional framework substance. Of the inorganic salts, the water-soluble alkali metal or alkali polyphosphates, in particular pentasodium triphosphate, are still of importance. The organic builder substances include sequestering agents of the aminopolycarboxylic acid type, such as, for example. Nitrilotriacetic acid, ethylenediaminetetraacetic acid, and higher homologues. Suitable phosphorus-containing organic complexing agents are the water-soluble salts of alkane polyphosphonic acids, amino and hydroxyalkane polyphosphonic acids and phosphonopolycarboxylic acids, such as, for. B. the compounds methanediphosphonic acid, dimethylaminomethane-l, l-di-phosphonic acid, aminotrimethylenephosphonic acid, ethylenedia intetramethylene-phosphonic acid, diethylenetriaminepentamethylenephosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-l, 2,4-tricarboxylic acid. These sequestrants can also be present in smaller amounts as stabilizers for per compounds. Among the organic framework substances, the N- and P-free polycarboxylic acids that form complex salts with calcium ions are of particular importance. These include low molecular weight compounds, such as. B. citric acid, 2,2'-0xydisuccinic acid or carboxymethyloxy succinic acid, and polymeric polycarboxylic acids with a molecular weight of 350 to about 1,500,000 in the form of the water-soluble salts. 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 include compounds such as, for. B. polyacrylic acid, poly-alpha-hydroxyacrylic acid and polymaleic acid, and the copolymers of the corresponding monomeric carboxylic acids with one another, for example from acrylic acid and maleic acid, or with other ethylenically unsaturated compounds, such as. B. with vinyl methyl ether. In addition, the water-soluble salts of polyglyoxylic acid should also be mentioned. E

Suitable water-insoluble inorganic builders are in particular the finely divided synthetic zeolite A-type sodium aluminosilicates containing bound water described in German patent application DE 2412837 as phosphate substitutes for detergents and cleaning agents. The cation-exchanging sodium aluminosilicates are used in the usual hydrated, finely crystalline form, i.e. H. they have practically no particles larger than 30 μm and preferably consist of at least 80% of particles smaller than 10 μm. Their calcium binding capacity, which is determined according to the information in DE 24 12837, is in the range from 100 to 200 mg CaO / g. The zeolite NaA can be used in particular, also the zeolite NaX and mixtures of NaA and NaX. However, the zeolites are preferably only used in the agents according to the invention if no inorganic peroxides, in particular perborate, are present.

Suitable inorganic, non-complexing salts are the bicarbonates, also known as "washing alkalis", carbonates, borates, sulfates or amorphous silicates of the alkalis. Other structural substances that are also used 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, of sulfobenzoic acids, sulfophthalic acid, sulfoacetic acid, sulfosuccinic acid and the salts of acetic acid or lactic acid.

Examples of foam regulators which may be mentioned are the salts of fatty acids with 20 to 24 C atoms or long-chain N-alkylaminotriazines with essentially 8 to 18 C atoms in the alkyl radical or aliphatic Ci8-40 ketones. Paraffin and silicone oil dispersions are preferred, which can optionally be made up with microfine silica. The content, for example in the case of soaps, can be up to 5% by weight of the total composition, in the case of the paraffins and silicone oils it is usually substantially less, for example 0.05 to 0.5% by weight.

Above all, graying inhibitors are cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed ethers, such as To mention methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxy ethyl cellulose, furthermore mixtures of various cellulose ethers, in particular mixtures of carboxymethyl cellulose and methyl cellulose.

In order to strengthen the bleaching effectiveness of the agents according to the invention, they may contain bleach activators in addition to inorganic peroxide. These are acylating agents which react with hydrogen peroxide in the wash liquor to form peroxycarboxylic acids or their salts. Examples of common bleach activators are tetraacetylethylene diamine, pentaacetyl glucose and diacetyl dioxohexahydrotriazine. In addition to N-acyl compounds and O-acyl compounds, anhydrides can also be used. Bleach activators are preferably used which remain largely undissolved in the liquid portion of the detergent and are therefore predominantly in suated form. The amounts of bleach activators are preferably not more than 6% by weight, in particular between 2 and 5% by weight, based on the total agent.

Optical brighteners which are particularly suitable for detergents are alkali metal salts of 4,4-bis- (2 "-anilino-4" -morpholino-l, 3,5-triazinyl-6 "-amino) stilbene-2,2'-disulfonic acid or of a similar structure Compounds which carry a diethanola ino group instead of the morpholino group, and brighteners of the substituted diphenylstyryl type, for example the alkali metal salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis, are also suitable - (4-chloro-3-sulfostyryl) diphenyl and 4- (4-chlorostyryl-4 '- (2-sulfostyryl) diphenyls.

Detergent boosters are polar long-chain compounds which do not themselves have any surface-active properties, but are capable of increasing the cleaning action of the surfactants contained in the detergents. Examples of such compounds are coconut amine + 2 EO and the addition products of glycerol and long-chain oc-olefin epoxide.

Enzymes from the class of proteases, lipases and amylases or mixtures thereof can be used. From bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic substances obtained. The enzymes can be embedded in coating substances to protect them against premature decomposition.

The preparation of the agents according to the invention presents no difficulties. In the simplest case, it is carried out by mixing all the components, the components which later form the liquid phase are expediently premixed and the components to be suspended are then introduced into this liquid and mixed homogeneously therewith. The solid constituents of the composition are preferably already based on particle sizes such as are later to be present in the finished composition, but it is also possible to reduce the size of the suspended solid particles further by wet grinding the finished composition . The viscosity of the finished product depends primarily on the solid / liquid ratio in the finished product and on the viscosity of the liquid phase. This in turn can be varied within wide limits by choosing suitable components. For example, the viscosity can be reduced by adding organic solvents and the viscosity can be increased by adding constituents with a thickening effect, such as soaps. Liquid agents according to the invention preferably have viscosities between approximately 1,000 and approximately 5000 mPas, in particular between approximately 2000 and approximately 4000 mPas, the viscosity being measured at 20 ° C. using a Brookfield viscometer. The viscosities of the detergent in paste form, which are preferred because of their particularly high physical stability, go far beyond.

The agents according to the invention are primarily intended for use in textile washing. Depending on the content of active ingredients, they can be used as stand-alone detergents or as detergent additives. However, if the active ingredients are selected appropriately, they are also suitable for cleaning hard surfaces in the home or in the commercial sector. Due to the stability of the suspensions, the agents can also be metered automatically. «1 examples

The paste-like detergents A and B described below were prepared in batches of 50 g each by weighing all the components together and homogenizing the mixtures in a ceramic ball mill (running time 5 minutes).

Ingredients content in percent by weight

Crystalline layered disili- 19.1 21.1 kat (delta form) (SKS 6, Hoechst AG)

Nonionic surfactant Dehydol LST 80/20 10.5 18.0 (Henkel)

Polyethylene glycol 400 5.3 5.4

C] .2 / l3-alkylbenzenesulfonate-Na (55 ^% i9 ^e 33.3 14.5 aqueous paste)

Sodium perborate tetrahydrate 31.8 22.0

Sodium carbonate 9.0

Acrylic acid-maleic acid copoly erisat 5.0 (Sokalan CP5, BASF)

Tallow fatty acid Na soap 5.0

Both detergents were stored in closed polyethylene bags at 40 ° C for 4 weeks. No signs of phase separation were seen after this time. Obtaining the crystalline layered ^• ^

The structure of the disilicate was demonstrated with the help of the X-ray reflexes. A loss of active oxygen could not be determined by manganometric titratio.

Claims

1. Liquid or pasty detergent containing crystalline layered sodium silicate of the general formula NaMSi _x 02χ ₊ ι ^* yH2Ö in which M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, suspended in one liquid phase, di nonionic surfactants of the formula R- (0-CH2-CH2-) _n 0H, in which R is a long-chain primary or secondary alkyl radical having 8 to 20 carbon atoms and a number between 3 and 20, and optionally organic Contains solvents from the group of glycols and glycol ethers and glycerol and not more than 30% by weight, based on the total composition, of water.

2. Detergent according to claim 1, in which the crystalline, layered sodium silicate corresponds to the formula NaMSi2Ü5 * yH2θ.

3. Detergent according to claim 2, in which the beta and / or the delta modification of Na2Sι ^* 2θ5 is contained as a crystalline, layered sodium silicate.

4. Detergent according to one of claims 1 to 3, in which the water content is not more than 20% by weight, preferably not more than 10% by weight.

5. Detergent according to one of claims 1 to 3, containing

10 to 50, preferably 20 to 40% by weight of crystalline, layered sodium silicate, 10 to 60, preferably 10 to 40% by weight of nonionic surfactant

Formula (I), 5 to 30, preferably 10 to 25% by weight of inorganic peroxide, 0 to 30, preferably 0.5 to 10% by weight of organic solvent, 0 to 30, preferably 0.5 to 20% by weight % Water and 0 to 50, preferably 0.5 to 20 wt .-% of other usual

Detergent ingredients. 1Y

6. Detergent according to claim 5, in which the nonionic surfactant is selected from the group of addition products from 4 to 10 mol of ethylene oxide and 1 mol of long-chain alcohol having 10 to 18 carbon atoms.

7. Detergent according to claim 5, in which the inorganic peroxide is selected from the group sodium perborate monohydrate, sodium percarbonate and mixtures thereof.

8. Detergent according to claim 5 in paste form.