DE2009722A1 - Softening detergent - Google Patents

Abstract

A softening detergent contains anionic tensides of sulphonate and/or sulphate type & opt. amphoteric and/or non-ionic tensides and/or soaps and builder substances and opt. other conventional constituents, and also a bisquaternary ammonium cation (where R1 and R2 are pref. satd. alkyl with 8-24C, pref. 12-20C, or RNH(CH2)n- where R is fatty acid radical with 6-18C and n is 2-10, R3-6 are 1-8, pref. 1-3C alkyl, or mono- or dihydroxyalkyl with 2-4C, R7 and R8 are H or 1-10C, pref. 1-3C alkyl, Y is a single bond or opt. branched alkylene with 1-22, pref. 1-10C, or hydroxymethylene, ethylene, acetylene, p-phenylene, dimethylenoxy, p-diphenylenoxy or beta-diphenylene-sulphonyl).

Description

Softening detergent and process for its manufacture Washing in modern washing machines, especially drum washing machines, will do that Items to be washed are subjected to intense mechanical movement, which is what happens when they are used from common heavy-duty detergents, especially with repeated washing treatments, to one unwanted hardening of the washed laundry leads, so that this after drying has an unsatisfactory softness. The unwanted hardening of the laundry can be avoided by adding a generally liquid one to the last rinsing bath Fabric softener based on quaternary ammonium compounds with at least adds two longer-chain alkyl radicals in the molecule. So are liquid fabric softeners In trade, the effective component dialkyldimethylammonium haiogenide in aqueous Containing dispersion, however, a follow-up treatment with such fabric softeners will be Generally perceived by the user as annoying and time-consuming, since the washing process takes place must be monitored in order to add the fabric softener in time for the last rinse to be able to. In addition, the user must ensure that the correct amount of fabric softener used and a larger excess of it is avoided because of overdosing the fabrics often become water-repellent and greasy to the touch.

It is obvious that a detergent with a cleaning and softening effect at the same time would be of great advantage to the user from the standpoint of convenience and safety of use. However, it is known to the person skilled in the art that the currently available cationic fabric softeners cannot be used in the washing bath in the presence of conventional detergents. In addition to the cleaning effect, it also has a satisfactory softening effect on the laundry, in particular on textiles made of cellulose materials such as cotton and linen, thus preventing the washed laundry from hardening or restoring the desired softness and grip properties to hardened fabrics by washing found that does not have the disadvantages described. The softening detergent according to the invention is characterized in that it contains a bisquaternary ammonium cation of the formula I together with anionic surfactants of the sulfonate and / or sulfate type and optionally zwitterionic and / or nonionic surfactants and / or soaps as well as builder substances and optionally other conventional detergent ingredients, in which R1 and R2 are preferably saturated alkyl radicals with 8 - 24, preferably 12 - 20 carbon atoms, or the radical RNH (CH2) n-, in which R is a fatty acid radical with 6 - 18 carbon atoms and n is a number from 2 - 10, R5 - R6 is alkyl radicals with 1-8, preferably 1-3 carbon atoms, or mono- or dihydroxyalkyl radicals with 2-4 carbon atoms, R and R8 are hydrogen or alkyl radicals with 1-10, preferably 1-3 carbon atoms, Y is a single bond or a straight-chain or branched one Alkylene radical with 1-22, preferably 1-10 carbon atoms, or a hydroxymethylene, ethylene, acetylene, p-phenylene, dimethyleneoxy, p-diphenyleneoxy or p-diphenylenesulfonyl radical.

In formula I, the radicals R1 and R2 are straight-chain or branched Alkyl radicals of synthetic or natural origin such as the octyl, Decyl, lauryl, myristyl, palmityl, oleyl-J stearyl, arachidyl radicals individually or as a mixture. Particularly preferred alkyl radicals R1 and R2 are those derived from hydrogenated sebum fatty acids. The radical R is preferably a saturated one Fatty acid residue, in particular a residue of hardened tallow fatty acid. The remnants of R3 - R6 is preferably methyl, ethyl or propyl; in particularly preferred compounds of the formula I, all four radicals R5-R6 are the same.

Among the other common detergent ingredients included in the Agents according to the invention can be contained, for example, dirt carriers, Enzymes, brighteners, antimicrobial agents, fragrances, dyes and water Understood.

When washing with the softening detergent according to the invention the items to be washed are given the desired softness and grip properties, without that there is a deterioration in the absorbency of the textiles, like that possible in the event of an overdose of fabric softener. With the invention Softening detergent can be used in a simple and convenient way Prevent washed laundry from hardening or fabric hardened by washing make it soft and fluffy again. In addition, the textiles retain their softening properties Detergent antistatic properties.

The invention further relates to a process for the production of the softening detergent, which is present in powder to granular 1 μm form, and has the above-specified composition. The process is characterized in that a bisquat ammonium compound of the formula Ta in which the radicals R1 "R8 and Y have the meaning given in formula I, and X- is the anion of a surfactant of the sulfonate or sulfate type> optionally also a soap, or an inorganic or non-surfactant organic anionic radical, with the other detergent ingredients in mixed in a known manner.

Of the surfactants defined below, there are anionic surfactant residues X the anionic residues of the surfactants of the sulfonate and sulfate type, in particular alkylbenzenesulfonates, Alkanesulfonates, fatty acid sulfonates, fatty acid ester sulfonates, olefin sulfonates, fatty alcohol sulfates, Fatty alcohol polyglycol ether sulfates, alkanediol disulfates and, if appropriate, also the soaps made from natural or synthetic fatty acids.

The inorganic radicals X in the formula Ia include, for example Chloride, bromide, sulfate, phosphate, pyrophosphate, polyphosphate, borate, etc. understood. The non-surfactant organic anionic radicals X are aliphatic or cycloaliphatic Acid residues containing groups with less than 6 carbon atoms such as Acetates lactate, citrate, tartrate, glycolate, sulfoacetate, methosulfate, ethosulfate, Methanesulfonate, ethanesulfonate, etc. as well as non-surfactant aromatic sulfone or Sulfocarboxylic acid residues such as benzene, toluene or xylene sulfonates, sulfobenzoate etc. into consideration.

In compounds of the formula Ia which are preferably used, there is the inorganic one or non-surfactant organic radical X from an anion, as is the case with the usual Quaternization reactions of tertiary amines are introduced.

The inventive method for producing the plasticizing agents described Detergent can be carried out by various methods known per se.

For example, the powder can be more or less fine or bisquaternary ammonium compounds of the formula Ia in the form of granules Mix the remaining detergent ingredients, which are also powdered.

Most of the technical manufacturing methods for powdery or granular detergents are made into an aqueous slurry of the detergent constituents or a part of it and converts it into a dry product. Included one can hydratable inorganic salts in such amounts in the aqueous approach incorporate that they all present in the approach water as crystal water can bind. Such an approach solidifies into one without any further action Product, whereby you can accelerate this process by cooling can. 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 immediately falls into powder form 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> the usual quiet ones in detergents can be used as structural substances.

Another manufacturing method can be powdered or granular hydratable salts with an aqueous mixture of the remaining detergent constituents spray and get a mostly granular product.

Finally, you can dry the aqueous approach hot in the usual way, what can happen on hot surfaces or in a stream of hot air. This latter Variant is currently the preferred method.

If you put the detergent according to the invention on the way over a aqueous formulation of the ingredients by hot drying, then certain detergent ingredients are such as foam inhibitors, bleaches, enzymes etc. not in the aqueous Approach incorporated, but subsequently added to the powder detergent. This type of incorporation is also recommended for those to be used according to the invention bisquaternary ammonium compounds of formula Ia.

It may be advantageous to use the compounds of the formula Ia by mixing with one of the hydratable salts mentioned first in a transferring dry powdery preliminary product.

The composition of the detergent according to the invention is in general in the range of the following formulation: 5 - 80, preferably 8 - 40 wt. Surfactant combination consisting of: 20 - 90, preferably 50 - 80 wt .- anionic surfactants from the sulfonate and / or sulfate type and optionally zwitterionic and / or nonionic surfactants, 0 - 6o> preferably 5 - 50 wt. Soaps with 10 - 26, preferably 12 - 22 carbon atoms, 80-10, preferably 70-30% by weight of a bisquaternary ammonium cation of the formula I, O - 10, preferably 0.2 - 5% by weight of non-surfactant foam inhibitors, o - 10, preferably 0.2-5% by weight foam stabilizers, 95-20, preferably 90-45 % By weight of builders, at least some of these builders being alkaline reacts, and the amount of the alkaline to neutrally reacting builder substances preferably 0.5 to 7 times, and particularly 1 to 5 times the whole Surfactants, and O - 30, preferably 1 - 15% by weight of other detergent ingredients, such as 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 that ill - the above formulation is regarded as part of the structural substance.

The bleaching component can include any stabilizers that may be present and / or activators-2-55, preferably 7-50% by weight of the total detergent turn off.

The for the production of the white laughing detergents according to the invention usable bisquaternary compounds of the formula Ia in which X is an inorganic or non-surfactant organic anionic radical are known in some cases partly-new connections. You can choose from. Corresponding bistertitarian amines by quaternization with alkylating agents such as Alkyl halides or dialkyl sulfates or alkyl esters of aromatic or aliphatic Sulphonic acids are produced.

The bisquaternary ammonium compounds which can be used according to the invention of the formula Ia, in which X is the anion of a surfactant of the sulfonate or sulfate type, optionally also means a ßSaife, can by implementing the above Compounds of the formula Ia in which X is an inorganic or non-surfactant organic anion means with the alkali salts of the above-mentioned anionic Surfactants are obtained. For this purpose, for example, the aqueous solutions of the starting materials mixed, the mixture optionally heated, the reaction product of the aqueous Phase separated, optionally washed with water and dried. In In practice, the moist reaction product can also be used directly for the preparation of the products according to the invention Laundry detergents are used by first using it to bind moisture a solid granular carrier on the basis of a water-soluble hydratable Salt that can be used as a structural substance in detergents, such as Sodium sulfate, sodium tripolyphosphate "sodium pyrophosphate, sodium orthophosphate, Sodium carbonate, mixed to a dry powdery precursor ~.

Contain the anionic, zwitterionic or nonionic surfactants in the molecule at least one hydrophobic residue of usually 6 - 26, preferably 10 - 22 and in particular 10-18 carbon atoms and at least one anionic, nonionic or zwitterionic water-solubilizing group. The preferably saturated hydrophobic The remainder is usually aliphatic, possibly also alicyclic, temperature; he can connected to the water-solubilizing groups directly or via intermediate links be. There are e.g. benzene rings, carboxylic acid ester or carbonamide groups as intermediate links, ether- or ester-like bonded residues of polyhydric alcohols, such as those of ethylene glycol, of propylene glycol, g @ cerine or corresponding polyether residues.

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 obtained from, among other things, preferably straight-chain aliphatic Hydrocarbons with 9-15, in particular 10-14, carbon atoms by chlorination and alkylating benzene or from corresponding terminal or internal olefins obtained by alkylating benzene and sulfonating the resulting alkylbenzenes. Furthermore, aliphatic sulfonates are of interest, such as are preferred for example from saturated, 8-18 and preferably 12-18 carbon atoms in the molecule Hydrocarbons by sulfochlorination with sulfur dioxide and chlorine or sulfoxidation with sulfur dioxide and oxygen and converting the products obtained in this way into the sulfonates are accessible.

Alkensul £ onates and hydroxyalkanesulphonate are also used as aliphatic sulphonates Mixtures containing d1sulfonates can be used, e.g. those obtained from terminal or intermediate C8 to C18 and preferably C12 to C18 olefins by sulfonation with sulfur trioxide and obtain acidic or alkaline hydrolysis of the sulfonation products. With the so The sulfonate group is found in many of the aliphatic sulfonates produced on a secondary carbon atom; but you can also by repositioning more terminal Olefins with; Use bisulfite obtained sulfonates with a terminal sulfonate group.

The sulfonates to be used according to the invention also include Salts, preferably dialkali salts, of α-sulfofatty acids and salts of esters of these acids with mono- or polyvalent, 1-10, preferably 1-4 and especially Alcohols containing 1 - 2 carbon atoms.

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 - 8 carbon atoms containing aliphatic or aromatic sulfomono- or -dicarboxylic acids, the AlkylglYceläthersulronate as well as the salts of the amide-like -Koyldensations produkc e of fatty acids or sulfonic acids with aminoethanesulfonic acid.

As surfactants of the sulfate type are fatty alcohol sulfates, especially the Coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol and diol disulfates, those produced from fatty alkyl-1,2-diols should be mentioned. Also from final or internal C8 to C18 olefins - useful sulfonation products of the sulfate type are available.

This group of surfactants also includes sulfated fatty acid alkylolamides or fat: acid monoglycerides and sulfated alkoxylation products of alkylphenols (C8 to C15 alkyl), fatty alcohols, fatty acid amides or fatty acid alkylolamides, those in the molecule 0.5-20, preferably 1-8 and especially 2-4 ethylene and / or May contain propylene glycol residues.

Suitable anionic surfactants of the carboxylate type are e.g. Fatty acid esters or fatty alcohol ethers of hydroxycarboxylic acids and the amide-like ones Condensation products of fatty acids or sulfonic acids with aminocarboxylic acids, e.g. with glycocolla, sarcosine or with protein hydrolysates.

Anionic detergent active substances of the soap type are those from natural or synthetic fatty acids, optionally also from resin or Naphthenic acids useful, especially when these acids have iodine numbers of at most 50 and preferably less than 10.

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, alkylolamide groups and also 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 ether residues, especially ethylene glycol ether residues may contain per SiolekUl. In addition, in these polyether chains or on the ends of which contain propylene or butylene glycol ether residues or polyether chains be.

The nonionics also include those under the trade name "Pluronics" or "Tetronics" known products. They are obtained from water-insoluble per se Polypropylene glycols or from water-insoluble propoxylated lower, 1 - 8, preferably 3 to 6 carbon atoms containing aliphatic alcohols or from water-insoluble alcohols propoxylated alkylenediamines. These water-insoluble (i.e., hydrophobic) propylene oxide derivatives are converted into the nonionios mentioned by ethoxylation until they are water-soluble. Finally, nonionics are also those known as "Ucon fluids", some of which are still water-soluble Reaction products of the abovementioned aliphatic alcohols with propylene oxide can be used, The inionics also include fatty acid or sulfonic acid alkylolamides, which z. B, from mono- or diethanolamine, from dihydroxypropylamine or other polyhydroxyalkylamines, z. B. derive the Glycaminen. They can be replaced by amides from higher primary or replace 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.

Zwltterionische Tenside contain in the molecule both acid and basic hydrophilic groups. The acidic groups include carboxyl, sulfonic acid, Sulfuric acid half ester, 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 sulfobetaines obtained for example, by reacting tertiary, 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 especially 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 which are in the medium temperature range are of particular practical importance up to about 6500 still foaming, but when transitioning 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 ()) soaps on the other hand, nci combinations of the components (1) and (2) bw. (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, their amount at least 5% by weight, preferably at least 10% by weight of the total, The proportion of soap present in the surfactant combination can make up a stronger one Foam absorption, especially in the higher temperature range, is achieved.

The foaming power of the surfactants can, however, also be increased by additives better known, not. Reduce surfactant foam inhibitors. These include optionally chlorine-containing N-alkylated aminotriazines, which can be obtained by reacting 1 Moles 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. - Aminotriazine act similarly- or mclamine derivatives that contain propylene glycol or butylene glycol ether chains, whereby 10-100 such glycol residues can be contained in the molecule. You get such compounds, for example, by adding appropriate amounts of propylene and / or butylene oxide on aminotriazines, in particular on melamine. Preferred are e.g. 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. Products have proven to be particularly effective proven, which can be obtained by adding 5-10 moles of propylene oxide to 1 mole of melamine and further addition of 10- '50 moles of butylene oxide to this propylene oxide derivative is obtained.

Also other, non-surfactant, water-insoluble organic compounds, such as paraffins or haloparaffins with melting points below 100 ° C., aliphatic C18 to C40 ketones and aliphatic carboxylic acid esters, which are in the acid or alcohol radical, possibly also in each of these two radicals, contain at least -18 carbon atoms (e.g. Triglycerides or fatty acid fatty alcohol esters) can be used, especially in combination made from anionic synthetic surfactants and soaps, used as foam inhibitors the Non-surfactant foam inhibitors are often only fully effective at temperatures in which they are in the liquid state, so that the foam behavior of the Products can be controlled in a similar manner by choosing suitable foam inhibitors such as by choosing soaps made from fatty acids of suitable chain lengths.

If you combine foam stabilizers with temperature-dependent foam inhibitors, so one gets good at low temperatures, with increasing approach to the Cooking temperature, products that foam less and less.

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 Reactive salts are, for example, bicarbonates, carbonates or silicates deriAlkalien, also mono-, di- or trialkali orthophosphates, di- or tetraalkali pyrophosphates, as complexing agents known metaphosphates, alkali sulfates and the alkali salts of organic, non-capillary-active sulfonic acids containing 1 - 8 carbon atoms, carboxylic acids and sulfocarboxylic acids. 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 and 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 citra-corsic 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 as well as the alkaline reacting polyphosphates, especially the tripolyphosphate.

They can be completely or partially replaced 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, combinations of different complexing agents can also be used. The other known complexing agents also include di- and polyphosphonic acids of the following constituents: wherein R is alkyl and -R 'is 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 -OH, -NH2 or -NXR. The following compounds are particularly suitable for practical use: methylenediphosphonic acid, 1-hydroxyethane-1, 1-diphosphonic acid, 1-aminoethane-1, 1-diphosphonic acid, amino-tri- (methylenephosphonic acid), methylamino- or ethylamino-di- (methylenephosphonic acid) and ethylenediamine tetra (methylenephosphonic acid). All of these complexing agents can be present as free acids, preferably as alkali salts. Na Among the preferably inorganic per compounds used as bleaching agents, sodium perborate tetrahydrate (NaBO2. H2O2. 3 H2O) is particularly practical. Meaning. In its place you can partially or completely, ie up to NaBO2. H2O2 dehydrated perborates can be used. They are also the NaBO2 borates described in DBP 901 287 and USP 2,491,789. H2O2 in which the ratio Na2O: B205 is less than 0.5: 1 and preferably in the range from 0.4-0.15: 1, while the ratio H2O2: ila in the range from 0.5-4 : l falls. All of these perborates can be wholly or partly replaced by other inorganic per compounds, in particular peroxyhydrates, for example the peroxyhydrates of ortho-, pyro- or polyphosphates, especially tripolyphosphates, and carbonates.

It is recommended -in 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: SiO2 = 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 are the organic complexing agents, the amount of which is 0.25 - 5, can preferably make up 0.5 - 2.5 ffi 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 can be used on alkali silicates.

The detergents according to the invention contain monopersulfates and chlorides active chlorine is thus 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 stirs, in particular a CO or S02 group. These connections include Dichloro and trichlorocyanuric acid or salts thereof, chlorinated alkylguanides or alkyl biguanides, chlorinated lIydantoins and chlorinated melamines.

Dirt carriers can also be used in the preparations according to the invention be included, which suspends the dirt detached from the fiber in the liquor hold and thus prevent graying. For this purpose, water-soluble colloids are usually used of an organic nature, such as, for example, the water-soluble salts of polymeric materials 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 strength. Water-soluble polyamides containing acidic groups are also useful suitable for this purpose. Soluble starch preparations and others can also be used use as the above starch products, such as 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 neutral to clearly alkaline, so that the pH value of a 1 show 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 made more alkaline (pH = 9.5 - 12, preferably 10 - 11.5) are.

The weavable brighteners are mostly, if not exclusively, Derivatives of diaminostilbene sulphonic acid, diarylpyrazolines and aminoeumarines.

Examples of brighteners from the class of the diaminostilbene 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 "lipatic, aromatic or heterocyclic, primary or secondary amine, and radicals of aminosulfonic acids, aliphatic radicals present in the above groups preferably from 1-4 and in particular 2-4 C "Contain atoms, whereas the heterocyclic ring systems are mostly 5- or 6-membered rings. The aromatic amines are preferably the radicals of aniklins, anthranilic acid or anilinesulfonic acid. Lighteners derived from diaminostilbene sulfonic acid are mostly used as cotton lighteners. The following products derived from formula II are commercially available, where Al represents the radical -NH-C6H5 and R2 can mean 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-SO3H , -OCH3. With regard to fiber affinity, some of these brighteners are to be regarded as transition types to the polyamide brighteners, for example the brighteners with R2 = -NH-C6H5.

To the cotton helper of the diaminostillbene sulfonic acid type also belongs the compound 4,4-bis - (- 4-phenyl-vicinaltriazolyl-2 -) - stillbedinsulfonic acid-2,2 '.

The polyamide brighteners, some of which in turn have a certain affinity for cotton fibers, include diarylpyrazolines of formulas III and IV: 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 carry further substituents can, 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 W, where the radical R7 can represent the groups C1, -SO2-NH2, -SO2-CH = CH2 and -COO-CH2-CH2-O-CH3, while the rest 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-phenyl7-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.

If the brighteners are used together with other components of the invention Products as an aqueous solution buw. Paste present and solid by hot drying 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 usually provide a mixture of different enzymatic active ingredients. Depending on their effect they as proteases, carbohydrases, esterases, lipases, oxidoreductases, catalases, Peroxidases, irreases, isomerases, lyases, transferases, desmolases or nucleases designated.

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 usually supplied by the manufacturers as aqueous solutions de Active ingredients or with the addition of diluents brought onto the market as a powder. Sodium sulphate, sodium chloride, alkali ortho-, pyro- or polyphosphates, especially tripolyphosphate. Often you bring the still damp ones Prepare enzymes with calcined salts, which then agglomerate if necessary the existing particles to larger particles the existing crystal water and bind the enzymatic agent.

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 use the enzymes in the powder of the detergent according to the invention to tie. A mixture is preferably sprayed for this purpose from the respective product and the enzymatic active ingredient with the above nonionic substances, or the enzyme preparation is dispersed in said non-ionic substance and combines this dispersion with the other components of the product. If these remaining components of the product are solids, it can the dispersion of the enzymatic substances in the nonionic component is also possible Spray onto 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 LVU / g and / or amylase activities of 20 - - 5,000, preferably 50 - 2,000 SKBE / g and / or lipase activities of 2 - 1,000, preferably 5-500 TE / g.

These details about ci: ie enzyme activities result from the activities of those enzyme preparations which on the day of registration for use in the detergent sector 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 needed so that the activities with proteases and amylases e.g. up to 5 times, with lipases E.g. up to 10 times the maximum values given above. Therefore, preparations with high activities should also be available in the future from an economic point of view appear suitable for use in the detergent sector, so the enzyme activity can be increased as required.

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, as well as R.M. Sandstedt, E. Kneen and M.J. Blish "Cereal Chemistry", Volume 16 (1939), pages 712-723; Determination of the activity of the lipases R. Willstätter, E Waldschmidt - Leitz and Ms.

Hemmen: "Hoppe-Seyler's Journal for Physiological Chemistry", Volume 125 (1925), pages 110-117; R. Boissonas: "Helvetica Chimica Acta", Volume 31 (1948), pages 1571-1576. - EXAMPLE The following examples describe compositions of some preparations according to the invention. Except for those in it salt-like components contained in the fabric softener - salt-like surfactants, Other organic salts and inorganic salts are present as sodium salts, provided nothing else is expressly stated. The related names respectively.

Abbreviations mean: "ABS" the salt one made by condensing straight-chain olefins with benzene and sulfonation of the resulting alkylbenzene obtained alkylbenzenesulfonic acid having 10-15, essentially 11-15, carbon atoms in the alkyl chain; Alkanesulfonate "one made from paraffins with 12-16 carbon atoms sulfonate obtained by sulfoxidation; "Fs-ester sulfonate" obtained from the methyl ester of a hardened tallow fatty acid by sulfonation with SO3 Sulfonate; "Olefin sulfonate", from mixtures of olefins having 2-18 carbon atoms by sulfonating with SO3 and hydrolyzing the sulfonation product with lye obtained sulfonate, consisting essentially of A Ikensul fonat and Hydroxyalkansul fonat, but also contains small amounts of disulfonates. Each An olefin sulfonate-containing preparation was made using two different types of olefin sulfonate manufactured; one was made from a mixture of straight-chain terminal olefins, the other was made from a mixture of internal olefins; "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 "are the sulfated additive products of 2 IloL of ethylene oxide to 1 mole of coconut fatty alcohol or 3 moles of ethylene oxide to 1 mole Taigfettalkohol or from 2 moles of ethylene oxide to 1 mole of oleyl alcohol, "sulfobetaine" produced by reacting a Kokosalkyldimethylamtns with propane sultone Betains; "OA + 5 ÄO", "OA + 10 ÄO", "KA + 20 ÄO" and "KA + 9 ÄO + 12 PO" represent the addition products of ethylene oxide (ÄO) or

Propylene oxide (PO) on technical oleyl alcohol (OA), or

Coconut alcohol (KA); "Perborate" is a substance containing about 10% active oxygen Product of approximate composition NaBO2.H2O2.3H2O; "NTA", "EDTA" or "HEDP" the salts of nitrilotriacetic acid, ethylenediaminetetraacetic acid and hydroxyethane diphosphonic acid; "Soap A or B" is one made from a fatty acid mixture of 9% by weight of C18, 14% by weight of C20 and 77% by weight of C22 (iodine number) (A); or 18% by weight C16, 32% by weight C18, 12% by weight C20 and 48% by weight C22 (iodine number 4) (13) manufactured soap; "CMC" the salt of carboxymethyl cellulose.

A mixture is used as a non-surfactant foam inhibitor in the examples from about 45% of an N, N'-di- (alkylamino) -chlorotriazine and about 55% of an N, N ', N "-tri (alkylamino) -triazine used. In these triazine derivatives, the alkyl radicals are a mixture of homologues with 8-18 carbon atoms. The 'monochiortriazine derivative or use the trialkylaminotriazine separately. Provided the products described The others may contain synthetic sulfates or sulfonates along with soap non-surfactant foam inhibitors mentioned in the description are used, such as paraffin oil or paraffin .. In the manufacture of detergents the show inhibitor is dissolved in a suitable organic solvent or in the molten state by means of a nozzle on the agitated powdery preparation sprayed on.

In all examples, the quantities given relate to the pure Surfactants and textile softeners. These substances can be production-related by-products such as water, sodium sulfate, sodium chloride, sodium carbonate, etc. Since such accompanying substances do not affect the effectiveness of the individual substances in any way 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 wt% ABS, (2) 3.1 wt% OA + 10 AO, (3) 4.5 Soap B by weight, (4) 35.8% by weight sodium tripolyphosphate, (5) 4.0% by weight Na2O. 3.3 SiO2, (6) 1.1 wt .-% CMC, (7) 0.2) wt .-% EDTA, (8) 0.20 wt .-% optical brightener, (9) 18.3% by weight perborate, (10) 15.0% by weight fabric softener, (11) 0.15% by weight fragrance, Remainder sodium sulfate and water.

The detergent according to the above recipe is made by mixing a atomization-dried powder detergent consisting of the aforesaid ingredients (1) to (8) with the remaining components (9) to (11). As a textile softener the following active ingredients are used: A: propylene-1,3-bis (N, N-dimethyl-N-tallow alkylammonium hexyl sulfate); B: propylene-1,3-bis (N, N-dimethyl-N-laurylammonium-capric acid-α-sulfonate); C: propylene-1,3-bis (N, N-dimethyl-N-laurylammonium) -decanediol 1,2-disulfate; D: 2-butynylene-1,4-bis (N, N-dimethyl-N-tallow alkylammonium dodecylbenzenesulfonate).

The textile softening effect of the detergents according to the invention according to Example 1 is demonstrated using the following wash test: In a wash liquor with 7.2 g / l of the detergent from Example 1 ground in a drum washing machine Samples of new full cotton terry cloth as well as samples of pre-washed (hardened) Cotton terry fabric at a temperature of 90 ° C and a liquor ratio washed 1: 5. A laundry detergent free of textile softeners is used for comparison used, in which the amount of Textilweiciinlacher according to the above recipe through Sodium sulfate is replaced. After each wash, the samples are rinsed and hung dried.

Then 4 people independently assess the grip, with grades between .1--. full and very what grip and very hard grip are awarded. The mean values are calculated from the individual assessments, which are shown in the table below for the 1st, 3rd, 5th and 10. laundry are put together. The limit values 1 and 6 are defined as follows: Samples of new cotton terry fabric are treated for 240 hours in a washing machine under high-temperature washing conditions in water with the addition of small amounts of tripolyphosphate.After drying, the fabric that has been prewashed in this way is given a grade of 6. Samples of new cotton terry fabric are de-treated and treated with a solution of 0.5 g / l ditallow alkyldimethylammonium chloride. The fabric softened in this way is given a rating of 1. Accordingly, the samples of the new, untreated cotton terry fabric used in the test have hand grades in the range 1.5-2. Detergent number of! Touch tone Example 1 washes t new prewashed items with active substance tissue tissue A 1 1.4 5.0 3 1.5 4.5 5 5 1.1 4.6 10 1.6 4.4 B 1 1.4 4.1 5 1.4 5 1.5 4.4 10 | 1.5 | 4.3 C 1 1.5 4.8 5 1.5 5 1.9 4.8 10 1.8 4.8 D 1 1.3 4.1 3 1.5 4.0 5 1.2 3.7 10 1.3 Comparison 1 2.2 (without active ingredient 5 2.3 5 | 2.5 | 5.9 10 2.7 6, not specified Examples 2-7 describe further detergents according to the invention. The active ingredients AD are used as textile softeners in the examples. The following active ingredients, for example, can also be used as fabric softeners with similar success: propylene 1,3-bis (N, N-dimethyl-N-palmitylammonium dodecyl benzenesulfonate); Decamethylene-1,10-bis (N, N-dimethyl-N-palmitoylammoniumdodecylbenzenesulfonate) dodecamethylene-1,12-bis (N, N-dimethyl-N-tallowalkylammonium-octylsulfate); Propylene-1,3-bis (N, N-dimethyl-N-myristylammonium lauryl sulfate); Hexamethylene-1,6-bis (N, N-dimethyl-N-palmitoylammonium decyl sulfate); Ethylene-1,2-bis (N, N-diethyl-N-stearylammonium dodecylbenzenesulfonate); Propylene 1,3-bis [N, N-dimethyl-N (3-palmitoylaminopropyl) ammonium dodecylbenzenesulfonate]; Propylene-1,3-bis (N3N-dimethyl-TT-laurylammonium laurate); Propylene-1,3-bis (N, N-dimethyl-N-laurylammonium decanesulfonate); Propylene-1,3-bis (N, N-dimethyl-N-laurylammonium-caprylic acid-M methyl ester-α-sulfonate). 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-EO-sulfate | - | - | - | 1.5 | - | - Scife A 3.5 - 4.2 3.8 - - Soap B - 4, o - - - - OA + 5 00 - 2.5 - - - - OA + 10 AO 3.0 - - - - 3.0 KA + 20 ÄO - - - - 3.5 - KA + 9 ÄO +12 PO - - - 2.5 - - Fabric softener 10.0 15.0 10.5 7.5 15.0 12.0 non-surfactant - 0.5 - o.8 0.2 0.3 Foam inhibitor Na2SO4 - - 22.5 18.0 - - Na2O. 3.3 SiO2 3.5 4.0 - 4.5 5.0 Na5P3010 36.5 35.5 - 40.5 20.5 35.0 - - 25.0 - - - Na2P2O7 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 nest; As a brightener, their amount. Depending on the intended use of the softening detergents, cotton brighteners, polyamide brighteners, polyester brighteners and their combinations are used.

If preparations with a content of enzymes are to be manufactured, in this way one uses commercially available products which, insofar as they are solid Enzyme concentrates, from the manufacturer by adding inorganic salts, mostly of sodium sulfate or sodium polyphosphate, in amounts of 7-15% by weight, for example are set for the following activities: One protease with 125,000 LVU / g, one Amylase m-4.t 75,000 SKBE / g, a lipase with 10,000 IU / g.

Claims (14)

Patent claims 1. Softening detergent, characterized in that it, together with anionic surfactants of the sulfonate lmd / or sulfate type and optionally zwitterionic and / or nonionic surfactants and / or soaps as well as structural substances and optionally other customary ingredients, a bisquaternary ammonium cation of the formula I contains in which R1 and R2 are preferably saturated alkyl radicals with 8 - 24, preferably 12 - 20 carbon atoms, or the radical RNH (CH2) n-, in which R is a fatty acid radical with 6 - 18 carbon atoms and n is a number from 2 - 10, R3 - R6 is alkyl radicals with 1-8, preferably 1-5 carbon atoms, or mono- or dihydroxyalkyl radicals with 2-4 carbon atoms, R7 and R8 are hydrogen or alkyl radicals with 1-10, preferably 1-3 carbon atoms, Y is a single bond or a straight-chain or branched one Alkylene radical with 1 to 22, preferably 1 to 10 carbon atoms, or a hydroxymethylene, ethylene, acetylene, p-phenylene, dimethyleneoxy, p-diphenyleneoxy or p-diphenylenesulfonyl radical. 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: 20-90, preferably 50-80% by weight of anionic Surfactants of the sulronate and / or sulfate type and optionally zwitterionic and / or nonionic surfactants, 0 - 6o, preferably 5 - 50% by weight soaps with 10 - 26, preferably 12-22 carbon atoms, 80-10, preferably 70-30% by weight of one bisquaternary ammonium cation of the formula I, O - 1Q, preferably Q, 2 - 5% by weight non-surfactant foam inhibitors, 0-10, preferably 0.2-5% by weight foam stabilizers, 95-20, preferably 90-45 wt. Builder substances, at least some of which this builder substance reacts alkaline, and the amount of alkaline up neutrally 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, with the proportion 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; marked that the framework substances to at least 30%, in particular to at least 50% of their Weight of condensed phosphates, preferably tripolyphosphate and / or organic Complexing agents exist. 4. Detergent according to claim 1-3, characterized in that the Builder substances contain a bleaching component, including any present Stabilizers and / or activators 2-35, preferably 7-30% by weight of the total Detergent. 5. Detergent according to claims 1-4, characterized in that it Propylene-1,3-bis (N, N-dimethyl-N-tallowalkylammoniumhexylsulfate) contains. 6. Detergent according to claim 1-4, characterized in that it Propylene-1,3-bis (N, N-dimethyl-N-laurylammonium) -capric acid - contains sulfonate. 7. Low-foaming detergent according to claim 1 - 6, characterized in that that the fatty acid residues present in the soaps of the surfactant component are at least 5% by weight, preferably at least 10% by weight, of fatty acid residues with 20-26, preferably 20-22 carbon atoms. 8. Detergent according to claim 1-7, characterized by a further Content of enzymes. 9. Detergent according to claim 1-8, characterized in that the non-surfactant foam inhibitors as discrete particles with the other ingredients the detergent are mixed. 10. Detergents in a solid, pourable consistency according to claim 9, characterized in that the foam inhibitors with solid particles of the detergent or a fixed component of the detergent are connected, wherein the foam inhibitors completely or partially envelop the solid particles mentioned can. 11. Process for the preparation of the detergent according to claim 1-10, characterized in that one bisquaternary Ar., Monium compound of the formula Ia in which the radicals R1 - R8 and Y have the meaning given in formula I of claim 1 and X is the anion of a surfactant of the sulfonate or sulfate type, optionally also a soap, or an inorganic or non-surfactant organic anionic radical, with the other detergent ingredients mixed in a manner known per se. 12. The method according to claim 11, characterized in that the water-containing reaction product of a compound of the formula Ia in which X is a means inorganic or non-surfactant organic radical, and a surfactant of the sulfonate or sulfate type, optionally also a soap, by mixing with a water soluble hydratable salt into a dry powdery product transferred and this mixed with the other detergent ingredients. 13. The method according to claim 11, characterized in that one Compound of the formula Ia used in which X is an inorganic or non-surfactant represents an organic radical, as is usually the case in quaternization reactions is introduced by tertiary amines. 14. The method according to claim 11-13, characterized 'that one the compound of the formula Ia with a detergent powder produced by hot drying and optionally with other detergent ingredients such as foam inhibitors, Bleach, enzymes mixed together.