EP0158260B1 - Detergent for coloured textiles - Google Patents

Description

The present invention relates to a detergent suitable for washing colored textiles, the surfactant component of which is a combination of nonionic surfactants with acylcyanamide salts, and which contains certain water-soluble polymers for preventing dye transfer from colored textiles to white or light-colored textiles during the washing together.

The transfer of dyes when washing colored and white or light-colored textiles together has been a problem for a long time, for which there have already been some proposed solutions, but not all of them can be fully satisfactory, because they are only marginal compared to a number of colors or textiles Have effect. So z. B. from DE-AS 22 32 353 a means known, the discoloration-inhibiting additive is polyvinylpyrrolidone. DE-OS 24 20 561 describes a detergent with a combination of alkali metal percarbonate and polyethylene glycol of a certain molecular weight and / or polyvinyl pyrrolidone. DE-OS 23 09 099 relates to an agent with proportions of two different organic compounds that contain basic nitrogen atoms in the molecule. In US Pat. Nos. 4,005,029 and 4,006,092 agents are described which contain per compounds which have a discoloring effect.

In DE-OS 30 26 090 it was proposed to add cationic starch ethers to prevent dye transfer to liquid detergents based on certain nonionic surfactants and textile-softening quaternary ammonium compounds. DE-OS 28 28 619 describes a discoloration-inhibiting detergent composed of three different types of surfactant, namely 1. nonionic surfactants, 2. zwitterionic or semipolar and 3. cationic surfactants, which must be present in certain proportions. DE-OS 3124 210 relates to a liquid detergent based on nonionic or zwitterionic surfactants; this detergent contains certain water-soluble polymers to prevent dye transfer. A textile detergent containing acylcyanamide salts, nonionic surfactants and optionally other conventional detergent components, including water-soluble colloids which act as graying inhibitors and which are mostly derived from cellulose or starch, is described in the earlier European patent application EP-A-131 137, published on January 16, 1985 published.

It has now been found that a textile detergent for colored textiles containing synthetic nonionic surfactants, water-soluble organic polymers, acylcyanamide salts and other conventional detergent components, which is characterized in that the detergent contains 1 to 30% by weight of alcylcyanamide salts, 1 up to 30% by weight of nonionic surfactants and 1 to 15% by weight of water-soluble, synthetic organic polymers which contain compounds from monomers with more than one amino group or their reaction products with aldehydes or dicarboxylic acid, with the further proviso that the agent contains no more than 5% by weight of strong electrolytes and sulfate or sulfonate surfactants which has particularly good discoloration-inhibiting effects.

Water-soluble polymers suitable for the agent according to the invention, which can be used individually or preferably in combination with one another or with the polyvinylpyrrolidone known as a discoloration inhibitor, are known, synthetically produced compounds which are used, for example, in the paper industry as retention agents for better separation of the paper fiber raw materials and fillers will. According to their structural structure, these polymers can be divided into four groups: polyethyleneimines, polyamines, polyaminamides and polyacrylamides.

Suitable polyethyleneimines are obtained by acid-catalyzed polymerization of ethyleneimine and can be modified by urea and epichlorohydrin or dichloroethane. Polyethyleneimines can contain primary, secondary and tertiary amino groups as well as quaternary ammonium groups. Aqueous solutions of polyethyleneimines react basicly. The molecular weight can be up to 100,000.

Polyamines are addition or condensation products from polyvalent aliphatic amines and substances with several reactive groups, e.g. B. epichlorohydrin or alkylene dihalides. They therefore always contain several secondary, tertiary or quaternary nitrogen atoms, and possibly also hydroxyl groups in the molecule. Accordingly, they are hydrophilic, polar compounds that behave like polyelectrolytes and are water-soluble unless they contain large hydrophobic groups in the molecule. The polyamines react basicly in aqueous solution. Suitable compounds are described, for example, in US Pat. No. 2,969,302.

Polyaminamides contain amino and amide groups in the molecule at the same time. They are produced, for example, by the condensation of polybasic acids, e.g. B. dibasic, saturated, aliphatic C _s - to C _s acids, and polyamines, and with substances that contain several reactive groups, such as epichlorohydrin. These compounds also react basicly in aqueous solution. Suitable polyaminamides are e.g. B. described in U.S. Patent 2,926,154.

Suitable polyacrylamides are high molecular weight polymers with molecular weights of several million. Anionic polyacrylamides are obtained by incorporating carboxyl groups, which are formed, for example, by partial hydrolysis, in addition to amide groups; Polyacrylamides containing amino groups react basicly in aqueous solution. Amino groups can be e.g. B. by reaction with alkali and hypobromite or hypochlorite.

Of the polymers mentioned, the polyethyleneimines and polyamines which react strongly in water are particularly suitable. Examples of commercially available particularly suitable polyethyleneimines are "Retaminol E ^(R) " and for polyamines, e.g. B. "Retaminol K ^(R) ", from Bayer, Leverkusen, Federal Republic of Germany.

The water-soluble reaction products of polyethylene or polypropyleneimine (molecular weight 300-6,000) with certain polycarboxylic acids having 2 to 10 carbon atoms described as graying inhibitors in DE-OS 19 22 450 are also very suitable.

Other very suitable products are the water-soluble reaction products of melamine or urea or dicyandiamide or guanidine and formaldehyde, e.g. B. the commercial products “Pressal R 50 ^(R) ”, “Melan 125 ^(R) ” or “Stabifix WE ^(R) ” from Henkel KGaA, Düsseldorf, Federal Republic of Germany.

Other polymers which can be used as retention aids in papermaking and are suitable for the detergents according to the invention are described, for example, in “Encyclopedia of Polymer Science and Technology”, Vol 9, pp. 762 ff, John Wiley & Sons, Inc., New York, 1968. The addition of these polymers to the detergents according to the invention likewise has an effect which inhibits discoloration.

The concentration of the polymers mentioned in a detergent according to the invention based on acylcyanamide salts and nonionic surfactants is in the range from 1 to 15% by weight, preferably 2 to 6% by weight. The application concentration of the detergent is in the range from 1 to 10 g / l of wash liquor, preferably in the range from 3 to 6 g / l.

The detergent according to the invention contains only a small amount or no strong electrolytes at all. In the context of this invention, “strong electrolytes” means the salts of strong bases with strong acids. Among these, soluble builder salts, e.g. B. alkali phosphates, sulfates, sulfonates, but not silicates or carbonates or the alkali aluminum silicates of the zeolite A, X, Y or P type known as water-insoluble detergent builders.

Heavy metal complexing agents of the polycarboxylate type, which also include aminopolycarboxylates, e.g. B. nitrilotriacetic acid or ethylenediaminotetraacetic acid or their salts with strong bases are not strong electrolytes. In contrast, the known anionic sulfate or sulfonate surfactants are strong electrolytes, i. H. the detergent according to the invention is largely or completely free of synthetic surfactants of the sulfate or sulfonate type and of soluble builder salts of the sulfate, sulfonate, phosphate type. The extensive or complete absence of strong electrolytes contributes significantly to the good discoloration-inhibiting effect of the detergent according to the invention. Strong electrolytes in and sulfate or sulfonate surfactants For the purposes of the present invention, the detergent according to the invention contains at most 5% by weight, preferably not more than 3.5% by weight.

The detergent according to the invention contains a combination of synthetic nonionic surfactants and acylcyanamide salts as the surfactant component.

Addition products of 2 to 40, preferably 2 to 20 moles of ethylene oxide with 1 mole of fatty alcohol or oxo alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide can be used as nonionic surfactants. The addition products of 5 to 16 moles of ethylene oxide with coconut oil or tallow fatty alcohols, with oleyl alcohol or with secondary alcohols with 8 to 18, preferably 12 to 18 carbon atoms, and with mono- or dialkylphenols with 6 to 14 carbon atoms in are particularly important the alkyl residues. In addition to these water-soluble nonionics, non-fully or not fully water-soluble polyglycol ethers with 1 to 4 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or small amounts of anionic surfactants.

Furthermore, the non-ionic surfactants are the water-soluble adducts of ethylene oxide with polypropylene glycol (= Pluronics ^(R) ), alkylenediamine-polypropylene glycol (= Tetronics ^(R) ) and alkylpolypropylene glycols with 1 to 10 C atoms, containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups useful in the alkyl chain in which the polypropylene glycol chain acts as a hydrophobic residue.

Nonionic surfactants of the amine oxide or sulfoxide type can also be used.

in der Me Natrium oder Kalium bedeutet und R einen Alkyl- oder Alkenylrest mit 9 bis 23 C-Atomen darstellt, der durch Hydroxyl- oder Alkoxygruppen substituiert sein kann.Acylcyanamide salts which are used in the detergents according to the invention in combination with nonionic surfactants are compounds of the formula 1

in which Me is sodium or potassium and R represents an alkyl or alkenyl radical having 9 to 23 carbon atoms, which may be substituted by hydroxyl or alkoxy groups.

The acylcyanamide salts used according to the invention can be obtained from carboxylic acid derivatives and cyanamide with subsequent neutralization by means of suitable bases (see German patent specification 708 428 or AE Kretov and AP Momsenko, Journal of Organic Chemistry of the USSR (1965), pages 1765 ff) be won.

Preparation is easier by reacting salts of cyanamide with carboxylic acid esters, as described in DE-OS 32 02 213. This process can also be advantageous for the further use of the acylcyanamide salts in the production of detergents and cleaning agents, since it supplies the salts in anhydrous form.

In addition to being easy to produce, the acyl cyanamide salts have the advantage that they can be produced from renewable raw materials, here fatty acid derivatives, and from cyanamide, which is easily accessible from calcium cyanamide. This reduces the dependence of detergent manufacturers on petroleum-based raw materials when using these surfactants. B. in the still most important anionic surfactant alkylbenzenesulfonate is noticeable. In addition, acyl cyanamide salts are readily biodegradable and toxicologically safe.

The sodium salts of acylcyanamides have particularly favorable properties with regard to the objectives of this invention, in particular those in which the radical R in formula I is an essentially unsubstituted alkyl or alkenyl radical having 11 to 17 carbon atoms. Such salts can be easily prepared industrially from monosodium cyanamide and the methyl esters of natural fatty acid mixtures, such as tallow fatty acid methyl ester and palm kernel fatty acid methyl ester.

When using acylcyanamide salts in combination with nonionic surfactants, a particularly good cleaning effect is achieved with agents which contain 3 to 15% by weight of acylcyanamide salts with 2 to 15% by weight, nonionic surfactant from the group of alcohol ethoxylates and alkylphenol ethoxylates, among other usual components Detergents and cleaning agents included.

Agents in which the acylcyanamide salts are present in combination with nonionic surfactants of the alcohol ethoxylate type have a very particularly high cleaning power against grease and pigment soiling in combination with a pronounced discoloration-inhibiting action.

• a) 5 bis 18 Gew.-% eines Alkylpolyglykolethers der Formel
  
  in der R¹ eine geradkettige Alkylgruppe und R² zu 20 bis 75 Gew.-% - bezogen auf den dem Alkylpolyglykolether zugrunde liegenden Alkohol- eine C₁-C₄-Alkylgruppe und im übrigen Wasserstoff bedeuten, wobei die Gesamtzahl der Kohlenstoffatome in R¹ und R² 11 bis 15 beträgt, und n einen Wert von 5 bis 9 bedeutet, und wobei n so ausgewählt ist, daß der Ethylenoxidanteil des Alkylpolyglykolethers etwa 50 bis 65 Gew.-% beträgt.
• b) 5 bis 18 Gew.-% eines Alkylpolyglykolethers der Formel II, in der R¹ eine geradkettige Alkylgruppe und R² entweder Wasserstoff, oder zu 20 bis 75 Gew.-% -bezogen auf den dem Alkylpolyglykolether zugrunde liegenden Alkohol- eine C₁-C₄-Alkylgruppe und im übrigen Wasserstoff bedeuten, wobei die Gesamtzahl der Kohlenstoffatome in R¹ und R² 6 bis 10 beträgt und n einen Wert von 3 bis 8 bedeutet, und wobei n so ausgewählt ist, daß der Ethylenoxidanteil des Alkylpolyglykolethers etwa 55 bis 70 Gew.-% beträgt.

In a liquid embodiment of the detergent according to the invention, which is preferred to powdery agents, the surfactant component consists of a combination of two different nonionic surfactants, as described in DE-PS 28 17 834, and of acylcyanamide salts of the formula 1. This particularly preferred wax agent according to the invention contains as nonionic surfactant a mixture of:

• a) 5 to 18 wt .-% of an alkyl polyglycol ether of the formula
  
  in which R ^{1 is} a straight-chain alkyl group and R ² is 20 to 75% by weight, based on the alcohol on which the alkyl polyglycol ether is based, a C ₁ -C ₄ -alkyl group and, moreover, hydrogen, the total number of carbon atoms in R ¹ and R ^{2 is} 11 to 15, and n is a value of 5 to 9, and where n is selected so that the ethylene oxide content of the alkyl polyglycol ether is about 50 to 65% by weight.
• b) 5 to 18% by weight of an alkyl polyglycol ether of the formula II in which R ^{1 is} a straight-chain alkyl group and R ^{2 is} either hydrogen, or 20 to 75% by weight, based on the alcohol on which the alkyl polyglycol ether is based, a C ₁ -C ₄ alkyl group and hydrogen mean, where the total number of carbon atoms in R ¹ and R ^{2 is} 6 to 10 and n is a value from 3 to 8, and wherein n is selected so that the ethylene oxide content of the alkyl polyglycol ether about 55 is up to 70% by weight.

The quantitative ratio of a): b) is preferably 2: 1 to 1: 2.

This mixture of nonionic surfactants in combination with c) is 2.0 to 7.0% by weight of acylcyanamide salts of the formula 1 in which R is an alkyl or alkenyl radical having 9 to 23, preferably 11 to 17, carbon atoms and Me sodium or potassium, preferably sodium.

The alkyl polyglycol ethers of the formula II which are suitable as constituent a) are derived from alcohols which are prepared by reacting linear olefins with carbon monoxide and hydrogen in accordance with the known oxo process by hydroformylation and subsequent hydrogenation. Commercially available oxo alcohol mixtures which are suitable for the preparation of the surfactant component a) are, for example, the oxo alcohols available from Deutsche Shell Chemie Gesellschaft under the trade name "Dobanol ^(R) _", which contain approx. 25% by weight of 2 Other suitable oxo alcohols are alcohol mixtures which are available under the name “Synprol ^(R) ” from Imperial Chemical Industries Ltd. and contain about 50 to 70% by weight of 2-alkyl branches. Other suitable products based on oxo alcohols are z. B. Various «Lutensol ^(A) » types from BASF with approx. 30 to 35% by weight branched alcohols and some «Lia ^(R) » types from Liquichimica SpA with approx. 60% by weight branched alcohols.

As component a), particular preference is given to alkyl polyglycol ethers which are ethylene oxide condensates of the aforementioned oxo alcohols having 13 to 15 carbon atoms and an average ethylene oxide content of approximately 55 to 65% by weight. Typical preferred products are, for example, «Dobanol 45-7 ^(R) », which consists of at least 95% by weight of C ₁₄ / C ₁₅ oxo alcohol with an average of 7 moles of ethylene oxide, and «Lutensol AO-8 ^(R) » , which is a C ₁₃ / C ₁₅ oxo alcohol ethoxylate with an average of 8 moles of ethylene oxide.

As component b), preference is given to alkyl polyglycol ethers whose alcohol base is natural or synthetic primary fatty alcohols or oxo alcohols which contain 9 to 12 carbon atoms and have an ethylene oxide content of approximately 60 to 70% by weight. Typical preferred products are e.g. B. the commercial product "Marlipal KF ^(R) " (Chemische Werk Hüls), which is a C ₁₀ / C ₁₂ fatty alcohol ethoxylate with an average of 6 moles of ethylene oxide, and the "Lutensol ON-70 ^(R) ", which is a C ₉ / C ₁₁ oxo alcohol ethoxylate with an average of 7 moles of ethylene oxide. Suitable fatty alcohols as the basis for preferred alkyl polyglycol ethers are also the commercial products “Lorol C-8 ^(R) to Lorol C-12 ( ^R )” (Henkel).

The ratio of the amount of component a) used to the amount of component b) essentially determines the parameters of washing power and foaming behavior. Optimal results are obtained if the ratio of a): b) is between 2: 1 and 1: 2.

In general, amounts of component a) and component b) of 10 to 30% by weight, based on the total weight of the detergent, are used, an amount of 15 to 30% by weight being preferred.

Water is preferably used as the solvent for the preferred liquid detergents. However, organic solvents can also be used in amounts of up to 20, preferably up to 16% by weight of the total liquid detergent. Such additional solvents are either lower alkanols or lower diols or polyols such as ethanol, isopropyl alcohol, ethylene glycol, propylene glycol or glycerin. Optionally, polyols with ether linkages such as methyl, ethyl; Butyl or diethylene glycol or their acetates (for example products of the “Cellosolve ^(R) ” type from Union Carbide Corp.) are used.

To improve the solubility of the surfactants, it is often expedient to use solubilizers, so-called hydrotropes, in addition to or instead of the organic solvents mentioned above. As a hydrotrope z. B. Suitable for urea Hydrotopes are added in amounts of 2 to 12, preferably 3 to 9 wt .-%, based on the total liquid detergent.

To improve certain properties, further auxiliaries, which are likewise usually active in small amounts, can be added to the detergents according to the invention; These are, for example, opacifiers and viscosity regulators, which are usually contained in the detergent at about 0.05 to 2% by weight. These are, for example, esters of alkanols or partial esters of polyols with longer-chain fatty acids, such as palmitic or stearic acid. A typical product is ethylene glycol stearate.

Formalin is usually used as a preservative in an amount of 0.05 to 1% by weight.

In order to avoid discoloration of the detergents during prolonged storage, which can be caused by contamination with heavy metal ions during manufacture, for example, complexing agents for heavy metal ions are added. Common complexing agents are the sodium, potassium or triethanolamine salts of aminopolycarboxylic acids, such as, for example, ethylenediaminetetraacetic acid or nitrilotriacetic acid. They are used in amounts of 0.1 to 1% by weight.

Examples of suitable fragrances are substances with a floral / fresh or fruity fragrance or those designated as cosmetic or creamy.

Simultaneously cleaning and softening detergents additionally contain 1 to 10% by weight of fabric softening compounds, for example nonionic fabric softening agents or preferably quaternary ammonium compounds derived from ammonia or imidazoline with 2 alkenyl or alkyl residues with 10 to 24 carbon atoms, the residues also being substituted or by heteroatoms can be interrupted.

• a) 7,5 bis 12,5 Gew.-% eines Alkylpolyglykolethers der Formel II, in der R¹ und R² zusammen 11 bis 13 Kohlenstoffatome aufweisen und wobei der durchschnittliche Ethylenoxidgehalt des Alkylpolyglykolethers 55 bis 65 Gew.-% beträgt,
• b) 7,5 bis 12,5 Gew.-% eines Alkylpolyglykolethers der Formel II, in der R^l 7 bis 10 Kohlenstoffatome aufweist, R² = H ist und wobei der durchschnittliche Ethylenoxidgehalt des Alkylpolyglykolethers 60 bis 70 Gew. % beträgt,
• c) 3,0 bis 5,0 Gew.-% Acylcyanamidsalz der Formel I, in der R einen substituierten Alkyl- bzw. Alkenylrest mit 11 bis 17 Kohlenstoffatomen und Me Natrium bedeuten,
• d) 1,0 bis 6,0 Gew.-% wasserlösliche synthetische, in Wasser stark basich reagierende Polyethylenimine und/oder Polyamine,
• e) 1,0 bis 6,0 Gew.-% wasserlösliche polymere Umsetzungsprodukte von Melamin und/oder Harnstoff und/oder Dicyandiamid und/oder Guanidin mit Formaldehyd,

An agent which is particularly preferred with regard to balanced product properties has the following composition:

• a) 7.5 to 12.5% by weight of an alkyl polyglycol ether of the formula II in which R ¹ and R ² together have 11 to 13 carbon atoms and the average ethylene oxide content of the alkyl polyglycol ether is 55 to 65% by weight,
• b) 7.5 to 12.5% by weight of an alkylpolyglycol ether of the formula II in which R ^{1 has} 7 to 10 carbon atoms, R ² = H and the average ethylene oxide content of the alkylpolyglycol ether is 60 to 70% by weight,
• c) 3.0 to 5.0% by weight of acylcyanamide salt of the formula I in which R is a substituted alkyl or alkenyl radical having 11 to 17 carbon atoms and Me sodium,
• d) 1.0 to 6.0% by weight of water-soluble synthetic water-strongly reacting polyethyleneimines and / or polyamines,
• e) 1.0 to 6.0% by weight of water-soluble polymeric reaction products of melamine and / or urea and / or dicyandiamide and / or guanidine with formaldehyde,

Remainder water and organic solvents as well as, where appropriate, other customary additives present in small amounts, such as, for example, colorants and fragrances, hydrotopic agents, complexing agents for traces of heavy metals, and preservatives, opacifiers and viscosity regulators.

In addition to the surfactants, powdery or granular detergents according to the invention generally contain so-called builders, also known as builders, whose task is to enhance the cleaning action of the surfactants and to eliminate the negative effects of water hardness. Suitable framework substances can be water-soluble or water-insoluble. Water-soluble compounds are, above all, alkali carbonate and alkali silicate, and also organic compounds from the compound classes of the hydroxycarboxylic acids, aminocarboxylic acids, polycarboxylic acids, carboxyalkyl ethers, the polymeric polycarboxylic acids and the substituted and unsubstituted alkane di- and polyphosphonic acids. Typical examples of these classes of compounds are citric acid, nitrilotriacetic acid, mellitic acid, carboxymethyloxy succinic acid, polyacrylic acid, polymethacrylic acid, poly-a-hydroxyacrylic acid, polymaleic acid and the corresponding copolymers and hydroxyethane diphosphonic acid. These compounds are mostly used in the form of their water-soluble salts.

entsprechen und die ein Calciumbindevermögen von 100 bis 200 mg CaO/g (bezogen auf die wasserfreie Substanz) aufweisen. Zu diesen feinteiligen, hydratisierten Natriumalumosilikaten gehören insbesondere die Zeolithe NaA und NaX. In großem Maßstab wird vor allem der Zeolith NaA eingesetzt. ^. In recent years, the finely divided, cation-exchanging, crystalline, water-containing sodium aluminosilicates described in German Offenlegungsschrift 24 12 837 for the first time as phosphate substitutes for detergents and cleaning agents have acquired particular practical importance

correspond and which have a calcium binding capacity of 100 to 200 mg CaO / g (based on the anhydrous substance). These finely divided, hydrated sodium aluminosilicates include, in particular, the NaA and NaX zeolites. The zeolite NaA is mainly used on a large scale.

In the detergent according to the invention, the builder component is generally contained in an amount of 3 to 70% by weight; individual builder substances, for example organic builder substances such. B. alkane polyphosphonates or aminocarboxylic acids can also be used in much smaller amounts, i. H. present in amounts of 0.1 to 3% by weight.

The detergent according to the invention can additionally contain graying inhibitors. As graying inhibitors, water-soluble colloids of mostly organic nature are suitable, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose, or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Carboxymethylated cellulose or starch in the form of their sodium salts, methyl celluloses and polymers and copolymers of (meth) acrylic acid and maleic acid are preferred. Furthermore, soluble starch preparations and other starch products than those mentioned above can be used, such as. B. degraded starch, aldehyde starches, etc. Discoloration inhibitors of the polyvinylpyrrolidone type can also be present in the agent according to the invention. In combination with the water-soluble polymers of detergents composed according to the invention, polyvinylpyrrolidone can even intensify the discoloration-inhibiting effect; Agents with an additional content of polyvinylpyrrolidone are therefore preferred.

To remove certain vegetable stains, bleaching agents can be present in the washing and cleaning agents according to the invention. Known peroxide-type bleaching agents such as sodium perborate, sodium carbonate perhydrate, potassium peroxomonosulfate and organic percarboxylic acids are particularly suitable. These bleaching agents can be present alone or can also be used in conjunction with known stabilizers, such as magnesium silicate, sodium ethylenediaminetetraacetate or sodium salts of polyphosphonic acids, which have the task of preventing the premature decomposition of the per compounds by heavy metal salts and the damage to the tissues.

In addition, bleach activators can be used together with the bleaching agents. Of the numerous proposals in the literature, anhydrides, carboxamides and carboxylic acid esters are particularly suitable as activators, which have an acylating effect on H ₂ O ₂ in the wash liquor and thus increase the bleaching power of the liquor. Examples of suitable activators are phthalic anhydride, tetraacetylethylenediamine, tetraacetylglycoluril and pentaacetylglucose.

The amount of activators in the agents is not more than 1, in particular 0.1 to equivalent, based on the amount of per-compound present. The per-compounds themselves are preferably 1 to 30% by weight, the stabilizers 0.01 to 5% by weight.

In addition to the constituents already mentioned, the washing and cleaning agents according to the invention may also contain other customary auxiliaries, in particular foam regulating agents, enzymes, Perfume oils, microbicidal agents and optical brighteners.

The following substances can be considered as foam-inhibiting additives: soaps with 20 to 24 carbon atoms, long-chain alkyl melamines, low-foam nonionic surfactants, paraffin hydrocarbons, microcrystalline waxes and silicone defoamers. Foam-damping soaps and silicone compounds are particularly important, here again the polysiloxanes activated by finely divided Si0 ₂ .

20% by weight of additive is always sufficient for effective foam regulation, preferably 0.05 to 10% by weight.

All enzymes which can be used to enhance the cleaning action, such as proteases, lipases and amylases, can be present as enzymes. Enzymes with an optimum activity in a pH range, as is achieved when the agents are used, and those enzymes which retain their activity even at elevated temperatures are preferred.

Microbicides can be components of such agents, which should also have a disinfectant effect when used. Typical bactericides and fungicides come into consideration as microbicides, provided they are compatible with the other components of the agents.

Optical brighteners are used in the agents according to the invention when the aim is to use these agents to increase the whiteness of the treated objects also optically. Numerous compounds have been described in the literature as being useful for this purpose. The derivatives of diaminostilbenedisulfonic acid or its salts, for example 4,4-bis- (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2, are particularly suitable for textile detergents 'disulfonic acid and brightener of the substituted 4,4'-distyrylbiphenyl type, for example 4,4'-bis (4-chloro-3-sulfostyryl) biphenyl.

The agents according to the invention can be produced using the methods customary for conventional washing and cleaning agents. In the simplest case, solid agents can be assembled simply by mixing the powdery or granular individual components. Products with better flow behavior, which also have less dust, can be obtained by granulation or spray drying. In all cases, the preparation of the agents is very simplified by the use of the acylcyanamide salts in anhydrous form, in which they can be easily produced technically. The good temperature stability of the acylcyanamide salts also has a positive effect on the spray drying process. The production of pasty liquid agents is also possible using conventional methods. In general, both pre-dissolved and solid components are used, which are optionally mixed and homogenized with further solvent, usually water. By applying heat and mechanical energy, the homogenization process can be accelerated, which is already greatly facilitated by the good solubility of the acylcyanamide salts. For the dissolution of other organic constituents, the addition of water-miscible organic solvents, such as ethanol or isopropanol, and the addition of hydrotropes for setting certain viscosities may be expedient.

Examples

• AO-EO : C₁₄/C₁₅-Oxoalkohol-Ethoxylat mit durchschnittlich 58 Gew.-% Ethylenoxid (« Dobanol 45-7^(R) », Shell),
• FA-EO: C₁₀/C₁₂-Fettalkohol-Ethoxylat mit durchschnittlich 60 Gew.-% Ethylenoxid (« Marlipal KF^(R) », Chem. Werke, Hüls),
• TA 5: Talgalkohol-Ethoxylat mit 5 Mol Ethylenoxid,
• TA 14: Talgalkohol-Ethoxylat mit 14 Mol Ethylenoxid,
• AMS-T :)Acylcyanamid-Natriumsalze nach Formel I auf Basis,
• AMS-HT :)von Talgfettsäure (T), hydrierter Talgfettsäure,
• AMS-ST:) (HT), Stearinsäure (ST),
• CMC : Vergrauungsinhibitor auf Basis Carboxymethylcellulose und Methylcellulose,
• SASIL^(R) : Natriumalumosilikat vom Typ Zeolith NaA, Ethylendiamintetraessigsäure-Natriumsalz,
• HEDP : Dinatriumsalz der 1-Hydroxyethan-1,1-diphosphonsäure,
• Seife : Gemisch von Salzen langkettiger Fettsäure mit 16 bis 22 C-Atomen,
• PB : Technisches Natriumperborat-Tetrahydrat,
• DMDSTAC: Dimethyldistearylammoniumchlorid,
• LM : Lösungsmittelgemisch aus Ethanol/1,2-Propylenglykol,
• MGS : Magnesiumsilikat,
• WG : Natriumsilikat der Zusammensetzung Na₂O · 3,35 Si0₂,
• RK : 25 %ige wäßrige Lösung eines stark basisch reagierenden Polyamins (« Retaminol K^(R)», Bayer),
• MEL: Melamin/Formaldehyd-Kondensationsprodukt, Molverhältnis 1 : 5, (« Melan 125^(R) », Henkel),
• PR: Melamin/Hamstoff/Formaldehyd-Kondensationsprodukt (« Pressal 50^(R) », Henkel).
• STA: Dicyandiamid/Formaldehyd-Kondensationsprodukt (« Stabifix WE(R) », Henkel),

The following examples describe compositions of some detergents according to the invention and not according to the invention, for reasons of space the list of some constituents not essential to the invention, such as perfume, water, enzymes, stabilizers, builders, preservatives and colorants, has been dispensed with. The names and abbreviations used in the tables have the following meanings:

• AO-EO: C ₁₄ / C ₁₅ oxo alcohol ethoxylate with an average of 58% by weight of ethylene oxide (“Dobanol 45-7 ^(R) ”, Shell),
• FA-EO: C ₁₀ / C ₁₂ fatty alcohol ethoxylate with an average of 60% by weight ethylene oxide (“Marlipal KF ^(R) ”, Chem. Werke, Hüls),
• TA 5: tallow alcohol ethoxylate with 5 moles of ethylene oxide,
• TA 14: tallow alcohol ethoxylate with 14 mol ethylene oxide,
• AMS-T:) based on acylcyanamide sodium salts according to formula I,
• AMS-HT :) of tallow fatty acid (T), hydrogenated tallow fatty acid,
• AMS-ST :) (HT), stearic acid (ST),
• CMC: graying inhibitor based on carboxymethyl cellulose and methyl cellulose,
• SASIL ^(R) : zeolite NaA sodium aluminosilicate, ethylenediaminetetraacetic acid sodium salt,
• HEDP: disodium salt of 1-hydroxyethane-1,1-diphosphonic acid,
• Soap: mixture of salts of long-chain fatty acids with 16 to 22 carbon atoms,
• PB: technical sodium perborate tetrahydrate,
• DMDSTAC: dimethyldistearylammonium chloride,
• LM: solvent mixture of ethanol / 1,2-propylene glycol,
• MGS: magnesium silicate,
• WG: sodium silicate with the composition Na ₂ O.3.35 Si0 ₂ ,
• RK: 25% aqueous solution of a strongly basic polyamine ("Retaminol K ^(R) ", Bayer),
• MEL: melamine / formaldehyde condensation product, molar ratio 1: 5, (“Melan 125 ^(R) ”, Henkel),
• PR: Melamine / urea / formaldehyde condensation product ("Pressal 50 ^(R) ", Henkel).
• STA: dicyandiamide / formaldehyde condensation product ("Stabifix WE (R)", Henkel),

ANZ: condensation products of adipic acid and polyethyleneimine, molecular weight 900 (= ANZ 145) or molecular weight 600 (= ANZ 148), molar ratio 1: 1.

Examples 1 to 5

These examples show how the discoloration-inhibiting effect of a liquid detergent based on nonionic surfactants increases as a result of the combination according to the invention of nonionic surfactants, acylcyanamide salts and certain water-soluble polymers. Example 1 relates to a known liquid detergent without acylcyanamide salts and without water-soluble polymers. With this detergent, white test textiles made of cotton terry fabric (B) and cotton, finished (Bv), were washed in an automatic drum washing machine (type Miele W 433) at 60 ° C in water of 16 ° d. The test textiles were washed in 20 liters of water in the input process together with 3.5 kg of clean laundry and with a rag dyed with Sirius light red F 4 BL (intensive dye which tends to strongly transfer dye). The reflectance in% was then measured as a measure of the discoloration of the washed and dried test textiles using a photometer, type RFC 3/18 with filter 46 (460 nm). The result is the measure of the dye transfer of a detergent of the prior art. Examples 2 and 3 relate to detergents containing acylcyanamide salts. Examples 4 and 5 relate to detergents according to the invention with a combination of nonionic surfactants, acylcyanamide salts and water-soluble salts. The detergents had the following composition (essential components):

The reflectance of the washed test textiles B and Bv is listed in Table II.

The detergents according to the invention of Examples 4 and 5 have a significantly better discoloration-inhibiting effect than the detergents without water-soluble polymers (Examples 1 to 3). If more than 5% by weight of strong electrolytes were added to the detergents, the discoloration was significantly increased.

Examples 6 to 10

The liquid detergent of Example 6 is a detergent of the prior art, which in a further test series with the test textiles cotton (B), polyamide (PA) and polyurethane / polyamide (PUA) compared to the detergents according to the invention of Examples 7 to 10 as was used in Examples 1 to 5. The detergents had the following composition (essential components).

The reflectance of the test textiles B, PA and PUA is listed in Table IV.

The detergents 7 to 10 according to the invention lead to significantly less discolored test textiles than the detergent of the prior art. The addition of anionic surfactant caused a significant increase in discoloration.

Examples 11 to 17

Example 11 relates to a liquid softening mild detergent of the prior art with dimethyldistearylammonium chloride as textile-softening active ingredient. As in the previous examples, cotton and polyurethane / polyamide test textiles are washed with this detergent in comparison to detergents composed according to the invention. The essential composition of the detergents and the reflectance values for the discoloration are listed in Tables V and VI.

The distinctive inhibition of discoloration of the detergents composed according to the invention can also be seen in the softening mild detergent of experiments 11 to 17.

Examples 18-22

The powder detergents of Examples 18 to 20 are detergents without water-soluble polymers, of which the detergents of Examples 19 and 20 contain nonionic surfactants and acylcyanamide salts as the surfactant, while the detergent of Example 18 contains only nonionic surfactants (see Table VII). The powder detergents of Examples 21 and 22 are detergents according to the invention.

As described above, washing tests were carried out with the test detergents using the test textiles cotton terry toweling fabric (B) and polyamide fabric (PA). The remission results are shown in Table VIII.

The addition of acylcanamide salts (Examples 19 and 20) to the basic formulation (Example 18) partially leads to an increase in dye transfer. The reinforcement is not only compensated for by the detergents composed according to the invention, but rather overcompensated, which is shown in significantly higher reflectance values (Examples 21 and 22).

Examples 23 to 25

The following Examples 23 to 25, like Examples 18 to 22, describe the discoloration-inhibiting action of powdered detergents (24 and 25) composed according to the invention in comparison with a detergent of known composition (see Tables IX and X)

With these powder detergents, too, the discoloration-inhibiting effect compared to the detergent of the prior art is clearly recognizable.

Claims (12)

1. A detergent for coloured fabrics containing synthetic nonionic surfactants, water-soluble organic polymers, acyl cyanamide salts and other standard detergent ingredients, characterized in that it contains

1 to 30 % by weight acyl cyanamide salts,

1 to 30 % by weight nonionic surfactants,

1 to 15 % by weight water-soluble, synthetic organic polymers in the form of compounds of monomers containing more than one amino group or reaction products thereof with aldehydes or dicarboxylic acid,
with the further proviso that the detergent contains no more than 5 % by weight strong electrolyte and sulfate or sulfonate surfactants.

2. A detergent as claimed in claim 1, characterized in that it contains polyethyleneimines or polyamines as the water-soluble polymers.

3. A detergent as claimed in claim 1, characterized in that it contains reaction products of polyethyleneimine or polypropyleneimine with polycarboxylic acids as the water-soluble polymers.

4. A detergent as claimed in claim 1, characterized in that it contains reaction products of melamine and/or urea and/or dicyanodiamide and/or guanidine with formaldehyde as the water-soluble polymers.

5. A detergent as claimed in any of claims 1 to 4, characterized in that it contains the water-soluble polymers in combination with one another or with polyvinyl pyrrolidone.

6. A detergent as claimed in any of claims 1 to 5, characterized in that it contains the water-soluble polymers in quantites of from 2 to 6% by weight.

7. A liquid detergent as claimed in any of claims 1 to 6, characterized in that it contains as the surfactant component

a) 5 to 18% by weight of an alkyl polyglycol ether corresponding to the following formula

in which R¹ is a straight-chain alkyl group and R², to a level of 20 to 75 % by weight, based on the alcohol of the alkyl polyglycol ether, is a C_1-4 alkyl group and, for the rest, hydrogen, the total number of carbon atoms in R¹ and R² amounting to between 11 and 15 and n has a value of 5 to 9, n being selected in such a way that the ethylene oxide content of the alkyl polyglycol ether amounts to between about 50 and 65 % by weight,

b) 5 to 18 % by weight of an alkyl polyglycol ether corresponding to formula II, in which R¹ is a straight-chain alkyl group and R² is either hydrogen or, to a level of 20 to 75 % by weight, based on the alcohol of the alkyl polyglycol ether, is a C_1-4 alkyl group and, for the rest, hydrogen, the total number of carbon atoms in R¹ and R² amounting to between 6 and 10 and n having a value of 3 to 8, n being selected in such a way that the ethylene oxide content of the alkyl polyglycol ether amounts to between 55 and 70 % by weight,

c) 2.0 to 7.0 % by weight acyl cyanamide salts corresponding to the formula

in which R is an alkyl or alkenyl radical containing 9 to 23 and preferably 11 to 17 carbon atoms and Me is sodium or potassium, preferably sodium,
the quantitative ratio of a) to b) being from 2 : 1 to 1 : 2.

8. A liquid detergent as claimed in any of claims 1 to 7, characterized in that it additionally contains from 1 to 10 % by weight of fabric-softening quaternary ammonium compounds containing two C_10-24 alkyl or alkenyl radicals derived from ammonia or imidazoline.

9. A liquid detergent as claimed in any of claims 1 to 8, characterized in that it contains

a) 7.5 to 12.5 % by weight of an alkyl polyglycol ether corresponding to formula II, in which R¹ and R² together contain 11 to 13 carbon atoms and the average ethylene oxide content of the alkyl polyglycol ether is from 55 to 65 % by weight,

b) 7.5 to 12.5 % by weight of an alkyl polyglycol ether corresponding to formula II, in which R¹ contains 7 to 10 carbon atoms, R² = H and the average ethylene oxide content of the alkyl polyglycol ether is from 60 to 70 % by weight,

c) 3.0 to 5.0 % by weight acyl cyanamide salt corresponding to formula I, in which R is an unsubstituted alkyl or alkenyl radical containing 11 to 17 carbon atoms and Me is sodium,

d) 1.0 to 6.0 % by weight water-soluble, synthetic polyethyleneimines and/or polyamines showing a strongly basic reaction in water,

e) 1.0 to 6.0 % by weight water-soluble polymeric reaction products of melamine and/or urea and/or dicyanodiamide and/or guanidine with formaldehyde, balance water and organic solvents and, optionally, other standard additives present in small quantities, such as for example dyes and fragrances, hydrotropic agents, complexing agents for heavy metal traces and also preservatives, opacifiers and viscosity regulators.

10. A powder-form or granular detergent as claimed in any of claims 1 to 6, characterized in that it contains 3 to 70 % by weight builders, preferably cation-exchanging crystalline sodium alumosilicate, more especially zeolite NaA.

11. A detergent as claimed in claim 10, characterized in that it contains from 0.1 to 3 % by weight organic builders.

12. A detergent as claimed in claim 10 or 11, characterized in that it contains as auxiliaries redeposition inhibitors, bleaching compounds, bleach activators, foam regulators, enzymes, perfume oil, microbicides and optical brighteners, either individually or in combination with at least one other auxiliary.