DE2025944A1 - Detergent compsns for textiles - with combined cleaning - and softening actions,contng quaternary ammonium salts of unsatd carb - Google Patents

Abstract

In addition to usual surface active agents, soaps, builders, etc., the compsns. contain esters of unsatd. acids, of formula : (in which R1 is satd. 10-24 alkyl, pref. 12-20C alkyl; R2 is satd. 1-24C alkyl, pref. 1-18C alkyl; R3 is 1-4C alkyl; X- is the anion of an inorganic or non-surfactant organic acid; n is 1 or 2 and A is an alkenyl or alkenylene group with 2-5C atoms). Prefd. compsns. contain 2-30, pref. 5-20% of the above material, with 5-80% mixed detergents, 95-20% builder substances and 0-30% of various additives such as dirt carriers, enzymes, brighteners, etc. The compsns. retain the desired softness and feel of fabrics or restore these to fabrics hardened by washing, and give antistatic props.

Description

"Softening detergent" When washing in modern washing machines, drum washing machines in particular, the items to be washed are subjected to an intensive mechanical process Exposed to movement, especially when using ordinary heavy duty detergents with repeated washing treatment, to an undesirable hardening of the washed Laundry leads, so that it has an unsatisfactory softness after drying. The undesired hardening of the laundry can be reversed that to the last rinse a generally liquid fabric softener on the Based on quaternary ammonium compounds with at least two longer-chain alkyl radicals clogs in the molecule So are liquid fabric softeners on the market that are effective Component Difettalkyldimethylammoniumhalogenide contained in aqueous dispersion. However, after-treatment with such fabric softeners is generally accepted by the user Perceived as annoying and time-consuming, as the washing process is monitored must be in order to be able to add the fabric softener in time for the last rinse. In addition, the user must take care to avoid excess fabric softener, because overdosing the tissue often becomes water-repellent and greasy Get a grip.

It is obvious that a laundry detergent with detergent at the same time and softening effect for the user from the standpoint of convenience and Application security would mean a huge benefit.

The invention is therefore based on the object of a plasticizing agent To develop detergent that is used during the washing process, especially during the Use in washing machines, in addition to the cleaning also a satisfactory softening Effect on the laundry, especially on textiles made from cellulose materials such as Cotton and linen exerts and so without impairing the absorbency of the fabrics prevents hardening of the laundry or one that has already hardened from washing Fabric gives the desired softness and grip properties again.

A laundry detergent containing textile softeners has now been rounded off, which is characterized in that it, together with anionic surfactants of the sulfonate and / or sulfate type and optionally zwitterionic and / or nonionic surfactants and / or soaps and builder substances, optionally other conventional detergent ingredients serving as textile softeners, esters of unsaturated Contains carboxylic acids of the formula I, in which R1 is a preferably saturated alkyl radical with 10-24, preferably 12-20 carbon atoms, a preferably saturated alkyl radical with 1-24, preferably 1-18 carbon atoms, a lower alkyl radical with 1-4 carbon atoms, X is the anion of an inorganic or non-capillary organic Acid, n is the number 1 or 2, and A is an alkenyl or alkenylene radical having 2-5 carbon atoms.

Among the other usual detergent ingredients that are in the Agents according to the invention can be contained, for example, dirt carriers> foam regulating substances, enzymes, brighteners, antimicrobial agents, fragrances and dyes as well as water.

In formula 1, the alkyl radical R1 is straight-chain or branched can be, for example the lauryl, myristyl, cetyl, oleyl, stearyl, arachidyl, Behenyl, lignoceryl, etc. Radical. R1 preferably denotes an alkyl radical which is derived from natural fatty acids, especially hardened tallow fatty acids or coconut fatty acids descends. The alkyl radical R2 can be identical to R1 or a similar long-chain one Mean alkyl radical; or it can be a lower or middle alkyl radical such as for example represent the methyl, ethyl, propyl, butyl, hexyl, octyl radical. The lower alkyl radical R3 is preferably methyl.

An alkenyl radical A is, for example, the vinyl, allyl, Isopropenyl, l-propenyl, 2-butenyl, 1,3-butadienyl radical. As an alkenylene radical A comes, for example, the vinylene, methyl vinylene-f the 1,4-butadienylene, (1,3) radical etc. into consideration. The radicals A can be in both the cis and the trans form are present.

The particularly preferred compounds of the formula I are are esters of acrylic, methacrylic and crotonic acid, 3-butene carboxylic acid and 3-methyl-3-butenecarboxylic acid and the maleic, fumaric itaconic> mesaconic, methylenemalonic, Citraconic, muconic acid etc ..

The active ingredients which can be used according to the invention can be not claimed here are produced.

For example, the compounds of the formula I can be passed through Reaction of the alkali salts of the unsaturated carboxylic acids with 3-chloro-2-hydroxypropyltrialkylammonium halide or by reacting the unsaturated carboxylic acid with glycidyl trialkylammonium halide obtain. Furthermore, the compounds from the unsaturated carboxylic acid, a Epihalohydrin, for example epichlorohydrin, and a tertiary amine by reaction can be obtained in an inert solvent.

The compounds of formula I are generally used in the preparation as halides, especially chlorides or bromides. Preferably the compounds of the formula I also incorporated as halides in the agents according to the invention; in a mixture with the other components of the funds, in particular liquid funds, however, at least a portion of the halide anions are replaced by other acid residues that are generally incorporated into the preparations according to the invention as alkali salts and in this form represent the usual constituents of detergents, replaces, as Carboxylic acid esters of the formula I can, for example, be used as follows: 1. Methacrylic acid [2-hydroxy-3- (dimethylhexadecylammonium) propyl] ester chloride; 2. Acrylic acid [2-hydroxy-3- (dimethyl-octadecylammonium) propyl] ester chloride; 3. Methacrylic acid [2-hydroxy-3- (dimethyl tallow alkylammonium) propyl] ester chloride; 4th Crotonic acid-t2-hydroxy-3- (dimethylhexadecylammonium) propyl ester chloride; 5. Crotonic acid 2-hydroxy-3- (dimethyl-octadecylammonium) propyl] ester chloride; 6th Methacrylic acid w [2-hydroxy-3- (dimethyl-coeosalkylammonium) propyl] ester chloride; 7. Crotonic acid [2-hydroxy-3-dimethyl-cocoalkylammonium) propyl] ester chloride; 8. Maleic acid bis [2-hydroxy-3- (di-dodecyl-methylammonium) propyl] ester dichloride; 9. Maleic acid bis [2-hydroxy-3- (dimethyl-tetradecylammonium) propyl] ester dichloride; 10. Maleic acid bis [2-hydroxy-3- (dimethylhexadecylammonium) propyl} ester dichloride; 11. Maleic acid bis [2-hydroxy-3- (dimethyl tallowalkylammonium) propyl] ester dichloride; 12. Fumaric acid-his- [2-hydroxy-) - (dimethyl-dodecylammonium-apropyl-7-ester-dichloride; 13. Fumaric acid bis {2-hydroxy-3 (dimethylhexadecylammonium) propyl] ester dichloride; 14. Itaconic acid-bis-f2-hydroxy-3 (dimethylhexadecylammonium) propyl] ester dichloride; 15. Muconic acid bis [2-hydroxy-3- (dimethyl-tetradecylammonium) propyl] ester dichloride; 16. Muconic acid bis [2-hydroxy-3- (dimethyl tallow alkylammonium) propyl] ester dichloride; 17. Itaconic acid bis [2-hydroxy-3- (dimethyl-tetradecylammonium) propyl] ester dichloride0 When washing with the softening detergent according to the invention, the items to be washed the desired softness and grip properties, without it becoming one Deterioration in the absorbency of the textiles occurs, as does that with use commercially available fabric softener may be possible. With the invention Softening detergent can be used in a simple and convenient way Prevent the laundry from hardening or fabric that has already hardened by washing make it soft and fluffy again. In addition, the textiles are given by the softening Detergent antistatic properties.

The composition of the detergent according to the invention is in general in the range of the following formulation: 5 - 80, preferably 8 - 40% by weight of a surfactant combination consisting of: 20 - 90, preferably 50 - 80% by weight of anionic surfactants from the sulfonate and / or sulfate type and optionally zwitterionic and / or nonionic surfactants, 0-60, preferably 5-50% by weight of soaps with 10-26, preferably 12-22 carbon atoms, 80-10, preferably 70-30% by weight of a carboxylic acid ester of the formula I, 0 - 10, preferably 0.2-5% by weight of non-surfactant foam inhibitors, 0-10, preferably 0.2-5% by weight foam stabilizers, 95-20, preferably 90-45% by weight builders, where at least some of these builder substances react alkaline, and where the amount of alkaline to neutrally reacting builder substances, preferably that 0.5 to 7 times and especially 1 to 5 times the total surfactants, and 0-30, preferably 1-15% by weight of other detergent ingredients, such as s.B. Dirt carriers, enzymes, brighteners, antimicrobial agents, fragrances and dyes, Water, the proportion of the compound of the formula I in the total detergent 2 - 30, preferably 5 - 20% by weight.

The structural substances are preferably at least 30%, in particular at least 50% of their weight from condensed phosphates, preferably tripolyphosphate and / or organic complexing agents.

The detergents can also contain a bleaching component, which is included in The above formulation is seen as part of the structural substances a The bleaching component can including any stabilizers and / or activators 2 - 35, preferably make up 7-30% by weight of the total detergent.

Damped foam suitable for use in drum washing machines Detergents according to the recipe above contain either a combination of Surfactants of the sulfonate and / or sulfate type and soap in a ratio of 30: 1 to 1 . 52 preferably 20: 1 to 1. 2 2, and / or a non-surfactant foam inhibitor. In such low-foam detergents, the soaps of ge; satiated Fatty acids with 20 26 9, preferably 20 - 22 carbon atoms, fractions derived from, the amount of which is at least 5% by weight, preferably at least 10% by weight of the total Amount of soap.

The detergents according to the invention can be used as liquids, pastes or powder present. Preferred detergents according to the invention are solid, powdery texture. Such detergents can be methods known per se can be produced0 For example, the as more or less fine powder or individual components present as granules bring together by mixing to powder detergents.

Most of the technical manufacturing methods for powdery Detergent is an aqueous slurry of detergent ingredients or one Part of it and converts it into a dry product. You can use the aqueous approach hydratable inorganic salts as part of the builder substances incorporate in amounts such that they contain all of the water present in the batch can bind as crystal water. Such an approach freezes without further action to a solid product, whereby this process can be accelerated by cooling. The solid product is then comminuted in the usual way. Will be one of those Approach processed according to the principle of cold atomization> then occurs immediately powdery product.

The hydratable inorganic salts are water-soluble salts into consideration that form solid stable hydrates, for example sodium tripolyphosphate, Sodium pyrophosphate, sodium sulfate, sodium carbonate, which are also used as builders, as described below are known.

According to the technically preferred production method for detergents at the moment the aqueous approach is dried hot in a known manner, which is hot Surfaces or in a stream of hot air. If you put the invention Detergent on the way via an aqueous approach of the ingredients by hot drying here, the textile softener of the formula used in accordance with the invention is preferably used I and certain other detergent ingredients such as non-surfactant Soap inhibitors, bleaching agents> enzymes etc. not incorporated into the aqueous mixture but afterwards added to the powder detergent. It is against If necessary an advantage, especially for gentle incorporation smaller Amounts of substances that are intended to make the product more effective or attractive, such as enzymes, antimicrobials, detergents and fragrances, such substances by mixing with some of the structural substances first into a dry powdery one Transfer precursor, which is then added to the detergent powder in the usual way will.

The following are the Bn contained in the detergents according to the invention Ingredients sorted by substance class are described in more detail the anionic, zwitterionic or nonionic surfactants contain at least in the molecule a hydrophobic residue of mostly 8-26, preferably 10-22 and especially 10 - 18 carbon atoms and at least one anionic, nonionic or zwitterionic water-solubilizing group.

The preferably saturated hydrophobic residue is usually more aliphatic, possibly also of an alicyclic nature; he can work with the water-solubilizing groups directly or connected via intermediate links. As intermediate links come z. B.

Benzene rings, carboxylic acid ester or carbonamide groups, ether or ester-like bonded residues of polyhydric alcohols, such as. B. that of ethylene glycol, of propylene glycol, glycerine or corresponding polyether residues.

The hydrophobic group is preferably an aliphatic hydrocarbon group with about 10-18, preferably 12-18 carbon atoms, but depending on the nature of the respective surfactant, deviations from this preferred range of numbers are possible.

As an anionic active washing substance, soaps are made from natural or synthetic fatty acids, ggr; also useful from resin or naphthenic acids, in particular if these acids have iodine numbers of at most 30 and preferably less than 10 exhibit.

Of the synthetic anionic surfactants, the sulfonates have and sulfates of particular practical importance.

The sulfonates include, for example, the alkylarylsulfonates, in particular the alkylbenzenesulfonates, which are known, inter alia. from preferably straight-chain aliphatic Hydrocarbons with 9 - 15> in particular 10 - 14 carbon atoms by chlorination and alkylation of benzene or of corresponding terminal or internal oils obtained by alkylating benzene and sulfonating the resulting alicyibenzenes. Furthermore, aliphatic sulfonates are of interest, like them z. B. from preferably saturated, 8-18 and preferably 12-18 carbon atoms in the molecule containing hydrocarbons by sulfochlorination with sulfur dioxide and chlorine or sulfoxidation with sulfur dioxide and oxygen and conversion of the resulting Products in the sulfonates are accessible. As aliphatic sulfonates are still Mixtures containing alkene sulfonates, hydroxyalkanesulfonates and disulfonates can be used, which one z. B. from terminal or intermediate C818 and preferably C12-18 olefins by sulfonation with sulfur trioxide and acidic or alkaline hydrolysis of the sulfonation products receives. The sulfonate group is found in the aliphatic sulfonates produced in this way often on a secondary carbon atom; but you can also implement it of terminal olefins with bisulfite obtained sulfonates with a terminal sulfonate group insert.

The sulfonates to be used according to the invention also include Salts, preferably dialkali salts, of i-sulfofatty acids and salts of esters of these Acids with mono- or polyvalent, 1-4 and preferably 1-2 carbon atoms Alcohols.

Further useful sulfonates are salts of fatty acid esters of oxethanesulfonic acid or of dioxypropanesulfonic acid, the salts of the fatty alcohol esters of lower, 1 - Aliphatic or aromatic sulromono- or -dicarboxylic acids containing 8 carbon atomsX the alkyl glyceryl ether sulfonates and the salts of the amide-like condensation products of fatty acids or sulfonic acids with Aminoäthansulfonsäure0 as Surfactants of the sulfate type are fatty alcohol sulfates, in particular from coconut fatty alcohols, Tallow fatty alcohols or made from oleyl alcohol. Also from final or internal C8-18 olefins are useful sulfonation products of the sulfate type available. Farther This group of surfactants includes sulfated fatty acid alkylolamides or fat -acid monoglycerides and sulfated alkoxylation products of alkylphenols (C8-15-alkyl), Fatty alcohols, fatty acid amides or fatty acid alkylolamides; which in the molecule 0.5 - 20> preferably 1-8 and especially 2-4 ethylene and / or propylene glycol residues Can contain, As anionic surfactants of the carboxylate type are, for. B. the fatty acid esters or fatty alcohol ethers of hydroxycarboxylic acids and the amide-like Condensation products of fatty acids or sulfonic acids with aminocarboxylic acids z. B. with glycocolla, sarcosine or with protein hydrolysates.

To the nonionic surfactants, here for the sake of simplicity as "Nonionics" products, whose water solubility is due to the presence of polyether chains, Amine oxide, sulfoxide or phosphine oxide groups and alkylolamide groups as well as whole generally owe to an accumulation of hydroxyl groups.

Of particular practical interest are those caused by the addition of ethylene oxide and / or glycide on fatty alcohols, alkylphenols, fatty acids, fatty amines, Fatty acid or sulfonic acid amides, these nonionics 4 - 100, preferably 6 - 40 and in particular 8 - 20 atomic residues, especially ethylene glycol ether residues may contain per molecule.

In addition, in these polyether chains or at the end of these, propylene or butylene glycol ether residues or polyether chains may be present. Farther belong to the nonionics under the trade names "Pluronics" or "Tetronics" well-known products. They are obtained from water-insoluble polypropylene glycols or from water-insoluble propoxylated lower, 1 - 8, preferably 3 - 6 carbon atoms containing aliphatic alcohols or from water-insoluble propoxylated Alkylenediamines. These water-insoluble (i.e., hydrophobic) propylene oxide derivatives are converted into the nonionics mentioned by athoxylating until they are water-soluble. Finally, nonionies are also those scanned as "Ucon fluid", some of which are still water-soluble Reaction products of the abovementioned aliphatic alcohols with propylene oxide can be used.

The nonionics also include fatty acid or sulfonic acid alkylolamides, which z. B. from mono- or diethanolamine, from dihydroxypropylamine or others Polyhydroxyalkylamines, e.g. B. Derive the glyeamines They can be derived from amides from higher primary or secondary alkylamines and polyhydroxycarboxylic acids.

The capillary-active amine oxides include, for. B. those of higher tertiary, a hydrophobic alkyl radical and two shorter, up to 4 carbon atoms each containing alkyl and / or products derived from amines containing alkylol radicals.

Zwitterionic surfactants contain both acidic and basic hydrophilic groups. The acidic groups include carboxyl, sulfonic acid, Sulfuric acid half-ester-J phosphonic acid and phosphoric acid partial ester groups. As a basic Groups come primary, secondary, tertiary and quaternary ammonium groupings in question. Zwitterionic compounds with quaternary ammonium groups belong to the Type of betaine.

Carboxy, sulphate and sulphonate betaines are well tolerated of particular practical interest with other surfactants. Suitable sulfobaine receives you sort, for example, by reacting, at least one hydrophobic alkyl radical containing amines with sultones, for example propane or butane sultone. Appropriate Carboxybetaine receives one by implementing the said tertiary Amines with chloroacetic acid, its salts or with chloroacetic acid esters and columns the ester bond.

The foaming power of the surfactants can be determined by a combination of suitable Increase or decrease the surfactant types, as well as the addition of non-surfactant types organic substances can be changed.

Foam stabilizers are particularly suitable for surfactants from the sulfonate or sulfate-type capillary-active carboxy- or sulfobetaines as well as those mentioned above Alkylolamide type nonionics; in addition, fatty alcohols or higher are used for this purpose terminal diols have been proposed.

Products with reduced foaming power are mainly intended for use Determined in washing machines and dishwashers, sometimes with limited foam absorption sufficient, while in other cases a stronger foam suppression is desirable can. Products in the medium temperature range are of particular practical importance It still foams up to about 650c, but on transition to higher temperatures (70 - 100 ° C) develop less and less foam.

A reduced foaming power is often obtained with combinations different types of surfactants, especially in the case of combinations of synthetic anionic ones Surfactants, especially from (1) sulfates and / or sulfonates or from (2) nonionics on the one hand and of (3) soaps on the other hand. When combining the components (1) and (2) or (1), (2) and (3), the foaming behavior can be determined by the respectively used Influence soaps: in the case of soaps preferably made of saturated fatty acids with 12 - 18 C atoms, the foam attenuation is lower, while soaps from saturated Fatty acid mixtures with 20 - 26, preferably 20-22 carbon atoms, the amount of which at least 5, preferably at least 10 wt. of the total, in the Surfactant combination can make up the existing soap content, a stronger foam dampening, especially in the higher temperature range.

The foaming power of the surfactants can, however, also be increased by additives known, non-surfactant foam inhibitors decrease. These include optionally chlorine-containing N-allcylated aminotriazines, which can be obtained by reaction of 1 mole of cyanuric acid chloride with 2-3 moles of a mono- and / or dialkylamine with 6-20, preferably 8-18 carbon atoms in the alkyl radical. act similarly Aminotriazine or melamine derivatives, the propylene glycol or butylene glycol ether chains contained, whereby 10-100 such glycol residues can be contained in the molecule. Compounds of this type are obtained, for example, by planting appropriate amounts Propylene and / or butylene oxide on aminotriazines, in particular on melamine, preferred are, for example, the reaction products of 1 mole of melamine with at least 20 moles of propylene oxide or at least 10 moles of butylene oxide can be used. Have proven to be particularly effective It has been shown that products can be obtained by adding 5-10 moles of propylene oxide to 1 mole of melamine and further adding 10-50 moles of butylene oxide to this propylene oxide derivative receives.

Also other, non-surfactant, water-insoluble organic compounds, such as paraffins or haloparaffins with melting points below 1000 C, aliphatic C18 to C40 ketones and aliphatic carboxylic acid esters, which are in the acid or alcohol radical, optionally also in each of these two radicals, at least 18 carbon atoms contain (e.g. triglycerides or fatty acid fatty alcohol esters), can, above all in combination with anionic synthetic surfactants and soaps, as foam inhibitors use.

The non-surfactant foam inhibitors are often only at temperatures fully effective, in which they are in the liquid state, so that the foaming behavior sleh control the products in a similar manner by choosing suitable foam inhibitors lets like by the choice of soaps made from fatty acids of suitable chain lengths.

If you combine foam stabilizers with temperature-dependent foam inhibitors> so you get well at lower temperatures, as you get closer to the cooking temperature increasingly weaker foaming products.

As particularly low-foaming nonionics, which can be used both alone and also in combination with anionic, zwitterionic and nonionic surfactants can be used and reduce the foaming power of better foaming surfactants, Addition products of propylene oxide to the capillary-active ones described above are suitable Polyethylene glycol ether as well as the Pluronic, Tetronic- and Ucon fluid types.

Weakly acidic, neutral and alkaline substances are suitable as structural substances reacting inorganic or organic salts, in particular inorganic or organic Complexing agents.

According to the invention, weakly acidic, neutral or alkaline reacting salts are for example the bicarbonates, carbonates, borates or silicates of alkalis, furthermore mono-, di- or.

Trialkali orthophosphates, di- or tetraalkali pyrophosphates, as complexing agents known metaphosphates, alkali sulfates and the alkali salts of organic, not capillary-active sulfonic acids, carbonic acids and sulfocarboxylic acids containing 1 - 8 carbon atoms. These include, for example, water-soluble salts of benzene, toluene or xylene sulfonic acid, water-soluble salts of sulfoacetic acid, sulfobenzoic acid or salts of sulfodicarboxylic acids as well as the salts of acetic acid, lactic acid, citric acid and tartaric acid.

Furthermore, the water-soluble salts are of higher molecular weight as structural substances Polycarboxylic acids can be used, in particular polymers of maleic acid, itaconic acid, Mesaconic acid, fumaric acid, aconitic acid, methylenemalonic acid and citraconic acid. Even Copolymers of these acids with one another or with other polymerizable Substances such as ethylene, propylene, acrylic acid, methacrylic acid, crotonic acid, 3-butenecarboxylic acid, 3-methyl-3-butenecarboxylic acid and with vinyl methyl ether, vinyl acetate, Isobutylene, acrylamide and styrene are useful.

Weak ones are also suitable as complex-forming structural substances acidic metaphosphates and alkaline polyphosphates, especially the tripolyphosphate.

They can be replaced in whole or in part by organic complexing agents. The organic complexing agents include, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediamine triacetic acid, polyalkylene-polyamine-N-polycarboxylic acids and other known organic complexing agents, and combinations of different complexing agents can also be used. The other known complexing agents also include di- and polyphosphonic acids of the following constitutions: where R is alkyl and R 'alkylene radicals with 1-8, preferably with 1-4 carbon atoms, X and Y represent hydrogen atoms or alkyl radicals with 1-4 carbon atoms and Z represents the groups -0H, -NH2 or -NXR. The following compounds are particularly suitable for practical use: methylenediphosphonic acid, l-hydroethane-l, l-diphosphonic acid, 1-aminoathane-1, 1-diphosphonic acid, amino-tri- (methylenephosphonic acid), methylamino- or ethylamino-di- (methylenephosphonic acid) and ethylenediamine tetra (methylenephosphonic acid). All these complexing agents can be present as free acids, preferably as alkali salts. The preparations according to the invention can also contain dirt carriers that keep the dirt released by the fibers suspended in the liquor and thus prevent graying. Water-soluble colloids, usually of an organic nature, are suitable for this, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatine, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acid sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and other starch products than those mentioned above can also be used, such as e.g. 13, degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.

The constituents of the detergents composed according to the invention, in particular the structural substances are usually selected so that the preparations react neutrally to clearly alkaline, so that the pH value 'a 1 own solution of the preparation is usually in the range of 7-12. Thereby, mild detergents usually have neutral to weakly alkaline reaction (pH = 7 - 9.5), while for example Cooking detergent set to be more alkaline (pH value = 9.5 - 12, preferably 10 - 11.5) are.

Among the preferably inorganic per compounds used as bleaching agents Sodium perborate tetrahydrate (NaBO2. H202. 3 H20) is of particular practical importance. In its place, partially or completely, i.e. up to NaBO2. H2O2 dehydrated Perborate can be used. There are also those in DBP 901 287 and USP 2,491,789 described borates NaB02. H202 usable in which the ratio Na2O: B2O3 is less than 0.5: 1 and preferably in the range 0.4-0.15: 1, while the H202: Na ratio falls in the range of 0.5-4: 1. All this perborate can be wholly or partially by other inorganic per compounds, in particular by peroxohydrates, e.g. the peroxohydrates of the ortho-, pyro- or Polyphosphates, especially tripolyphosphates, and carbonates.

It is advisable to use the products to stabilize the per compounds Usual water-soluble and / or water-insoluble stabilizers in amounts of 0.25-10% by weight to be incorporated.

As water-insoluble perstabilizers, 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: 5102 = 4: 1 to 1: 4> preferably 2: 1 to 1: 2 and in particular 1: 1.

In their place are other alkaline earth metal, cadmium or tin silicates appropriate composition usable. There are also hydrous oxides of tin suitable as stabilizers.

Water-soluble stabilizers, which together with water-insoluble may be present, the organic complex formers, the amount of which is 0.25 - 5, preferably 0.5 - 2.5 ß of the weight of the entire preparation.

The active chlorine compounds used as bleaching agents can be more inorganic or be organic in nature.

The inorganic active chlorine compounds include alkali hypochlorites, in particular in the form of their mixed salts or addition compounds to orthophosphates or to condensed phosphates such as pyro- and polyphosphates or The detergents according to the invention contain alkali silicates Monopersulfates. and chlorides, active chlorine is formed in aqueous solution.

The organic active chlorine compounds are in particular the N-chlorine compounds in question, in which one or two chlorine atoms are bonded to a nitrogen atom, where preferably the third valence of the nitrogen atoms is attached to an electron-withdrawing one Group leads, in particular to a CO or S02 group. Listen to these connections Dichloro and trichlorocyanuric acid or salts thereof, chlorinated alkylguanides or alkyl biguanides, chlorinated hydantoins and chlorinated melamines.

The brighteners that can be used are mostly, if not exclusively, Derivatives of diaminostilbene sulfonic acid, diarylpyrazolines and aminocoumarins.

Examples of brighteners from the class of diamino-benzene sulfonic acid derivatives are compounds according to formula II: In the formula, R1 and R2 can mean halogen atoms, alkoxyl groups, the amino group or radicals of aliphatic, aromatic or heterocyclic, primary or secondary amines and radicals of aminosulfonic acids} where the aliphatic radicals present in the above groups are preferably 1-4 and especially 2-4 C- Contain atoms, while the heterocyclic ring systems are mostly 5- or 6-membered rings. The radicals of aniline, anthranilic acid or anilinesulfonic acid are preferred as aromatic amines. Lighteners derived from diaminostilbene sulfonic acid are mostly used as cotton lighteners. The following products derived from formula II are commercially available, where R1 represents the radical —NH — C6H5 and R2 can represent the following radicals —NH2, —NH — CH3, —NH — CH2 — CH2OH, —NH — CH2 — CH2 -O-CH3, -NH-CH2-CH2-CH2-O-CH3, CH3-N-CH2-CH2OH, -N = (CH2-CH2OH) 2, morpholino-, -NH-C6H5, -NH-C6H4-SODH , -OCH. In terms of fiber affinity, some of these brighteners are to be regarded as transition types to the polyamide brighteners, for example the brightener with R2 = -NH-C6H5.

One of the diaminostilbene sulfonic acid type cotton whiteners furthermore the compound 4,4'-bis - (- 4-phenyl-vicinaltriazolyl-2 -) - stilbene disulfonic acid-2,2 '.

The polyamide brighteners, some of which have a certain affinity for cotton fibers, include diarylpyrazolines of the formulas [@] and TV: In formula III, R3 and R5 denote hydrogen atoms, optionally substituted by carboxyl, carbonamide or ester groups, alkyl or aryl radicals, R4 and R6 hydrogen or short-chain alkyl radicals, Ar1 and Ar2 aryl radicals such as phenyl, diphenyl or naphthyl> which can carry further substituents such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, carboxylic acid ester, sulfonic acid, sulfonamide and sulfone groups or halogen atoms. Commercially available brighteners of this type are derived from the formula IV, where the radical R7 can represent the groups Cl, -SO2-NH2, -SO2-CH = CH2 and -COO-CH2-CH2-O-CH3, while the remainder R8 denotes a chlorine atom in all cases. 9-cyano-anthracene is also commercially available as a polyamide brightener.

The polyamide brighteners also include aliphatic or aromatic ones substituted aminocoumarins, e.g. 4-methyl-7-dimethylamino- or 4-methyl-7-diethylaminocoumarin. The compounds 1- (benzimidazolyl-2 ') - 2- (N-hydroxyethyl-benzimidazolyl-2') - ethylene are also used as polyamide brighteners and 1-N-ethyl-3-phenyl-7-diethylamino-carbostyril can be used.

As brighteners for polyester and polyamide fibers, the compounds are 2,5-di- (benzoxazolyl-2 ') -thiophene and 1,2-di- (5'-methyl-benzoxazolyl-2') -ethylene suitable. provided the brighteners together with other ingredients of the invention Products are present as an aqueous solution or paste and, by hot drying, become solid State, it is recommended to stabilize the brightener organic Complexing agents in amounts of at least 0.1, preferably 0.2-1% by weight of the solids Incorporate products.

The enzymes to be used are usually a mixture of different ones of enzymatic active ingredients. Depending on their effect, they are used as proteases, carbohydrases, Esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, Lyases, transferases, desmolases or nucleases called.

Those from bacterial strains or fungi are of particular interest enzymatic agents obtained such as Bacillus subtilis and Streptomyces griseus, especially proteases or amylases. Preparations made from Bacillus subtilis have the advantage over others that they have the advantage over alkali, per compounds and anionic washing active substances relatively stable and at temperatures up to to 70 0C are still effective, enzyme preparations are mostly called by the manufacturers aqueous solutions of the active ingredients or with the addition of extenders as a powder placed on the market, Sodium sulfate, sodium chloride, Alkali ortho-, pyro- or polyphosphates, especially tri-polyphosphate. Vielrach the still moist enzyme preparations are brought together with calcined salts, the then possibly with agglomeration of the existing particles to form larger particles bind existing water of crystallization and the enzymatic active ingredient.

If the enzymatic active ingredients are in the form of a dry powder, then liquid, paste-like and possibly also solid, nonionic, preferably capillary-active, organic compounds, in particular those described above Nonionics send the enzymes to the powder of the detergents according to the invention to tie. For this purpose, a spray mix is preferred from the respective product and the enzymatic active ingredient with the above non-ionic substances, or the enzyme preparation is dispersed in the said non-ionic substance and combines this dispersion with the other components of the product. If these remaining components of the product are solids, can also the dispersion of the enzymatic active ingredients in the nonionic component Spray on the remaining solid components.

The enzymes, or combinations of enzymes with different effects, are generally used in amounts such that the finished products have protease activities from 50-5,000> preferably 100-2,500 LWE / g and / or amylase activities from 20-5,000, preferably from 50,000 SKBE / g and / or lipase activities of 2-1,000, preferably 5-500 IU / g.

These details about the enzyme activities result from the activities of those enzyme preparations which on the day of registration for use in the Wasohmittelgebiet Appear justifiable from an economic point of view. From the chemical-technical From the standpoint, the enzyme activities of the preparations can be increased as required, so that the activities with proteases and amylases e.g. 0 to 5 times, with lipases e.g. can be increased up to 10 times the maximum values given above0 Therefore, preparations with high activities should also be available in the future economically suitable for use in the detergent sector appear, the enzyme activities can be increased as needed.

Regarding the determination of the enzyme activities, see the following references referenced Determination of the activity of proteases according to Löhlein-Volhard: A. Künzel : "Gerbereichemisches Taschenbuch", 6th edition, Dresden and Leipzig 1955; determination the activity of amylases: J. Wohlgemuth: "Biochemische Zeitschrift" Volume 9, (1908), pages 1 - 9, and R.M. Sandstedt, E. Kneen and M.J. Blish: "Cereal Chemistry", Volume 16 (1939), pages 712-723; Determination of the activity of lipases: R. Willstätter, E. Waldschmidt - Leitz and Fr.

Quantities: "Hoppe-Seyler's Journal for Physiological Chemistry", Volume 125 (1923) pp. 110-117; R. Boissonas: "Helvetica Chimica Acta '", Volume 31 (1948), pages 1571-1576.

EXAMPLES The following examples describe the composition some preparations according to the invention. The salty ingredients it contains - salt-like surfactants, other organic salts and inorganic salts - lie as sodium salts, unless expressly stated otherwise. The related names or abbreviations mean: "ABS" the salt of a through Condensation of straight-chain olefins with benzene and sulfonation of the resulting Alkylbenzene obtained alkylbenzenesulfonic acid with 10 - 15> essentially 11 - 13 carbon atoms in the alkyl chain; "Alkanesulfonate" one made from paraffins with 12-16 carbon atoms sulfonate obtained by sulfoxidation; "Fs-ester sulfonate" is made from the methyl ester of a hardened tallow fatty acid Sulfonate obtained with SO3; "Olefin sulfonate" means a mixture of olefins with 13-18 carbon atoms by sulfonating with SO3 and hydrolyzing the sulfonation product Sulphonate obtained with lye, consisting essentially of alkene sulphonate and oxyalkane sulphonate exists, but also contains small amounts of disulfonates. Any containing olefin sulfonate Preparation was made using two different types of olefin sulfonate; one was made from a mixture of straight-chain terminal olefins, the other made from a mixture of internal olefins are produced; "KA sulfate" or "TA-sulfate" the salts of sulfated, by reduction of coconut fatty acid or Tallow fatty acid produced, essentially saturated fatty alcohols; "KA-ÄO-Sulphate" or "TA-ÄO-sulfate" or "OA-ÄO-sulfate" the sulfated addition products of 2 moles of ethylene oxide to 1 mole of coconut fatty alcohol or 3 moles of ethylene oxide to 1 mole Tallow fatty alcohol or from 2 moles of ethylene oxide to 1 mole of oleyl alcohol; "QA + 5 EO", "OA + 10 ÄO "," KA + 20 Ä0 "and" KA + 9 AO + 12 PO "are the addition products of ethylene oxide (ÄO) or propylene oxide (PO) on technical oleyl alcohol (OA) or coconut alcohol (KA); "Perborate" is a product of the approximate range containing about 10% active oxygen Composition NaBO2.H2O2.3 H20; "NTA", "EDTA" or "HEDP" are the salts of nitrilotriacetic acid, ethylenediaminetetraacetic acid or hydroxyethyl diphosphonic acid; "Soap A or B ″ one of a fatty acid mixture of 9 wt. C18, 14 wt., Cio C20 and 77 Weight C22 (Iodine Number 3) (A); respectively.

8% by weight C16, 32% by weight C18, 12% by weight C20 and 48% by weight C22 (iodine number 4) (B) manufactured soap; "CMC" the salt of carboxymethyl cellulose.

A non-surfactant foam inhibitor was used in the examples Mixture of about 45% of an N, N'-di (alkylamino) chlorotriazine and about 55% of one N, N ', N "-Tri- (alkylamino) -triazines are used. In these triazine derivatives lie the alkyl radicals as (; emic of homologues with 8-18 carbon atoms.

The monochlorotriazine derivative has been shown to be just as successful or use the trialkylaminotriazine. If the products described are synthetic Sulphates or sulphonates together with soap may contain the others in the description mentioned non-surfactant foam inhibitors are used, such as Paraffin oil or paraffins In the manufacture of the preparations, the non-surfactant was used Foam inhibitor dissolved in a suitable organic solvent or in molten form State sprayed onto the moving powdery preparation by means of a nozzle.

In all examples, the quantities given relate to the pure Substances. These substances can production-related accompanying substances such as Contain water, sodium sulfate, sodium chloride, sodium carbonate, etc. So means in the later following Table II the sign "+" in the line "Na2SO4" means that low Amounts of sodium sulfate are present as an accompanying substance to the anionic surfactants. There such accompanying substances in no way affect the effectiveness of the individual substances affect, they are not mentioned in the recipes. The term "remainder" stands therefore essentially for water and the aforementioned salts as well as for color and Fragrances.

Example 1 (1) 4.9% by weight ABS, (2) 3.1% by weight OA + 10 AO, (3) 4.5% by weight Soap B, (4) 35> 8 wt% sodium tripolyphosphate, (5) 4.0 wt% Na2O. 3.3 SiO2, (6) 1> 1% by weight CMC, (7) 0.23% by weight EDTA, (8) 0.20% by weight optical brightener, (9) 18.3% by weight perborate, (10) 15.0% by weight fabric softener, the remainder sodium sulfate and water.

The detergent according to the above formulation was prepared by mixing one atomization-dried powder detergent consisting of the aforesaid ingredients (1) to (8) with the remaining components (9) and (10). As a textile softener the following active ingredients were used: A: methacrylic acid [2-hydroxy-3- (dimethyl tallowalkylammonium) propyl] ester chloride; B: Crotonic acid [2-hydroxy-3- (dimethyl-octadecylammonium) propyl] ester chloride; C: Maleic acid bis [2-hydroxy-3- (di-dodecyl-methylammonium) -propyl-ester dichloride; D: Maleic acid bis [2-hydroxy-3- (dimethyl-tetradecylammonium) propyl] ester dichloride; E: Maleic acid bis [2-hydroxy-3- (dimethyl tallow alkylammonium) propyl] ester dichloride; F: Fumaric acid bis [2-hydroxy-3- (dimethylhexadecylammonium) propyl] ester dichloride; G: Itaconic acid bis [2-hydroxy-3- (dimethyl) hexadecylammonium) propyl] ester dichloride; H: Muconic acid bis [2-hydroxy-3- (dimethyl tallow alkylammonium) propyl] ester dichloride.

The textile softening effect of the detergents according to the invention according to Example 1 was demonstrated using the following wash test: In a wash liquor with 7.0 g / l of the detergent from Example 1 were in a drum washing machine Samples of new cotton terry fabric as well as samples of pre-washed (hardened) Cotton terry fabric at a temperature of 95 C and a liquor ratio of 1 5 washed five times for 30 minutes each time. A textile softener-free one was used for comparison Detergent used in which the amount of fabric softener according to the above recipe was replaced by sodium sulfate. After each wash, the samples were rinsed and spun and dried hanging. The grip was then independently assessed by 4 people, where the grades are between 1 - full and very soft grip and 6 = very hard grip were awarded. The mean values were calculated from the individual assessments are summarized in the table below. The limits 1 and 6 are Determined as follows: Samples of nQuem cotton terry cloth were used for 240 hours long in the washing machine under boiling wash conditions in water with an addition of 2 g / l tripolyphosphate treated. After drying, it was prewashed in this way Fabric given the grade 6. Samples of new cotton terry cloth were de- and finished and treated with a solution of 0.5 g / l ditallow alkyldimethylammonium chloride. To the Fabric softened in this way was given a rating of 1. The samples of the under test The new untreated cotton terry fabric used had hand notes in the range 1.5-2.

Table I. Detergent handle scores after 5 laundry compared to handle improvement according to Example 1, comparative detergent with active ingredient: new fabric pre-washed new fabric pre-washed Tissue tissue A 1.1 4.9 1.0 1.1 B 1.0 5.3 1.1 0.7 C 1.1 4.0 1.0 2.0 D 1.0 3.8 1.1 2.2 E 1.0 3.8 1.1 2.2 F 1.0 4.0 1.1 2.0 G 1.0 3.3 1.1 2.7 H 1.0 3.3 1.1 2.7 Comparison without 2.1 6.0 - - Fabric softeners The following examples 2-7 describe further detergents according to the invention. The active ingredients A - H were used as textile softeners. Other active ingredients of the formula I, such as, for example, the compounds listed above, can also be used with similar success. Table II Part of the% by weight component in the preparation Preparation example 2 3 4 5 6 7 ABS - - - - 3.0 - Alkanesulfonate 4.5 - - 7.5 - - Fs-ester sulfonate - - - - 2.5 - Olefin sulfonate - 5.4 - - - 7.0 KA sulfate - - 2.0 - - 2.0 TA sulfate - 1.5 - - - - KA-ÄO-sulfate - - - - 2.0 - TA-ÄO-sulfate - - 5.5 - - - OA-ÄO-sulfate - - - 1.5 - - Soap A Soap B OA + 5 AO | - | 2.5 | - | - | - | - OA + 10 A0 KA + 20 ÄO | - | - | - | - | 3.5 | - KA + 9 Ao + 12 PO - - - 2.5 - - Fabric softener | 10.0 | 15.0 | 10.5 | 7.5 | 15.0 | 12.0 non-surfactant Foam inhibitor Na2SO4 ++ 22.5-18.0 ++ Na2O. 3.3 SiO2 3.5 4.0 - 4.5 5.0 Na5P3O10 36.5 35.5 - 40.5 20.5 35.0 Na4P2O7 - - 25.0 - - - Perborate 20.4 22.3 - - 25.5 18.2 MgSiO3 1.0 1.2 - - 1.5 1.1 HEDP - - 5.5 - - - NTA 0.3 - 3.0 - 2.5 EDTA - 0.2 - - 8.5 - CMC 1.2 - 1.3 1.5 1.8 1.2 Brightener 0.22 0.35 0.3 0.4 0.3 0.25 Depending on the intended use of the softening detergents, cotton whiteners, polyamide whiteners, polyester whiteners and combinations thereof are used as whiteners, the amount of which can be in the range from 0305-1.4, preferably 0.1-0.8% by weight of the total agent.

If preparations with a content of enzymes are to be made, so one uses commercially available products, as far as they are solid enzyme concentrates acts by the manufacturer by adding inorganic salts, usually sodium sulfate or sodium tripolyphosphate, in amounts of 7-15% by weight, for example on the following Activities are set: A protease with 125,000 LVE / g, an amylase with 75,000 SKBE / g, a lipase with 10,000 tU / g.

Claims (6)

Patent claims 1. Softening detergent, characterized in that it, together with anionic surfactants of the sulfonate and / or sulfate type and optionally zwitterionic and / or nonionic surfactants and / or soaps, as well as builders and optionally other common constituents, esters of unsaturated carboxylic acids of the formula 1 contains in which R1 is a preferably saturated alkyl radical with 10-24, preferably 12-20 carbon atoms, Ra a preferably saturated alkyl radical with Jl -24, preferably t-18 carbon atoms, a lower alkyl radical with 1-4 carbon atoms, X- the anion of an inorganic or non-capillary organic acid, n is the number 1 or 2, and A is an alkenyl or alkenylene radical having 2-5 carbon atoms. 2. Detergent according to claim 1, characterized in that the composition is in the range of the following formulation: 5-80, preferably 8-40% by weight of one Surfactant combination consisting of: 20 - 902, preferably 50 - 80 wt. Anionic Surfactants of the sulfonate and / or sulfate type and optionally zwitterionic and / or nonionic surfactants, O - 60J preferably 5 - 50% by weight soaps with 10 - 26, preferably 12-22 carbon atoms, 80-10, preferably 70-30% by weight of one Carboxylic acid esters of the formula I, O-10, preferably 0.2-5% by weight of non-surfactant Foam inhibitors, 0-10, preferably 0.2-5% by weight foam stators, 95- - 20, preferably 90-45% by weight of builder substances, at least some of these Scaffold substances react alkaline, and the amount of alkaline to neutral reacting builder substances preferably 0.5 to 7 times and in particular 1 to 5 times the total surfactant, and 0-30, preferably 1-15 % By weight of other detergent ingredients such as dirt carriers, enzymes, Brighteners antimicrobial agents, fragrances and dyes, water being the proportion of the compound of the formula I on the total detergent 2 - 30, preferably 5 - 20 % By weight. 3. Detergent according to claim 1 and 2, characterized in that at least 38% of the structural substances> in particular at least 50% of theirs Weight of condensed phosphates, preferably tripolyphosphate and / or organic Complexing agents exist. 4. Detergent according to claim 1-3, characterized in that the Framework substances contain a bleaching component, including any present Stabilizers and / or activators 2-35, preferably 7-30% by weight of the total Detergent. 5. Low-foaming detergent according to claim 1 - 4, characterized in that that the fatty acid residues present in the soaps of the surfactant component are at least 5 Ge.t, preferably at least 10 wt. Of fatty acid residues with 20-26, preferably 20-22 carbon atoms. 6. Detergent according to claim 1-5, characterized by a further Content of enzymes.