DE2048330A1 - Textile detergent compsn - contains an n-alkylpropane1,3-diamine for softening during washing - Google Patents

Abstract

Textiles are washed and flexibilised using a bath at 20-100 degrees C contg. (a) 0.2-1.5g/l of anionic sulphonate and/or sulphate surfactants, with 8-18C hydrophobic radicals, soaps (to prevent foaming); (b) 0.05-1.2g/l of an N-(10-24C pref. 12-18C) alkyl (from coconut, tallow oil) propane 1,3-diamine (not an urea complex) to impart suppleness where amt of (a) => (b); (c) 0.2-6.0 g/l of active additives contg. a decolourant and having an alkaline reaction; (d) 0-0.5 g/l of suspending agents, foam controllers, enzymes, brighteners and antimicrobic agents. Suppleness is imparted in the same operation as washing and this reduces cost.

Description

"Softening detergent, especially for drum washing machines" The invention relates to a softening detergent, particularly for use in drum washing machines, containing N-alkyl-1,3-propanediamines as fabric softeners.

When washing in modern drum washing machines, the fabrics, especially those made of cellulosic materials such as cotton and linen, hardened and thereby undesirably changes their performance properties. It is common, this hardening by post-treatment of the laundry with a Weic detergent, which essentially contains N, N-difatty alkyl-N, N-dimethylammonium salts, reversed close. However, since this means an additional work step in practice, Numerous proposals have already become known in which the detergent itself a fabric softener is added. Quaternary ammonium salts were predominantly used here of the type mentioned is used.

Because of the known incompatibility of such quaternary ammonium salts However, with anionic surfactants, especially with alkylbenzenesulfonate, is an additive from quaternary ammonium compounds to the usual detergents, the mostly anionic ones Contain surfactants, of no practical importance.

The object of the invention was to provide a detergent with softening properties to develop that is a good cleaning agent even in the presence of anionic surfactants and has a softening effect on the laundry and thus the hardening of the laundry prevented.

It has now been found that N-alkyl-1,5-propanediamines eit 10-24, especially 12-18 carbon atoms in the alkyl radical in the washing bath are good fabric softeners Have properties and therefore as fabric softeners for detergents, in particular are suitable for detergents containing anionic surfactants. The softening detergent is characterized in that it is used together with at least one surfactant from the group the anionic surfactants of the sulfonate and / or sulfate type, the soaps or the zwitterionic Surfactants, optionally nonionic surfactants, framework substances and optionally N-alkyl-1,3-propanediamines serving as fabric softeners for other detergent components photographed with 10-24, in particular 12-18 carbon atoms in the alkyl radical.

Among the other usual detergent ingredients1 those in the Agents according to the invention can be contained, for example, dirt carriers, foam regulating substances, enzymes, optical brighteners, antimicrobial agents, Understood fragrances and dyes as well as water.

The N-alkyl-1,3-propanediamines which can be used according to the invention are known. You can, for example, by adding an alkylamine onto acrylonitrile to form 2-alkylamino-propionitrile and subsequent reduction (Houben-Weyl, methods of organic Chemie, 4th ed., Vol. 11/1, page 564). The N-alkyl-1,7-propanediamines are considered technical Products available. These technical products are essentially to those whose alkyl radicals are preferably straight-chain, saturated or unsaturated are, and their Alkylamino residues from the corresponding fatty acids such as lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, Oleic acid, linoleic acid, arachidic acid, behenic acid, erucic acid, lignoceric acid, etc. descend.

Of particular practical importance are N-alkyl-l, 3-propanediamines, whose alkyl radicals are derived from fatty acid mixtures of the fatty acids mentioned, such as they are made from coconut oil, tallow, soybean oil, linseed oil, palm oil, rapeseed and rapeseed oil, fish and whale oils, etc. can be obtained.

The N-alkyl-l, 5-propanediamines mentioned are available under the trade names Diam #, Kenamine #, Dinoram #, Genamin #, Duomeen #. Your use as agrochemicals, flotation agents, corrosion inhibitors, auxiliaries in road construction, Additive for disinfectants or for lubricating, cutting and drilling oils etc. i t known (see e.g. company publication "Armeens #, Duomeens W", Armor Hess Chemicals Ltd., 1962).

Washing with the detergent according to the invention can be used prevent hardening of the laundry in a simple and convenient way for the user or largely undo it again. In this case, those according to the invention prove useful N-alkyl-1,3-propanediamines as good fabric softeners, in particular for textiles made from cellulose materials such as cotton and linen. A significant one An advantage over known plasticizers is that they have their effect unfold in a detergent containing anionic surfactants. It has also been found that the text softeners that can be used according to the invention improve the absorbency of the fabric not harmful and also effective antistatic agents for textiles made of synthetic fibers such as polyamide, polyacrylonitrile, polyester fibers, etc. represent.

The composition of the softening detergent according to the invention is generally in the range of the following formulation: 5 - 80 wt .- / o of a surfactant combination consisting of: 20-90% by weight of at least one surfactant from the group of anionic surfactants of the sulfonate and / or sulfate type, the soaps or the zwitterionic Surfactants and optionally non-ionic surfactants existing surfactant component, 80-10% by weight of an N-alkyl-1,3-propanediamine defined above, 0-10% by weight non-surfactant Foam inhibitors, 95-20% by weight of other detergent ingredients, in particular alkaline to neutrally reacting structural substances, dirt carriers, and possibly Enzymes, brighteners, perfume, dye, water, the proportion of which is used as a fabric softener Serving N-alkyl,) - propanediamines on the total detergent 2 - 20, preferably 5-15% by weight.

Foam-suppressed ones, preferably suitable for use in drum washing machines Softening detergents are generally made up as follows: 5 - 80, preferably 8-40% by weight of a surfactant combination consisting of: 20-90, preferably 50-80% by weight of one consisting essentially of anionic surfactants from the sulfonate and / or Type of sulfate with preferably 8-18 carbon atoms in the hydrophobic radical, including soaps any existing foam inhibitor and saturated fatty acids with 20-26 carbon atoms derived soap content, and optionally non-ionic Surfactants existing surfactant component, 80-10, preferably 70-30 wt M-alkyl-1,3-propanediamines defined above, 0-10, preferably 0.2-5, by weight non-surfactant Foam inhibitors, 0-10, preferably 0.2-5, by weight foam stabilizers, where however, at least one of the two foam-inhibiting components is always present is, 95-20, preferably 90-45 wt .-% builder substances, with at least one Part of these structural substances reacts alkaline, and the amount of the alkaline to neutrally reacting builder substances preferably 0.5 to 7 times and especially 1 to 5 times the total surfactant, and 0-30, preferably 2 - 15% by weight of other detergent ingredients, such as dirt carriers, enzymes, Brighteners, antimicrobial agents, fragrances and dyes, water, with the proportion of the N-alkyl-1,3-propanediamine on the total detergent 2 - 20, preferably 5 - 15 Weight is.

If the detergents contain soap, the proportion is the same of the anionic surfactants of the sulfonate and / or sulfate type to soap in the range of 50: 1 to 1: 5, preferably 20: 1 to 1: 2.

The detergents can also contain a bleaching component, which is included in the above formulations is regarded as part of the builder substances, and those inclusive any stabilizers and / or activators present 2-55, preferably 7-30 Weight can make up the entire means.

There are preferably at least 15 of the other structural substances , in particular at least 50% of their weight from complex-forming structural substances, such as tripolyphosphate and / or organic complexing agents.

The detergents in which the fabric softeners according to the invention can be used as liquids, pastes or powders; preferred are solid, powdery detergents. Such powdery Detergents can be produced by various methods known per se, wherein the fabric softener is either admixed with a detergent powder or The softening detergent is made by mixing the ingredients and uberf watches in Powder form. In the simplest case one can, provided the components are considered more or less fine powder or granules are present, the softening detergent obtained by mixing these ingredients.

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 framework 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 using a cooler. 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, 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 softening Detergent by way of an aqueous mixture of the ingredients by hot drying here, the fabric softener used in the present invention is preferably above Definition as well as certain other detergent ingredients such as non-surfactant Foam inhibitors, bleaches, enzymes, etc. not incorporated into the aqueous approach but afterwards added to the powder detergent.

It may be of advantage here, especially for gentle treatment Incorporation of smaller amounts of substances that make the product more effective or attractive design, such as enzymes, antimicrobials, detergents and fragrances, such substances by mixing them with some of the structural substances first in transferring a dry powdery intermediate product, which is then used in the usual way Detergent powder is added.

The following are the ingredients of the softening detergent Described in more detail sorted by substance class.

Contain the anionic, zwitterionic or nonionic surfactants in the molecule at least one hydrophobic residue of mostly 8-26, 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 residue is usually more aliphatic, possibly also of an alicyclic nature; he can work with the water-solubilizing groups directly or be 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, possibly also from resin or naphthenic acids, especially useful if these acids have iodine numbers of at most 70 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 olefins obtained by alkylating benzene and sulfonating the resulting alkylbenzenes. We @ -terhin are a @@ phatic sulfonates from Inter @ sse, as they @ 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 transfer 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. of terminal or central C8-18 and preferably C1218-0 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-sulfo fatty acids and salts of esters of these acids with mono- or polyvalent, 1 to 4 and preferably 1 to 2 carbon atoms Alcohols.

Further useful sulfonates are salts of fatty acid esters of oxethanesulfonic acid or of dioxypropanesulforic acid, the salts of the fatty alcohol esters of lower, 1 - Aliphatic or aromatic sulfomono- or dicarboxylic acids containing 8 carbon atoms, the alkyl glyceryl ether sulfonates and the salts of the amide-like condensation products of fatty acids or sulfonic acids with aminoethanesulfonic acid.

Fatty alcohol sulfates are to be mentioned as surfactants of the sulfate type, in particular made from coconut fatty alcohols, tallow fatty alcohols or from oleyl alcohol. Even from terminal or internal C8-18 olefins are useful sulfonation products sulfate type available. This group of surfactants also includes sulfated surfactants Fatty acid alkylamides or fatty acid monoglycerides and sulfated alkoxylation products of alkylphenols (C8-15-alkyl), fatty alcohols, pettsa.uramides or fatty acid alkylolamides, those in the molecule 0.5-20, preferably 1-8 and especially 2-4 ethylene and / or odeH May contain propylene glycol residues.

Suitable anionic surfactants of the carboxylate type are, for. B. the 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. B. with glycocolla, sarcosine or with protein hydrolysates.

To the non-ionic surfactants, here for the sake of simplicity as "Nonicnics" 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 amide products, whereby these nonionics 4 - 100, preferably 6 - 40 and in particular 8 - 20 ether residues, especially ethylene glycol ether residues could contain per molecule.

In addition, propylene- or butylene glycol ether residues or polyether chains may be present.

The Nonionios 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 nonionios 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 Glycaminen. You can get through 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, 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 enthalpy 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 surfactant types, as well as adding 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 is sufficient, whereas in other cases a stronger foam dampening is desired can. Products which are in the medium temperature range are of particular practical importance Foam up to about 65 ° C, 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) nonionies on the one hand and from ()) soaps on the other. When combining the components (1) and (2) or (1), (2) and (3), the foaming behavior can be determined by the respectively used Affect soaps; for soaps made of preferably saturated fatty acids with 12 - 18 C atoms, the foam attenuation is lower, while soaps from saturated Fatty acid mixtures Illit 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-alkylated 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. ; Acting 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. Such compounds are obtained, for example, by adding appropriate amounts Propylene and / or butylene oxide on aminotriazines, in particular on melamine.

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. As special Products that can be obtained by adding 5 - 10 mol Propylene oxide on 1 mole of melamine and further addition of 10-50 moles of butylene oxide of this propylene oxide derivative.

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 in the 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, E5 I: 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 foam behavior 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 good at lower temperatures, as you approach 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 the alkalis, furthermore 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, carboxylic acids containing 1 - 8 carbon atoms and sulfocarboxylic acids. These include, for example, water-soluble salts of the 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, fumaric acid., Acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, aconitic acid, methylenemalonic acid and citraconic acid. Mixed poles of these acids with one another or with other polymerizable substances, such as s.B. with ethylene, propylene, 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 wholly or partially replaced by organic complexing agents will.

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, with combinations of different complexing agents being one. can be set. The other known complexing agents also include di- and polyphosphonic acids from the following institutions: 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.

Dirt carriers can still be found in the softening detergents be included, which suspends the dirt loosened from the fiber in the plot 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 mined starch, Aldehyde starches, etc. Polyvinylpyrrolidone can also be used.

The ingredients of the softening detergents, especially the Framework substances are usually selected so that the preparations are neutral to clear react alkaline, so that the pH value of a 1 show solution of the preparation mostly is in the range of 7-12. Detergents for mild detergents usually have neutral to weak colors alkaline reaction (pH = 7 - 9.5), while in general cooking detergents stronger alkaline (pK4lert = 9.5 - 12, preferably 10 - 11.5).

Among those used as bleaching agents, preferably inorganic ones Sodium perborate tetrahydrate (NaBO2. H2O2. 3 H20) has special compounds practical importance. In its place, partially or completely, i. until to the NaBO2. H202 dehydrated perborates can be used. There are also those in the DBP 901 287 or borates NaBO2 2 H2O2 described in USP 2,491,789, in which the ratio Na 2 O: B 203 is less than 0.5: 1 and preferably in the range of 0, - 0.15: 1, while the H 2 O 2: Na ratio is in the range of 0.5 - 4: 1 falls. All of these perborates can be wholly or partially replaced by other inorganic ones Per compounds, in particular by peroxohydrates, are replaced, e.g. the peroxohydrates the ortho-, pyro- or polyphosphates, especially tripolyphosphates, and the carbonates.

It is advisable to use the products to stabilize de 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 especially 1: 1.

In their place there are other alkaline earth metals, cadmium or tin il ikates of the appropriate composition can be used. Hydrous oxides of the Tin are suitable as stabilizers.

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

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 diaminostilbene sulfonic acid derivatives are compounds according to formula I: In the formula, R1 and R2 can denote halogen atoms, alkoxyl groups, the amino group or residues of aliphatic, aromatic or heterocyclic, primary or secondary amines and residues of aminosulfonic acids, aliphatic residues present in the above groups preferably being 1-4 and in particular 2-4 C- Atoms contain3 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 the formula I 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, ZNH-C6H4-SODH , -OCH Some of these brighteners are to be regarded as transition types to the polyamide brighteners in terms of fiber affinity, eg the brightener with R2 8 -NH-C6H5.

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

The polyamide brighteners, some of which in turn have a certain affinity for cotton fibers, include diarylpyrazolines of the formulas II and III In formula II, 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, hydroxyaltyl, 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 III> where the radical R7 can represent the groups C1, -SO2-NH2, -SOp-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-dirnethylamino- or 4-methyl-7-diethylaminocoumarin. The compounds 1- (Berzimidazolyl-2 ') - 2- (N-hydroxyethyl-benzimidazolyl-2') - ethylene are also known 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.

If the brighteners are used together with other components 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 (iew.- of the solid 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. Own preparation obtained from Bacillus subtilis over others the advantage that they over alkali, percompounds and anionic Active washing substances relatively stable and still effective at temperatures of up to 700C are.

Enzyme preparations are usually supplied by the manufacturers as aqueous solutions of the active ingredients or with the addition of diluents in the form of a powder brought. Sodium sulfate, sodium chloride, alkali ortlio, Pyro- or polyphosphates, especially tripolyphosphate. Often you bring that still moist enzyme preparations with calcined salts, which then if necessary under Agglomeration of the existing particles into larger particles, the existing crystalline 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, non-ionic, preferably capillary-active, organic compounds, in particular use the nonionics described above to attach the enzymes to the particles of the Powder detergent too tie. For this purpose it is preferable to spray a mixture of the respective product and the enzymatic active ingredient with the above named nonionic substances, or the enzyme preparation is dispersed in the named nonionic 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 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 to 500 IU / g.

These details about the enzyme activities result from the activities those enzyme preparations that were used in the detergent field on the day of registration 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. up to 5 times, with lipases e.g. can be increased up to 10 times the maximum values given above. Therefore, in the future, preparations with high levels of activity should also be available 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, 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 lipases: R. Willstätter, E. Waldschmidt - Leitz and Fr.

Memmen: "Hoppe-Seyler's Journal for Physiological Chemistry", Volume 125 (1923), pp. 110-117; R. Boissonas: "Helvetica Chimica Acta", Volume 31 (1948), pages 1571-1576. e e i s n i e 1 e The following examples describe the composition of some preparations according to the invention. The contained therein salty ingredients - salty surfactants, other organic salts, as well as inorganic ones Salts - present as sodium salts unless expressly stated otherwise; will. The related names or abbreviations mean: "ABS" the salt of a by condensing straight chain olefins with benzene and sulphonating the so resulting alkylbenzene obtained alkylbenzenesulfonic acid with 10-15, essentially 11-13 carbon atoms in the alkyl chain; "Alkanesulfonate" one from paraffins sulfonate with 12-16 carbon atoms 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 The preparation was prepared 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 has been 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; "OA + 5 EO", "OA + 10 ÄO "," KA + 20 ÄO "and" KA + 9 ÄO + 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 ß of active oxygen Composition NaBO2 # H2O2 # 3 H2O; "NTA", "EDTA" or "HEDP" are the salts of nitrilotriacetic acid, ethylenediaminetetraacetic acid or hydroxyethyl diphosphonic acid; "Soap A or B "cne from a fatty acid mixture of 9 wt .-% C18, 14 wt .-% G20 and 77 wt .-% 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 a mixture 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 synthetis.che Containing sulphates or sulphonates together with soap, the others can be described in the description mentioned non-surfactant foam inhibitors are used, such as Paraffin oil or paraffin.

In the preparation of the preparations, the non-surfactant foam inhibitor was used dissolved in a suitable organic solvent or in a molten 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 III the sign "+" in the line "Na2SO4" means that low Amounts of sodium sulphate are present as an accompanying substance to the anionic surfactants. There 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 The utility of the N-alkyl-1,3-propanediamines as a textile softener in detergents has been proven by washing tests.

For this purpose, two types of cotton terry fabric were used, Type A: new fabric, Type B: beverage pre-hardened by continuous washing in a laboratory washing machine (Launderometer) washed at 950 C 5 times for 30 minutes each time. Each was used as a detergent 7 g / l of a preparation with the following composition: (1) 5.5% by weight ABS, (2) 4.5% by weight Soap B, (3) 2.5 wt% OA + 10 AO, (4) 39.0 wt% sodium tripolyphosphate, (5) 2.0 wt% EDTA, (6) 5.0 wt% Na20. 3.3 SiO 2, (7) 1.0 wt% CMC, (8) 18.0 % By weight perborate, (9) 9> 0% by weight, Co textile softener, (io) the remainder sodium sulfate and water.

The detergent according to the above formulation was prepared by mixing one Spray-dried detergent powder consisting of all the cell-named components (1) - (7) and (10) with the perhorate (8) and the fabric softener (9). The N-alkyl-1,3-propanediamines listed below were used as fabric softeners of Table I are used.

A laundry detergent free from textile softeners was used for comparison. in which the amount of fabric softener according to the above recipe by sodium sulfate was replaced. After the wash, the samples were rinsed, spun and hung dried. The grip was then independently assessed by 4 people, whereby Grades between 1 = full and very soft handle and 6 = very hard handle are given became. The values after the 5th wash became those resulting from the use of the fabric softener resulting grip improvement is calculated.

The limit values 1 and 6 of the handle notes are defined as follows: Samples made of new cotton terry cloth were placed in the washing machine for 240 hours Treated Kochwasohbedingungen in water with an addition of 2 g / l tripolyphosphate. After drying, the fabric washed in this way was given a grade of 6 (type B). Samples of new cotton terry cloth were depressurized and treated with a solution treated by 0.5 g / l ditallow alkyldimethylammonium chloride. Your so softened Tissue was given a grade of 1. Accordingly, the samples had the one used in the test untreated cotton terry fabric (type A) handle grades in the range of 1.5-2.

It is clear from the values in Table I below that the use hardening of the N-alkyl-1,3-propanediamines in a detergent according to Example 1 practically prevented from new tissue and pre-hardened tissue considerably softer maaht, whereby the general properties of the laundry are essential be improved.

Table I. No. Detergent according to Example 1 with fabric type handle after 6 improvement in handle Fabric softener - active ingredient in washes compared to same detergent 1 N-dodecyl-1,3-propanedi- A 1.3 0.8 amine B 4.5 1.5 2 N-cocoalkyl-1,3-propane A 1.0 1.1 diamine B 2.5 3.5 3 N-tetradecyl-1,3-propane A 1.0 1.1 diamine B 2.8 3.2 4 N-hexadecyl-1,3-propane A 1.0 1.1 diamine B 2.5 3.5 5 N-tallow alkyl-1,3-propane A 1.1 1.0 diamine B 2.5 3.5 6 N-octadecyl-1,3-propane A 1.0 1.1 diamine B 2.5 3.5 7 DIAM 26 # from General A 1.3 0.8 Mills B 3.4 2.6 (N-tallow alkyl-1,3-propane diamine) 8 Dinoram S # from Pro-A 1.0 1.1 quinor SA B 3.0 3.0 (N-tallow alkyl-1,3-propane diamine) 9 Duomeen T # from Armor A 1.4 0.7 Hess Chemicals Ltd. B 3.3 2.7 (N-tallow alkyl-1,3-propane diamine) Table I (continued) No. Detergent according to Example 1 with fabric - type handle after 5 handle improvement Fabric softener - active ingredient in washes compared to same detergent 10 Genamin TAP 100 # der A 1.0 1.1 Fa. Farbwerke Hoechst B 3.3 2.7 (N-tallow alkyl-1,3-pro- pandiamine) 11 Kenamin D 974 # of A 1.1 1.0 Humko Products, B 3.1 2.9 (N-tallow alkyl-1,3-pro- pandiamine) 12 Kenamin D 970 # of A 1.1 1.0 Humko Products B 3.1 2.9 (N-hydrotalga alkyl-1,3- propanediamine) 13 Dinoram O # from A 1.0 1.1 Prochinor SA B 3.0 3.0 (N-oleyl-1,3-propane diamine) 14 Kenamin D 989 # from A 1.0 1.1 Humko Products B 3.3 2.7 (N-oleyl-1,3-propane diamine) 15 Comparative detergent A 2.1 without fabric softener B Table II Component of the preparation% by weight of the component Preparation according to the example 2 3 4 5 6 7 8 N-Tallowalkyl-1,3-propanedi- 7 7 7 7 7 7 15 amine ABS 14 14 14 14 14 14 12 Perborate 18 18 18 18 18 18 15 Sodium tripolyphosphate 25 NTA 25 50 20 EDTA - - - 25 25 25 22 Sodium polyacrylic acid1) - - 30 25 - - - Polyethylene polymaleic acid2) - - - - 25 - 22 Remainder: sodium sulfate and water 1) By transferring the polyacrylic acid size S # from

BASF product manufactured into the sodium salt.

2) Product produced by saponifying and converting the commercial product EMA, type 21 ÖR from Monsanto into the sodium salt. Table III Part of the% by weight of ingredients in the preparation Preparation according to the example 9 10 11 12 13 14 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 3.5 - 4.2 3.8 - - Soap B - 4.0 - - - - OA + 5 ÄO - 2.5 - - - - OA + 10 AO 3.0 - - - - 3.0 KA + 20 ÄO - - - - 3.5 - KA + 9 ÄO + 12 PO - - - 2.5 - - non-surfactant - 0.5 - 0.8 0.2 0.3 Foam inhibitor Fabric softener -10.0 15.0 10.5 7.5 15.0 12.0 Na2SO4 20.5 + 22.5 18.0 + 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 Na4P207 - - 25.5 - - - Perborate - 22.3 - - 25.5 - MgSiO3 - 1.2 - - 1.5 - 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 rest In the detergents of Examples 2-8, the total structural substance present consists to a considerable extent of organic complexing agents. Such detergents, in which the structural substance - excluding any per-compounds but including any non-complexing, preferably alkaline-reacting structural substances - consists of 15-100, preferably 20-100% by weight of organic complexing agents, are characterized by a good combination of washing effect and softening effect.

The examples in Table III can be used as fabric softeners incorporate the N-alkyl-1,3-propanediamines listed in Table I.

Depending on the intended use, the softening agents were used as brighteners Detergents cotton brighteners, polyamide brighteners, polyester brighteners and their combination used.

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

Claims (11)

Claims 1. Softening detergent, characterized in that that it is used together with at least one surfactant from the group of anionic surfactants of the sulfonate and / or sulfate type, soaps or zwitterionic surfactants, optionally nonionic surfactants, builder substances and optionally others N-alkyl-1,3-propanediamines serving as fabric softeners for conventional detergent ingredients with 10-24, in particular 12-18 carbon atoms in the alkyl radical. 2. Means according to claim 1, characterized in that the alkyl radicals the N-alkyl-1,3-propanediamines of fatty acid mixtures of natural fats such as e.g. Coconut oil, tallow, soybean oil, linseed oil, palm oil, rapeseed and rapeseed oil, fish and whale oils, etc. descend 3. Means according to claim 1 and 2, characterized gekennzei.chletS that it is N-tallow alkyl 1, 3-propanediamine contain. 4. Composition according to claim 1 and 2, characterized in that it is N-hydrotalga alkyl-1,3-propanediamine contain. 5. Means according to claim 1 and 4, characterized in that it as other common detergent ingredients dirt carriers, foam regulating substances, Enzymes, optical brighteners, antimicrobial agents or fragrances and dyes as well as water. 6, softening detergent according to claim 1 - 5, characterized in that that the composition is in the range of the following recipe: 5 - 80% by weight of a surfactant combination consisting of: 20-90% by weight of at least one from a surfactant from the group of anionic surfactants of the sulfonate and / or sulfate type, the soaps or the zwitterionic surfactants and optionally nonionic surfactants existing surfactant component, 80-10% by weight of an N-alkyl-1,3-propanediamine Claims 1-4, 0-10% by weight of non-surfactant foam inhibitors, 95-20% by weight other detergent ingredients, especially those with an alkaline to neutral reaction GerZDtsubstanzen, dirt carriers, and possibly enzymes, brighteners, perfume, dye, Water, the proportion of N-alkyl-1,3-propanediamine serving as fabric softener of the total detergent is 2 - 20, preferably 5 - 15% by weight. 7. Schaumgedä.mpft'es softening detergent according to claim 1 - 6, characterized in that the composition is in the range of the following recipe lies: 5 - 80, preferably 8 - 40% by weight of a surfactant combination consisting of: 20-90, preferably 50-80% by weight of an essentially anionic surfactant of the sulfonate and / or sulfate type with preferably 8-18 carbon atoms in the hydrophobic Remainder, soaps including any hot, which serves as a foam inhibitor and soap content derived from saturated fatty acids with 20-26 carbon atoms, and optionally nonionic surfactants existing surfactant component, 80 - 10, preferably 70-30% by weight of an N-alkyl-1,3-propanediamine according to claim 1-4, 0-10, preferably 0.2-5% by weight of non-surfactant foam inhibitors, 0 10, preferably 0> 2 -5% by weight of foam stabilizers, but always at least one of the two foam-inhibiting components is present, 95-20, preferably 90-45% by weight of builders, at least some of these builders reacts alkaline, and the amount of the alkaline to neutral reacting builder substances preferably 0.5 to 7 times, and particularly 1 to 5 times the whole Surfactants, and 0 - 30, preferably 2 - 15% by weight of other detergent ingredients, such as dirt carriers, enzymes, brighteners, antimicrobial agents, fragrances and Dyes, water, the proportion of N-alkyl-1,3-propanediamine in the total detergent 2 to 20, preferably 5 to 15% by weight. 8. Detergent according to claim 1-7, characterized in that it contain a bleaching component as part of the scaffolding substances, including the any stabilizers and / or activators present 2-35, preferably 7-30 Makes up% by weight of the total composition. 9. Detergent according to claim 1-8, characterized in that the other builders, i.e. without but including the bleaching component possibly existing non-complexing, preferably alkaline-reacting structural substances to at least 15, in particular to at least 50% of their weight of inorganic and / or organic complexing agents 10. Detergent according to claim 1 - 9, characterized in that the other structural substances according to Claim 9 to 15-100, preferably to 20-100 °, 4 of their weight from organic Complexing agents exist. 11. Detergent according to claim 1-10, characterized in that it from a mixture of the textile softeners according to claims 1-4 with a through Powdered detergents obtained by hot drying and, if appropriate, further detergents Detergent ingredients such as non-surfactant foam inhibitors, Bleaches, enzymes, etc.