DE2644289A1 - Compsn. for washing solid materials esp. textiles - contains tert. amine surfactant and allows redn. in detergent concn. - Google Patents

Abstract

Compsn. for washing and cleaning solid materials, esp. textiles, contains 0.5-40 wt. % tert. amine surfactant having formula R'R3CH-CHR2-N(CH2CHOH-CH2OH)2 (I) (where R' is 1-16C alkyl or alkenyl, R2 is H or 1-16C alkyl, R3 is H, 4-14C alkyl or OH. If R3 is H, or OH, alkyl gps. R'+R2 contain 6-20C. If R2 is H, the alkyl or alkenyl gp. R' contains 6-16C and R3 is H, OH or 4-14C alkyl, provided that alkyl gp. R3 is always 2C shorter than the alkyl gp. R') opt. as its water-soluble salt with an anion resistant to washing and dry-cleaning. (I) can be used in low-phosphate or phosphate free compsn. (I) have high surfactant activity and allow lowering of detergent compsns. A detergent compsn. was prepd contg. 4% N-dodecyl and 2% N-hexadecyl-N, N-bis(2,3-dihydroxypropyl)-amine.

Description

"Detergents and cleaning agents"

The invention relates to washing and cleaning agents, in particular low-phosphate and phosphate-free compositions.

By spreading new textile materials, for example from Polyester or finished cotton, and due to changing consumer habits, which are expressed, for example, in the increasing popularity of colorful textiles, the detergent specialist is given the task of creating the recipes for detergents and cleaning products to constantly review and improve to keep them changing To adapt to requirements.

In addition, the globally recognized problem of eutrophication is compelling of lakes and rivers due to insufficiently treated wastewater, whose phosphate content increases Some of them come from laundry detergents and cleaning products, and the skilled person can find new and effective products Develop compositions that contain no or significantly less phosphate than that commercially available products.

Numerous suggestions have already been made in the specialist literature the detergent phosphates, especially the most commonly used sodium triphosphate, to be substituted by other, similarly acting detergent builder substances. However, this substitution requires the use of other, usually more expensive compounds, which themselves raise new problems or are inferior to the triphosphate in their effect are.

It has now been found that certain by the novel use Amines and their salts as surfactants in detergents and cleaning agents are a solution of the Phosphate problem becomes possible in which the amounts of phosphate that are still common today are considerable reduced or can be replaced by smaller amounts of other ~ structural ~ substances without that there is a loss of performance in such detergents and cleaning agents.

It has also been found that the use of these amines or Amine salts as surfactants in detergents with a high phosphate content, for example in heavy-duty detergents with usually 40 wt. t of sodium triphosphate, a significant improvement in Washing effect is achieved over the formulations of the prior art, so that Satisfactory results can be achieved even with reduced detergent dosages without having to accept a reduction in performance, what can also lead to a reduction in the phosphate pollution of the wastewater.

The washing and cleaning agent according to the invention is characterized in that it is a tertiary amine of the formula I, optionally together with other surfactants from the group of anionic, nonionic and zwitterionic surfactants in which Rl is an alkyl or alkenyl group with 1-16 carbon atoms, R2 is hydrogen or an alkyl group with 1-16 carbon atoms, R3 is hydrogen, an alkyl group with 4-14 carbon atoms or the hydroxyl group, where in the case R3 = H or OH the The sum of the carbon atoms of the alkyl groups R1 and R2 is in the range 6-20, and where R2 = H, the alkyl or alkenyl group R1 has 6-16 carbon atoms and R3 in this case is hydrogen, the hydroxyl group or an alkyl group with 4-14 Can mean carbon atoms, with the further proviso that an alkyl group R3 is in each case 2 carbon atoms shorter than an alkyl group R1, optionally in the form of its water-soluble salt with an anion which is compatible with washing and cleaning.

Suitable tertiary amines can be prepared in a manner known per se, for example by reacting one mole of a primary amine of the formula II in which R1, R2, R3 have the meaning given in formula I, are obtained with 2 mol of glycide. Instead of glycid, a glycerol-a-halohydrin can also be used. The reaction can be carried out at room temperature or elevated temperature with or without the use of solvents.

The primary amines for the reaction with glycide are, for example, the technical easily accessible fatty amines with R2 = R3 = H in question.

It is also possible to use 2-hydroxyalkyl2mines, which are easily obtained can be obtained if terminal or internal epoxyalkanes react with ammonia leaves; in this case, R3 is a hydroxyl group and R2 is hydrogen or a Alkyl group, depending on whether one is from epoxides with terminal or internal Epoxy group goes out. The internal primary alkylamines are also suitable, obtained by reducing the corresponding nitroparaffins. R3 is then hydrogen and R2 is an alkyl group. Furthermore, "Guerbetalkylamines" such as 2-hexyldecylamine, 2-Octyldodecylamine are used, for the production of which one uses fatty alcohols goes out, their original carbon number for the production of surfactants to is short, and which is doubled by the Guerbet reaction. In this case it is R2 is hydrogen and R3 is an alkyl radical which has 2 carbon atoms less than R1.

Typical representatives of compounds of the formula I, which are in the inventive Agents that can be used are e.g.

N-decyl-N, N-bis (2,3-dihydroxypropyl) -amine, N-dodecyl-N, N-bis (2,3-dihydroxypropyl) -amine, N-tetradecyl-N, N-bis (2,3-dihydroxypropyl) -amine, N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) -amine, N-octadecyl-N, N-bis (2,3-dihydroxypropyl) -amine, N-cocoalkyl-N, N-bis (2,3-dihydroxypropyl) -amine, N-tallowalkyl-N, N-bis (2,3-dihydroxypropyl) -amine, N-2-hydroxydecyl-N, N-bis (2,3-dihydroxypropyl) -amine, N-2-hydroxydodecyl-N, N-bis (2,3-dihydroxypropyl) -amine, N-2-hydroxytetradecyl-N , N-bis (2,3-dihydroxypropyl) -amine, N-2-hydroxyhexadecyl-N, N-bis (2,3-dihydroxypropyl) -amine, N-2-Hydroxyoctadecyl-N, N-bis (2,3-dihydroxypropyl) -amine, N- (2-hydroxyi-C11-C14-alkyl) -N, N-bis (2,3-dihydroxypropyl) -amine (i = internal), N- (2-hydroxy-i-C15-C18-alkyl) -N, N-bis (2,3-dihydroxypropyl) amine, N-i-C10-C13-alkyl-N, N-bis (2, 3-dihydroxypropyl) -amine, N-i-C14-C15-alkyl-N, N-bis (2,3-dihydroxypropyl) -amine, N-i-C17-CXo-alkyl-N, N-bis (2,3-dihydroxypropyl) -amine, N-2-butyloctyl-N, N-bis (2,3-dihydroxypropyl) -amine, N-2-hexyldecyl-N, N-bis (2,3-dihydroxypropyl) -amine, N-2-octyldodecyl-N, N-bis (2,3-dihydroxypropyl) -amine.

Particularly preferred are compounds of the formula I, which one by Implementation of fatty amines or of 2-hydroxyalkylamines, their aliphatic radical Has 6-20, in particular 8-18 and very particularly 10-14 carbon atoms, with glycide receives.

The compounds of the formula I are notable for their use as Surfactants in detergents and cleaning agents due to their high washing effect, especially in low-phosphate and phosphate-free compositions, including low-phosphate compositions those with a calculated phosphorus content of at most 6% by weight, preferably not more than 5% by weight are to be understood. In recipes with a high phosphate content the compounds of formula I also bring about a significant improvement in the In addition, washing performance compared to agents that contain known surfactants was increased surprisingly found that the compounds of formula I compatible with common anionic surfactants in all mixing ratios are. This offers an extremely wide range of possible combinations, which allow the agents according to the invention to be cleaned as well as the substrates adapt to consumer habits and, in particular, to environmental requirements, without having to accept any loss of washing power, and without a real one Phosphate substitute would be required.

Compounds of the formula I, provided they are derivatives of fatty amines represent, and a method for their production, are known from DAS 1 004 194, in which these compounds - in the form of their salts - as wetting, emulsifying, cleaning and disinfectants are shown. The detergent was able to provide this information expert but no suggestion for the use of these substances according to the invention in particular not their combinability with anionic surfactants.

The washing and cleaning agents according to the invention contain the amines of the formula I in amounts of 0.5-40% by weight. Preparations are also of practical importance which contain the amines of the formula I in the form of surfactant combinations based on 1 Part by weight of amine of the formula I O -5, generally 0.1-3, and in particular 0.2 - 2 parts by weight of at least one other surfactant from the group of anionic, Have nonionic and zwitterionic surfactants. These surfactant combinations are in the agents according to the invention generally in an amount of 0.5-80 % By weight, preferably 5-35% by weight.

Contain detergents according to the invention with low foaming power 0.2-0.8% by weight of a non-surfactant foam inhibitor or 0.5-5% by weight an alkali soap consisting essentially of C18-C22 fatty acids, or a mixture of the non-surfactant foam inhibitor and the soap in an amount of 0.2-5 Wt%.

The agents according to the invention preferably contain at least one Another component of detergents and cleaning agents from the inorganic group and / or organic builders, optionally including a bleaching component, Enzymes, optical brighteners, graying inhibitors, foam regulators, antimicrobial Active ingredients, fragrances and dyes. Liquid embodiments can in addition to or instead of from water still low molecular weight, water-miscible organic solvents, in particular from the group of aliphatic alcohols, diols and ether alcohols contain.

The detergents and cleaning agents according to the invention generally have the following composition: 0.5-80% by weight of the surfactant combination defined above, 10-90% by weight of inorganic or organic water-soluble and / or water-insoluble Builders, 0-40% by weight bleaching substances and optionally activators and Stabilizers for the bleaching substances, the remainder up to 100% by weight of conventional carriers, auxiliaries and Fillers.

Particularly preferred surfactant combinations consist of 1 part by weight of an amine of the formula I and 0.2 to 2 parts by weight of a sulfonate surfactant and / or of a nonionic surfactant of the ethoxylated aliphatic C8-C20 alcohol type.

The particularly preferred low-phosphate and phosphate-free laundry detergents correspond to the following composition: 5 - 35% by weight of the surfactant combination defined above, 0.2-0.5% by weight of a foam inhibitor, consisting of 0.2-0.8% by weight of a non-surfactant Foam inhibitor, or 0.5-5% by weight of an alkali soap consisting essentially of C18-C22 fatty acids, or a mixture of the non-surfactant foam inhibitor and the soap, 0 - 20 wt .-% condensed phosphates, especially sodium triphosphate, 0.2-30 wt .-% another, non-phosphate-containing, preferably phosphorus-free, structural substance from the group of inorganic or organic water-soluble or water-insoluble Builder substances, 0-40% by weight of a bleaching component, including optionally existing activators and / or stabilizers, the remainder up to 100% by weight other common ones Components of powder, paste or liquid detergents and cleaning agents, where in the case of phosphate and / or phosphonate-containing compositions the arithmetic Phosphorus content is at most 6, preferably at most 5 wt .-%.

The agents according to the invention are powdery, pasty or liquid. Preparations of powdery nature are preferred. The powdered preparations can be prepared by various methods known per se. In the simplest If so, they can be made by mixing the ingredients.

A technically preferred method is an aqueous approach the components that are insensitive to water and heat in a known meadow, e.g. converted into a powder by spraying in a hot or cold air stream. The so obtained Powders are the ones that are sensitive to hydrolysis and heat or slightly volatile other components of the preparation subsequently mixed in. These include e.g. bleaching substances and activators for them, enzymes, antimicrobials Substances, fragrances, etc. Liquid means are created by dissolving the constituents in the liquid carrier substances, optionally produced with heating. at the production of pasty agents is the amount of liquid carrier substances chosen that a paste is obtained after mixing all the ingredients.

If one chooses to produce the agents according to the invention in powder form the method of drying an aqueous batch in a stream of hot air, see above it is expedient, the amines of the formula I in the form of their salts with a one or Use polybasic inorganic or organic acid, as the salts are Can be distributed better in the aqueous approach than the free amines. For salt formation with the amines of the formula I, for example, the following acids are suitable: hydrochloric acid, Hydrobromic acid, nitric acid, sulfuric acid, orthophosphoric acid, formic acid, Acetic acid, propionic acid, citric acid, oxalic acid, lactic acid, tartaric acid, benzene, Toluene and xylene sulfonic acid. But also other acids can in principle lead to salt formation can be used with the amines of formula I. The preparation of the salts can be done by Addition of the acid in question in an equivalent amount to the water / alcohol mixtures, if appropriate dissolved amines followed by concentration and drying of the salts. Man receives the salts in viscous, pasty to waxy solid form.

The invention further relates to a method for producing the washing and cleaning agents containing the compounds of the formula I. This process is characterized in that the compounds of formula I are in the form of their water-soluble salts with anions compatible with washing and cleaning, in particular as sulfates, acetates, propionates, citrates, lactates or hydrochlorides in the means incorporated.

These salts are preferred for the production of powdered compositions into an aqueous slurry of the hydrolysis and heat-resistant components of the product to be produced Introduced by means and this pulp - preferably by the method of hot air drying - converted into a pourable powder.

According to another preferred embodiment of the method for To prepare the powdery agents, aqueous solutions of the salts are sprayed on Amines of the formula I in suitable mixing devices for continuous or discontinuous mixing on powdery, water-binding constituents of the agent on.

The agents according to the invention can be used in particular as full, pre and use mild detergent. Preparations that are used as pre-wash agents should show - as well as the heavy-duty or high-temperature detergents - in 1% aqueous solution a pH value between 9.5 and 11, which is achieved by adding washing alkalis will. Preparations suitable as mild detergents are neutral in 1 of the above aqueous solution to slightly alkaline (pH 7 - 9.5), but sometimes also slightly acidic (pH 6 - 7). The cooking or heavy-duty detergents also differ from the other preparations by the content of a bleaching component, e.g. from a peroxy compound as active oxygen carriers, in particular sodium perborate, stabilizers and optionally Activators for the peroxy compound may consist of 10 to 40, in particular 15 to 35 wt .-% of the total detergent can make up.

The surfactants, in addition to the amine of the formula I in the inventive Agents can be contained, have at least one hydrophobic organic in the molecule Remainder and a water-solubilizing anionic, zwitterionic or nonionic Group up. The hydrophobic residue is usually an aliphatic one Hydrocarbon radical with 8-26, preferably 10-22 and in particular 12-18 C atoms or an alkyl aromatic radical with 6-18, preferably 8-16 aliphatic Carbon atoms.

As anionic surfactants, e.g. soaps made from natural or synthetic, preferably saturated fatty acids, especially those with substantially 10 - 18, preferably 12-16 carbon atoms, optionally also made of resin or Naphthenic acids useful. Suitable synthetic anionic surfactants are such of the sulfonate, sulfate and synthetic carboxylate type.

As surfactants of the sulfonate type are alkylbenzenesulfonates (C915-alkyl), Mixtures of alkene and hydroxyalkane sulfonates and disulfonates, as they are, for example from monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the Sulfonation products obtained into consideration. Also suitable are alkanesulfonates that from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins. Further useful sulfonate type surfactants are the esters of α-sulfo fatty acids, e.g. α-Sulphic acids from hydrogenated methyl or ethyl esters of coconut, palm kernel or tallow fatty acids.

Suitable surfactants of the sulfate type are the primary sulfuric acid monoesters Alcohols (e.g. from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol) and those of secondary alcohols. Sulphated fatty acid alkanolamides are also suitable, sulfated fatty acid monoglycerides or the sulfated reaction products of 1 - 4 moles of ethylene oxide with primary or secondary fatty alcohols or alkylphenols.

Other suitable anionic surfactants are the fatty acid esters or -amides of hydroxy- or amino-carboxylic acids or -sulphonic acids, such as 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 as soluble salts of organic bases, such as mono-, di- or triethanolamine are present.

Addition products of 4 to 40 are preferred as nonionic surfactants 4 - 20 moles of ethylene oxide in 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide can be used. The addition products are particularly important from 5 - 16 moles of ethylene oxide to primary alcohols such as coconut or tallow fatty alcohols, to oleyl alcohol and to C8-C20 oxo alcohols, or to secondary C8-C20 alcohols, as well as of mono- or dialkylphenols with 6-14 carbon atoms in the alkyl radicals. Besides these However, water-soluble nonionics are also not or not completely water-soluble Polyglycol ether with 1 - 4 ethylene glycol ether residues in the molecule of interest, in particular, when used together with water-soluble nonionic or anionic surfactants will.

Furthermore, the water-soluble, 20 - Containing 250 ethylene glycol ether groups and 10-100 propylene glycol ether groups Addition products of ethylene oxide with polypropylene glycol, with alkylenediamine polypropylene glycol, and on alkyl polypropylene glycols with 1 - 10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic residue.

There are also nonionic surfactants of the amine oxide or sulfoxide type usable, 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.

A reduced foaming power, which is desirable when working in machines is often achieved by combining the various surfactants with soaps, the foam-suppressing effect of the soaps with the degree of saturation and the C number of the fatty acid residue increases. These are therefore suitable as foam-inhibiting soaps Soaps of natural and synthetic origin, which have a high content of C18-C22 fatty acids have, for example the derivatives of hydrogenated fish oil and rapeseed oils. In the In practice, mostly fatty acid mixtures with a chain length distribution of C12 to C22. Under the term "soaps of fatty acids with essentially C18-C22 carbon atoms" soaps are to be understood here which are at least 50% by weight of C18-C22 fatty acid salts exist.

The non-surfactant foam inhibitors are generally around 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 - 3 mol of a mono- or dialkylamine with essentially 8-18 carbon atoms in the alkyl radical. Are suitable also propoxylated and / oret butoxylated aminotriazines, e.g. the reaction products of 1 mole of melamine with 5 - 10 moles of propylene oxide and an additional 10 - 50 moles of butylene oxide, as well as the aliphatic C18-C40 ketones such as stearone, the fatty ketones from hardened Tran fatty acid or tallow fatty acid, etc. The paraffins and haloparaffins are also suitable with melting points below 100 ° C. and in particular polymeric organosilicon Compounds of the silicone oil type.

The amphoteric or zwitterionic surfactants contain in the molecule both acidic groups, such as the carboxyl, sulfo, sulfuric acid half-ester, phosphono or phosphoric acid partial ester groups, as well as basic groups, such as amino, Imino or ammonium groups. Zwitterionic compounds with a fourfold substituted, i.e. quaternary ammonium groups are referred to as betaines if they also have a covalently bound acid group in the molecule and the positive one and negative charge is intramolecularly balanced. In a broader sense belong to Class of betaines also the correspondingly substituted quaternary phosphonium and tertiary sulfonium compounds.

Because of their good cleaning properties and their good compatibility with other surfactants, the carboxy, sulfonate and sulfate betaines have a special one practical importance. Surface-active betaines have at most nitrogen two, but generally only one, higher molecular weight aliphatic hydrocarbon radical with a hydrophobic character and at least one, but generally two, lower Alkyl radicals with 1 - 3 carbon atoms, which are represented by one or two hydroxyl groups substituted or connected to one another directly or via a heteroatom. The anionic, water-solubilizing acid group is above the fourth substituent, which usually consists of a short-chain, optionally a double bond or a hydroxyl group having aliphatic radical is connected to the ammonium nitrogen.

Typical representatives of such surface-active betaines are, for example the compounds 3- (N-hexadecyl-N, N-dimethylammonio) propane sulfonate; 3- (N-tallowalkyl-N, N-dimethylammonio) -2-hydroxypropanesulfonate; 3- (N-hexadecyl-N, N-bis (2-hydroxyethyl) ammonio) -2-hydroxypropyl sulfate; 3- (N-coconut alkyl-N, N-bis (2, 3-dihydroxypropyl) ammonio) propane sulfonate; N-tetradecyl-N, N-dimethyl-ammonioacetate; -N-hexadecyl-N, N-bis (2,3-dihydroxypropyl) ammonioacetate.

These surface-active betaines can be produced, for example, by combining the tertiary amine with the hydrophobic long-chain aliphatic hydrocarbon radical and the two lower alkyl or hydroxyalkyl radicals with quaternizing agents, such as 3-chloro-2-hydroxypropyl sodium sulfonate, 3-chloro-2-hydroxypropyl sodium sulfate, Sodium chloroacetate or propane sultone, butane sultone or carbyl sulphate.

Also suitable as surfactants are those sulfonate betaines in which the anionic, water-solubilizing group directly on the long-chain, for capillary activity responsible hydrophobic hydrocarbon residue is bound. Such sulfobetaines can be prepared, for example, from C8-C20-α-olefins by using them with Converts sulfur trioxide to a sultone and thus a tertiary amine with three short-chain ones aliphatic radicals quaternized in a known manner.

Weakly acidic, neutral or alkaline substances are suitable as structural substances reacting inorganic or organic salts, especially alkali salts, the calcium ions fail or be able to bind in a complex manner.

Of the inorganic salts, the water-soluble alkali metal or alkali polyphosphates, especially pentasodium triphosphate, in addition to the alkali ortho- and alkali pyrophosphates, of particular importance. These phosphates can be whole or be partially replaced by organic complexing agents for calcium ions. In addition include compounds of the aminopolycarboxylic acid type, such as nitrilotriacetic acid, Ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and higher homologues. Suitable Phosphorus-containing organic complexing agents are the water-soluble ones Salts of the alkane polyphosphonic acids of the amino and hydroxyalkane polyphosphonic acids and the phosphonopolycarboxylic acids, such as the salts of methanediphosphonic acid, Propane-7,2,3-triphosphonic acid, butane-d, 2,3,4-tetraphosphonic acid, polyvinylphosphonic acid, 1-aminoethane-1, 1-diphosphonic acid, 1-amino-1-phenylmethane-1,1-diphosphonic acid, aminotrimethylene triphosphonic acid, Methylamino- or ethylaminodimethylene diphosphonic acid, ethylenediaminotetramethylene tetraphosphonic acid, 1-hydroxyethane, 1 -diphosphonic acid, 1-phosphonoethane-1,2-dicarboxylic acid, 2-phosphonopropane-2,3-dicarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 2-phosphonobutane-2,3,4-tricarboxylic acid and Copolymers of vinyl phosphonic acid and acrylic acid.

Of particular importance are the nitrogen- and phosphorus-free, Polycarboxylic acids which form complex salts with calcium ions, including carboxyl groups containing polymers include. Citric acid, tartaric acid, benzene hexacarboxylic acid, for example, are suitable and tetrahydrofuran tetracarboxylic acid. Also containing carboxymethyl ether groups Polycarboxylic acids are useful, such as diglycolic acid, 2,2'-oxydisuccinic acid as well as polyhydric alcohols partially or completely etherified with glycolic acid or hydroxycarboxylic acids such as bis (O-carboxymethyl) ethylene glycol or carboxymethyltartronic acid, mono- or bis (O-carboxymethyl) -tartaric acid or the carboxymethylated derivatives of erythronic acid, trihydroxyglutaric acid, gluconic acid, Sugar acid, mucic acid etc. and carboxymethylated or oxidized polysaccharides. The water-soluble salts of polymeric carboxylic acids are also suitable a molecular weight of at least 350, such as polyacrylic acid, poly - «- hydroxyacrylic acid, Polymaleic acid, polyitaconic acid, polymesaconic acid, polyaconitic acid, polymethylene malonic acid, Polycitraconic acid and the like. Also copolymers of the corresponding monomers Carboxylic acids with one another or with ethylenically unsaturated Compounds such as ethylene, propylene, isobutylene, vinyl methyl ether, furan, acrolein, Vinyl acetate, acrylamide, acrylonitrile, methacrylic acid, crotonic acid etc. can be used, such as those from the 1: 1 copolymers of maleic anhydride and ethylene water-soluble salts obtainable or propylene or furan.

Usable phosphorus- and nitrogen-free organic complexing agents are also those composed essentially of acrylic acid and allyl alcohol units Polyhydroxycarboxylic acids obtained by copolymerization of acrolein and acrylic acid available in the presence of hydrogen peroxide and subsequent Cannizzaro reaction are.

Suitable inorganic, non-complexing salts - in general too called washing alkalis - are the bicarbonates, carbonates, borates, sulfates or alkaline silicates; The main alkali silicates are sodium silicates with a Na20: SiO2 ratio of 1: 1 to 1: 3.5 can be used.

Further structural substances because of their hydrotropic property are mostly used in liquid agents, are the salts of the non-capillary active, 1 - 8 carbon atoms containing sulfonic acids, carboxylic acids and sulfocarboxylic acids, for example the alkali salts of benzene, toluene or xyiolsulfonic acids, the sulfobenzoic acids, Sulfophthalic acid. Sulphoacetic acid, sulphosuccinic acid and the salts of acetic acid or lactic acid.

Complexing agents which are insoluble in water can also be used. These include phosphorylated cellulose and graft polymers of acrylic acid or methacrylic acid on cellulose, which can be in the form of woven or non-woven fabrics. Furthermore are spatially networked and thus made water-insoluble Copolymers acrylic, methacrylic, crotonic and maleic acid as well as other polymerizable polycarboxylic acids, optionally with other ethylenically unsaturated compounds in the form of sodium or potassium salts are suitable as insoluble complexing agents. These insoluble copolymers can be used as fleece, sponges or in the form of finely ground, specifically lighter There are foams with an open-cell structure.

The water-insoluble inorganic builder substances are suitable in DT-OS 24 12 837 as phosphate substitutes for detergents and cleaning agents described, finely divided, synthetically produced, water-insoluble silicates of the general formula 0.7 - 1.5 Cat2 / nO. Me2O. 0.8 - 6 SiO2, in the cat one with the calcium ion exchangeable cation of valency n and Me aluminum or boron mean, which additionally contain bound water and a calcium binding capacity contain from 50-200 mg CaOgg of the anhydrous silicate .. Used with preference the alkali aluminum silicates of this composition, especially the crystalline ones Sodium aluminum silicates with the composition 0.7 - 1.1 Na2O. Al203. 1.3-3.3 Si02, whose calcium binding capacity is in the range of 100 - 200 mg / g of the anhydrous Aluminum silicate is, the particle sizes of these aluminum silicates essentially below 40 V and in particular in the range from 10 to 0.1 ii.

Among the compounds that serve as bleaching agents and yield H202 in water have sodium perborate tetrahydrate (NaB02 H202. 3 H20) and monohydrate (NaB02 . H202) of particular importance. However, other H202-yielding borates can also be used, e.g. the Perborax Na2B407. 4 11202. These compounds can be partially or fully by other active oxygen carriers, in particular by peroxyhydrates such as peroxycarbonates (Na2CO3. 1.5 H202), peroxypyrophosphate, citrate perhydrate, urea-a202- or Melamine H2 0 2 compounds as well as peracid salts that supply H202, e.g. Caroate (KHSO5), perbenzoate or peroxyphthalate can be replaced.

It is advisable to use the usual water-soluble and / or water-insoluble Stabilizers for the peroxy compounds together with them in amounts of 0.25 - to incorporate 10% by weight.

As water-insoluble stabilizers, e.g. 1 - 8, preferably Make up 2 - 7% of the weight of the entire preparation, they are mostly suitable Precipitation of magnesium silicates obtained from aqueous solutions MgO: SiO2 = 4: 1 to 1: 4, preferably 2: 1 to 1: 2 and in particular 1: 1 other alkaline earth metal, cadmium or tin silicates of the same composition useful. Hydrous oxides of tin are also suitable as stabilizers. Water-soluble stabilizers that coexist with water-insoluble ones The organic complexing agents, the amount of which is 0.25-5, are preferred 0.5 - 2.5% of the weight of the entire preparation.

Means to be used for washing textiles at temperatures below 70 ° C can bleach activators from the class of the N- or O-acyl compounds, in particular Contain tetraacetylethylenediamine or tetraacetylglycoluril. The ones from the bleach activator or powder particles consisting of the per compound can be coated with coating substances, like water-soluble polymers or fatty acids coated to interact to avoid between the per compound and the activator during storage.

The detergents can be used as optical brighteners for cotton in particular Derivatives of diaminostilbene disulfonic acid or

contain their alkali metal salts. Examples of suitable salts are 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) stilbene-2,2'-disulfonic acid or similarly structured compounds that instead of the morpholino group is a diethanolamino group, a methylamino group or a Carry 2-methoxyethylamino group. These are used as brighteners for polyamide fibers of the 1,3-diaryl-2-pyrazoline type, for example the compound 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2 pyrazoline and similarly structured compounds that replace the sulfamoyl group e.g. the methoxycarbonyl, 2-methoxyethoxycarbonyl, the acetylamino or the vinylsulfonyl group wear. Usable polyamide brighteners are also the substituted aminocoumarins, e.g. 4-methyl-7-dimethylamino or 4-methyl-7-diethylaminocoumarin. Farther Polyamide brighteners are the compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) -ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyril can be used. As a brightener for polyester and Polyamide fibers are the compounds 2,5-di- (2-benzoxazolyl) -thiophene, 2- (2-benzoxazolyl) -naphtho [2,3-b] -thiophene and 1,2-di- (5-methyl-2-benzoxazolyl) -ethylene are suitable. You can also use brighteners of the substituted 4,4t-distyryldiphenyl type be present; e.g. the connection 4,41-bis (4-chloro-3-sulfostyryl) diphenyl. Also mixtures of the aforementioned brighteners can be used.

The enzyme preparations to be used are usually a mixture of enzymes with different effects, e.g. of proteases, carbohydrases, esterases, lipases, Oxidoreductases, catalase, peroxidases, ureases, isomerases, lyases, transferases, Desmolases or nucleases. Those from bacterial strains are of particular interest or enzymes obtained from fungi such as Bacillus subtilis or Streptomyces griseus, in particular Proteases or amylases that oppose alkali, percompounds and anionic surfactants are relatively stable and are still effective at temperatures of up to 70 ° C.

Enzyme preparations are usually supplied by the manufacturers as aqueous solutions the active ingredients or as a powder, granules or as cold atomized products in the Trade brought. They often contain sodium sulfate, sodium chloride, Alkali ortho-, pyro- or polyphosphates, especially tripolyphosphate. Special ones Value is placed on dust-free preparations; they are obtained in a manner known per se by incorporating oily or pasty nonionics or by granulating with the help of melting salts containing water of crystallization in your own water of crystallization.

Enzymes can be incorporated for a certain type of dirt are specific, for example proteases or amylases or lipases; preferred one uses combinations of enzymes with different effects, especially combinations from proteases and amylases.

The preparations may also contain graying inhibitors, which keep the dirt detached from the fiber suspended in the liquor and so on prevent the graying. Carboxymethyl cellulose is particularly suitable for this purpose, Methyl cellulose and hydroxyethyl cellulose, as well as water-soluble polyesters and polyamides from polybasic carboxylic acids and glycols or diamines, the free ones for salt formation have capable carboxyl groups, betaine groups or sulfobetaine groups and colloidal in water-soluble polymers or copolymers of vinyl alcohol, vinyl pyrolidone, Acrylamides and acrylonitrile. Other ingredients in the invention Agents that may be included are neutral salts, especially sodium sulfate, antimicrobial Active ingredients such as halogenated phenol ethers and thioethers, halogenated carbanilides, halogenated salicylanilides and halogenated diphenylmethanes, as well as dyes and fragrances.

Examples The first step is the preparation of an amine of the formula I and its conversion into the salt form. The manufacture of the other Compounds of the formula were carried out in an analogous manner.

Manufacturing instructions for N-dodecyl-N, N, -bis (2,3-dihydroxypropyl) -amine 370 g (2 mol) of dodecylamine were dissolved in 500 ml of ethanol and at the boiling point 356 g (4.8 mol) of glycide were added dropwise. After stirring for 2 hours At reflux, the ethanol was stripped off in vacuo. There could be no in the reaction product secondary or primary amine can be detected.

Manufacturing instructions for N-dodecyl-N, N-bis (2,3-dihydroxypropyl) amine hydrochloride 111 g (0.33 mol) of N-dodecyl-N, N-bis (2,3-dihydroxypropyl) -amine were at room temperature dissolved in 200 ml of ethanol. To this solution, a solution of 33 g became more concentrated Hydrochloric acid added to 100 ml of ethanol. After stirring for 5 minutes, the ethanol was im Vacuum removed. The product was obtained in the form of a light brown paste. For cleaning was dissolved in methanol and precipitated with ether.

The following examples describe compositions of some of the invention Middle.

"Amine": No. 1 N-dodecyl-N, N-bis (2,3-dihydroxypropyl) -amine No. 2 N-tetradecyl- "" No. 3 N-Cocoalkyl- "No. 4 N-Hexadecyl-" n No. 5 N-2-Hydroxydodecyl- "No. 6 N-2-hydroxyoctadecyl- "" II No. 1 A = 1 as salt of hydrochloric acid No. 2 A = 2 as Salt of hydrochloric acid No. 3 A = 3 as salt of sulfuric acid No. 4 A = 4 as salt of Acetic acid No. 5 A = 5 as the salt of sulfuric acid No. 6 A = 6 as the salt of acetic acid; "ABS": the salt of one obtained by condensing straight chain olefins with benzene and Sulfonating the resulting alkylbenzene with the alkylbenzenesulfonic acid obtained 10-15, preferably 11-13 carbon atoms in the alkyl chain; "Soap": one off the mixture of 60% hardened rapeseed oil fatty acids and 40% hardened palm kernel fatty acids manufactured Na soap; "C13-C15-OA + 8 ÄO": the adduct of 8 moles of ethylene oxide to 1 mole of C13-C15 oxo alcohol; "TA 14": the adduct of 14 moles of ethylene oxide to 1 mole of tallow fatty alcohol; "KA-ÄO-Sulphate": the sulphated addition product of 3 moles of ethylene oxide in 1 mole of coconut fatty alcohol as the sodium salt; "Betaine": N- (coconut alkyl) -N, N-dimethylammonioacetate; "NaTPP": sodium triphosphate, Na5P3O10; "PHAS": poly-α-hydroxyacrylic acid sodium salt (MW 35,000 to 40,000); "PLAC": a polylactone of α-hydroxyacrylic acid, degree of polymerization approx. 500, approx. 80% of the Acid groups lactonized; "CMT": the sodium salt of carboxymethyltartronic acid; "NTA": the sodium salt of nitrilotriacetic acid; "EDTA": the tetrasodium salt of ethylenediaminetetraacetic acid; "NA-Al-silicate": a compound with the composition 0t9 Na20. 1 Al203. 2.04 SiO2 . 4.3 H20 calcium binding capacity 170 mg CaO / g anhydrous substance, particle size 410 11; "Perborate": a product of the approximate range containing about 10% active oxygen Composition NaB02. H202. 3 H20; Water glass ": a sodium silicate of the composition Na20. 3.35 SiO2; "CMC": the Na salt of carboxymethyl cellulose with a degree of substitution from 0.7 - 0.8.

In the examples the recipes are 1, 2, 6 to 10, 13 to 15, 19 and 20 examples for heavy duty detergent recipes, 3 and 8 for mild detergent and 60 ° C detergent formulas, 4, 5 and 16 for pre-wash formulations, 11 and 12 for liquid detergent formulations and 17 for a cleaning agent. Of these are the Examples 6, 7 and 15 are low in phosphate and Examples 8, 9, 10, 14 and 20 are phosphate-free Recipes. The quantities given for the individual examples are percentages by weight.

Examples Component 1 2 3 4 5 6 7 8 9 Amine # 1 4 No. 2 No. No. 2 No. 5 10 No. 6 20 No. 1 A 12 No. 2 A 20 No. A No. 4 A No. 5 A No. 6 A 0 ABS 6 2 Soap 2 3.5 3 2 2.5 3.5 3 2 @ @@ @@ @ 8 ÄO C13 / C15OA + 8 AO TA 14 KA-EO sulfate Beta in Potassium toluene sulfonate NaTPP 40 45 40 60 55 20 20 Potassium pyro phosphate PHAS 20 PLAC 20 NTA 5 7 EDTA 0.2 0.25 0.2 0.3 0.3 0.2 Na-Al-silicate Perborate 24 26 28 22 24 24 Water glass 3.5 3 3 4 5 3 10 6 5 Soda 3 3 Mg-silicate 2 1.7 1.8 1.3 1.7 CMC 1.8 2.0 1.5 1.3 1.4 2 1.2 1.3 1.3 Isopropanol Rest: enzymes, opt. Brightener, perfume, Dye, water, Na sulfate to 100 Examples Component 10 11 12 13 14 15 16 17 18 19 20 Amine No. 1 12 4 2.0 No. 2 7 2.0 No. 3 10 No. 1 A 14 6 No. 2 A 3.5 No. 4 A 15 No. 5 A 8 No. 6 A SECTION Soap 2 3.5 3 3.5 2 0.8 3.5 3.5 C13 / C15OA + 8 AO 5 10.2 TA 14 3 KA-AO sulfate 1 Betaine 5 Potassium toluene sulfonate 4 NaTPP 0 Potassium pyro phosphate 10 20 PHAS CMT 20 NTA EDTA 0.3 0.2 0.2 0.2 0.2 0.3 0.25 0.4 Na-Al-silicate 20 20 20 Perborate 28 26 24 26 28 25 Water glass 4 3.5 3 3 4 5 2.5 5 Soda 1.5 Mg silicate 1.8 2 2 2 1.5 1.7 CMC 1.4 1.5 1.3 1 1.5 1.5 1.4 1.3 Isopropanol = Remainder: enzymes, opt remainder: Brightener, perfume water Dye, water Na sulfate

Claims (14)

Means for washing and cleaning solid materials, in particular textiles, characterized in that, optionally together with other surfactants from the group of anionic, nonionic and zwitterionic surfactants, a tertiary amine of the formula I in which R1 is an alkyl or alkenyl group with 1 to 16 carbon atoms, R2 is hydrogen or an alkyl group with 1 to 16 carbon atoms, R3 is hydrogen, an alkyl group with 4 to 14 carbon atoms or the hydroxyl group, where in the case R3 = H or OH the The sum of the carbon atoms of the alkyl groups R1 and R2 is in the range from 6 to 20, and where R2 = H, the alkyl or alkenyl group R1 has 6 to 16 carbon atoms and the substituent R3 in this case is hydrogen, hydroxyl or an alkyl group with 4 to Can mean 14 carbon atoms, with the further proviso that an alkyl group R3 is in each case 2 carbon atoms shorter than an alkyl group R1, optionally in the form of its water-soluble salt with an anion that is compatible with washing and cleaning. 2. Composition according to claim 1, characterized in that it is an amine of the formula I, in which R2 and R3 are hydrogen, and R1 is an alkyl or alkenyl group with 8 to 18, in particular 10 to 14 carbon atoms contains. 3. Means according to claim 1 and 2, characterized in that there is a Amine of the formula I in which R2 is hydrogen, R3 is the hydroxyl group and R1 is an alkyl group with 8 to 18, in particular 10 to 14 carbon atoms contains. 4. Means according to claim 1 to 3, characterized in that there is a Amine of the formula I in which R3 is the hydroxyl group and R1 and R2 are alkyl groups together 8 to 18, in particular 10 to 14 carbon atoms contains. 5. Means according to claim 1 to 4, characterized in that there is a Amine of the formula I in amounts of 0.5-40% by weight. 6. Means according to claim 1 to 5, characterized in that there is a Contains surfactant combination to 1 part by weight of an amine of the formula I 0 to 5, preferably 0.1 to 3, and in particular 0.2 to 2 parts by weight of at least one other surfactants from the group of anionic, nonionic or zwitterionic Has surfactants. 7. Means according to claim 1 to 6, characterized in that it is the The surfactant combination of claim 6 in an amount of 0.5 to 80, preferably 5 contains up to 35% by weight. 8. Means according to claim 1 to 7, characterized in that it is composed of 0.5-80% by weight of the surfactant combination according to claim 6, 10-90 % By weight of inorganic or organic, water-soluble and / or water-insoluble Builders, 0-40% by weight of bleaching substances and optionally activators and Stabilizers for the bleaching substances, and the remainder up to 100% by weight of the usual carrier, Auxiliaries and fillers. 9. Composition according to claim 1 to 8, containing a surfactant combination from 1 part by weight of an amine of the formula I and 0.2 to 2 parts by weight of a sulfonate surfactant and / or a nonionic surfactant of the ethoxylated aliphatic C8-C20 alcohol type. 10. Low-phosphate and phosphate-free laundry detergent according to claim 1 to 9, characterized by the following composition: 5 - 35 wt .- & one the surfactant combination according to claims 6 and 9, 0.2-0.5% by weight of a foam inhibitor, consisting of 0.2-0.8% by weight of a non-surfactant foam inhibitor, or 0.5 - 5 wt .-% of an alkali soap consisting essentially of C18-C22 fatty acids, or one Mixture of the non-surfactant foam inhibitor and the soap, 0 - 20% by weight condensed phosphates, especially sodium triphosphate, 0.2-30% by weight of another, non-phosphate, preferably phosphorus-free builder from the group the inorganic or organic water-soluble or water-insoluble builder substances, 0-40% by weight of a bleach component, including any present Activators and / or stabilizers, the remainder up to 100% by weight of other common ingredients of powdery, pasty or liquid detergents and cleaning agents, whereby in the case of compositions containing phosphate and / or phosphonate, the calculated one Phosphorus content is at most 6, preferably at most 5 wt .-%. 11. Composition according to claim 1 to 10, characterized in that it a bleaching component consisting of an oxygen-releasing per compound, in particular Sodium perborate, stabilizers and optionally activators, in amounts of 10 - 40, preferably 15-35 wt .-% contains. 12. A method for producing the agent according to claim 1 to 11, characterized in that the amines of the formula I in the form of their water-soluble Salts with anions that are compatible with washing and cleaning, especially as sulfates, Acetate, propionate, citrate, lactate or hydrochloride incorporated into the agent will. 13. The method according to claim 12, characterized in that the Amines of the formula I in the form of their salts in an aqueous slurry of hydrolysis and Brings heat-resistant ingredients, and this pulp by the method of hot air spray drying converted into a pourable powder. 14. The method according to claim 12, characterized in that one aqueous Solutions of the salts of the amines of the formula I in mixing devices for continuous or discontinuous mixing for powdery, water-binding ingredients of the agent sprayed on.