EP0131137B1 - Washing and cleaning agent with a content of acylcyanamide salts - Google Patents

Abstract

A detergent composition for fabrics containing at least one synthetic surfactant from the group comprising anionic and nonionic surfactants and at least one builder from the group comprising condensed phosphates and phosphate substitutes, wherein at least one acylcyanamide salt anionic surfactant is present.

Description

The development of modern textile detergents, which began in the 1930s, had led to an almost complete departure from the previous conventional detergents based on soap, soda and silicate. They were replaced by products which were characterized by a) synthetic anionic and nonionic surfactants, b) so-called builders, especially pentasodium triphosphate, and c) graying inhibitors, generally carboxymethyl cellulose, which improved the dirt-carrying capacity. Soap was added only to a small extent as a foam regulator. With these modern detergents, a significant improvement in the secondary washing behavior compared to the old detergents was achieved without a decrease in the primary washing action, which was particularly noticeable in a reduction in the incrustations on the fabrics.

Despite the high level of textile treatment achieved with these agents, efforts have always been made to further improve the quality of the agents and to adapt them to changing external conditions. Similar efforts can be observed in the entire field of detergents and cleaning agents. Examples of such improvements are the transition from poorly biodegradable to rapidly degradable surfactants and the replacement of soluble builder phosphates with insoluble sodium aluminum silicates of the zeolite A type.

The present invention has also made it a point to further develop the modern washing and cleaning agents and to adapt them better to today's and foreseeable future requirements. The primary goals are to enable the use of renewable raw materials and those from local sources to a greater extent than before by changing the surfactant base, to facilitate the production of the agents and at the same time to improve the application properties, in particular the cleaning ability and the dirt-carrying capacity of the fleet , as well as when used on fabrics to reduce incrustation and improve the grip of the washed fabrics.

It has now been found that these goals can surprisingly be achieved if, in modern washing and cleaning agents, an acylcyanamide salt with the general formula in which Me is sodium or potassium and R is an alkyl or alkenyl radical having 9-23 carbon atoms, which can be substituted by hydroxyl or alkoxyl groups, is used as the anionic surfactant. This is all the more surprising since, from the chemical structure and the chemical-physical properties, this surfactant is much more similar to soaps than the synthetic anionic surfactants of the sulfonate or sulfate type which have been used almost exclusively for over 20 years. The suitability of the acylcyanamides for modern washing and cleaning agents was therefore not to be expected.

The present invention relates to a washing and cleaning agent for solid materials, in particular for textiles, which contains at least one synthetic anionic surfactant and at least one builder, also called builder, from the group of condensed phosphates and phosphate substitutes and, if appropriate, a nonionic surfactant and in which the Part or all of the anionic surfactants consists of an acylcyanamide salt of the formula defined above.

Acylcyanamide salts are not new as compounds; the first homologues were described by O. Mertens in 1878 [J. practical chemistry (2) 17, 4]. The soap-like properties of the higher homologues, which make them suitable for wetting and dispersing agents, were also mentioned in the English patent specification 428 091 in 1935.

On the other hand, no publications are known from which the unusually good effects of these compounds in modern detergents could be derived. EP-A 24676, which describes a process for textile finishing, also includes the acylcyanamide salts of formula 1 in a very broad formula, but makes no reference to the surfactant properties of the compounds or to detergents. In the process mentioned there, the acylcyanamide grouping serves as a reactive group for fixing active substances to fibrous materials.

Also in EP-A 8475, which describes a bleaching process and bleaching agent with cyanamines as activators, the acylcyanamide salts of the present invention are also included in a broad formula. The cyanamines are used there with the aim of activating peroxide bleaching agents in order to increase the oxidizing power of the agents; no indication of surfactant properties is given.

The acylcyanamide salts according to the invention can be obtained from carboxylic acid derivatives and cyanamide with subsequent neutralization by means of suitable bases [see German Patent 708428 or A.E. Kretov and A.P. Momsenko, J. org. Chem. (USSR) 1, 1765 (1965)].

The preparation is simpler by reacting salts of cyanamide with carboxylic acid esters, as described in EP-A 84836. 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.

Acylcyanamidsalze den Vorzug, dass ihre Herstellung aus nachwachsenden Rohstoffen, hier Fettsäurederivaten, und dem aus Kalkstickstoff leicht zugänglichen Cyanamid möglich ist. Damit verringert sich beim Einsatz dieser Tenside die Abhängigkeit der Waschmittelhersteller von Rohstoffen auf Erdölbasis, die z.B. bei dem heute noch wichtigsten Aniontensid Alkylbenzolsulfonat spürbar ist. Darüber hinaus sind Acylcyanamidsalze gut biologisch abbaubar und toxikologisch unbedenklich.In addition to being easy to manufacture,

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. When using these surfactants, the detergent manufacturers' dependence on petroleum-based raw materials is reduced, which is noticeable, for example, with the most important anionic surfactant, alkylbenzenesulfonate. In addition, acyl cyanamide salts are readily biodegradable and toxicologically safe.

The sodium salts of acylcyanamides have particularly favorable properties with regard to the aims of this invention, in particular those in which the radical R in the formula is an essentially unsubstituted alkyl or alkenyl radical having 11-17 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.

The agents according to the invention can be used in numerous fields of technology and the household for a wide variety of cleaning tasks. Examples of such fields of application are the cleaning of devices, apparatus, pipelines and vessels made of wood, plastic, metal, ceramic, glass etc. in industry or in commercial companies, the cleaning of furniture, walls, floors, objects made of ceramic, glass , Metal, wood, plastic, the cleaning of polished or painted surfaces in the household etc. A particularly important area of application is the washing of all types of textiles in industry, in commercial laundries and in the household.

Suitable synthetic anionic surfactants which can be present in the agents according to the invention in addition to the acylcyanamide salts are, in particular, those of the sulfonate and sulfate type.

The surfactants of the sulfonate type are primarily the alkylbenzenesulfonates with C _9-15 -alkyl groups and the esters of a-sulfofatty acids, for example the a-sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Other useful surfactants of the sulfonate type are the alkanesulfonates which are obtainable from C ₁₂ -C ₁₈ -alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the olefinsulfonates, which are mixtures of alkene and hydroxyalkanesulfonates and disulfonates as obtained for example from monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.

Particularly suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols of natural and synthetic origin, ie of fatty alcohols such as e.g. Coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol, or the C _lo -C _2O oxo alcohols, and those of secondary alcohols of this chain length. In addition, the sulfuric acid monoesters of the aliphatic primary alcohols ethoxylated with 1-6 mol ethylene oxide or ethoxylated secondary alcohols or alkylphenols are suitable. Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.

All of these anionic surfactants are preferably used in the form of the salts, in particular in the form of the sodium salts, but also as potassium or ammonium salts or as soluble salts of organic bases, such as mono-, di- or triethanolamine.

Agents according to the invention which have 1-30% by weight, preferably 3-15% by weight, of acyl cyanamide salt and 1-30% by weight, preferably 3-15% by weight of synthetic anionic surfactant from the group of alkylbenzenesulfonates and ester sulfonates have particularly favorable performance properties , Alcohol sulfates and mixtures thereof in addition to other common constituents of washing and cleaning agents.

Suitable nonionic surfactants for the agents according to the invention are addition products of 1-40, preferably 2-20, moles of ethylene oxide with 1 mole of an aliphatic compound having essentially 10-20 carbon atoms from the group of alcohols, alkylphenols, carboxylic acids and carboxamides. The addition products of 8-20 moles of ethylene oxide with primary alcohols, such as coconut oil or tallow fatty alcohols, with oleyl alcohol, with oxo alcohols of the corresponding chain lengths, or with corresponding secondary alcohols, and with mono- or dialkylphenols with 6-14 C- Atoms in the alkyl radicals. In addition to these water-soluble nonionics, non-or not fully water-soluble polyglycol ethers with 2-7 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble nonionic or anionic surfactants. Because of their good biodegradability, the ethoxylation products of primary aliphatic alkanols and alkenols are of particular practical interest.

Typical representatives of the nonionic surfactants which can be used according to the invention and have an average degree of ethoxylation of 2-7 are, for example, the compounds coconut fatty alcohol 3-EO (EO = ethylene oxide), tallow fatty alcohol 5-EO, oleyl / cetyl alcohol 5-EO (iodine number 30-50 ), Tallow fatty alcohol 7-EO, synthetic C ₁₂ -C ₁₆ fatty alcohol 6-EO, C ₁₁ -C ₁₅ oxalcohol 3-EO, C ₁₄ / C ₁₅ oxo alcohol 7-EO, iC ₁₅ - C ₁₇ alkanediol-5-EO (i = internal); sec-C ₁₁ -C ₁₅ alcohol-4-EO.

Exemplary representatives of the nonionic surfactants with an average degree of ethoxylation of 8-20, in particular 9-15, are the compounds coconut fatty alcohol-12-EO, synthetic C ₁₂ / C ₁₄ fatty alcohol-9-EO, oleyl / cetyl alcohol-10 -EO, tallow fat. -Alcohol-14-EO, C ₁₁ -C ₁₅ -oxoalcohol-13-EO, C ₁₅ -C _'B -oxoalcohol-15-EO, iC ₁₅ -C ₁₇ -alkanediol-9-EO, C ₁₄ / C ₁₅ -oxalcohol-11-EO, sec.-C ₁₁ -C _1s -alcohol-9-EO.

Furthermore, the non-ionic surfactants which can be used are the water-soluble adducts of ethylene oxide with 20-250 ethylene glycol ether groups and 10-100 propylene glycol ether groups with polypropylene glycol, alkylenediamine-poly-propylene glycol and with alkylpolypropylene glycols with 1-10 carbon atoms in the alkyl chain, in which the polypropylene glycol chain acts as a hydrophobic radical .

Nonionic surfactants of the amine oxide or sulfoxide type can also be used, for example the compounds N-cocoalkyl-N, N-dimethylamine oxide, N-hexadecyl-N, N-bis- (2,3-dihydroxypropylamine oxide, N-tallow alkyl-N, N-dihydroxyethylamine oxide.

When using acyl cyanamide salts in combination with nonionic surfactants, an unusually good cleaning effect is achieved with agents which contain 1-30% by weight, preferably 3-15% by weight, acyl cyanamide salt with 1-30% by weight, preferably 2-15% by weight. %, nonionic surfactant from the group of alcohol ethoxylates and alkylphenol ethoxylates in addition to other common constituents of detergents and cleaning agents.

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 der R einen n-Alkyl- oder n-Alkenylrest mit 12-18 Kohlenstoffatomen darstellt und n einen Mittelwert mit der Grösse 4-15 bedeutet, im Gewichtsverhältnis 1:4 bis 4:1, vorzugsweise 2:3 bis 4:1, und sie ist in den Mitteln zu 2-50 Gew.%, insbesondere 5-30 Gew.% enthalten.This combination of surfactants contains acyl cyanamide salts and nonionic surfactants of the formula

in which R represents an n-alkyl or n-alkenyl radical having 12-18 carbon atoms and n is an average value with a size of 4-15, in a weight ratio of 1: 4 to 4: 1, preferably 2: 3 to 4: 1, and it is contained in the agents at 2-50% by weight, in particular 5-30% by weight.

This special cleaning ability against grease and pigment soiling is of particular importance, since these types of soiling represent the majority of the soiling on washable textiles and they cannot be sufficiently removed in all cases even with the detergents available today.

Agents according to the invention in which both synthetic anionic and nonionic surfactant are present in addition to the acylcyanamide salt have a very broad activity, i.e. they remove numerous types of soiling in a satisfactory manner. In addition to other conventional detergent components, such compositions contain 1-30% by weight, preferably 3-15% by weight, of acylcyanamide of the formula I, 1-30% by weight, preferably 3-15% by weight, of synthetic anionic surfactant, in particular from the group of alkylbenzenesulfonates, Ester sulfonates, alcohol sulfates and mixtures thereof and 1-30% by weight, preferably 2-15% by weight 96 nonionic surfactant, in particular from the group of alcohol ethoxylates, alkylphenol ethoxylates and mixtures thereof.

As modern washing and cleaning agents, the agents according to the invention contain, in addition to the surfactants, so-called builders, also called builders, whose task is to increase the cleaning action of the surfactants and to eliminate the negative effects of water hardness.

So far, condensed phosphates, especially pentasodium triphosphate, have had an excellent position among the framework substances. These phosphates have excellent performance properties and can be present in the agents as the only framework substances. In these agents, however, they can also be replaced in whole or in part by phosphate substitutes, especially if the pollution of the waste water with the phosphates, which leads to the eutrophication of standing waters, is thereby reduced or avoided.

Inorganic and organic compounds which have a builder effect at least partially equivalent to sodium tripolyphosphate are suitable as phosphate substitutes. The suitable water-soluble inorganic compounds are essentially the alkali carbonates and alkali silicates. Useful water-soluble organic compounds can be found in the compound classes of the hydroxycarboxylic acids, aminocarboxylic acids, polycarboxylic acids, carboxyalkyl ethers, the polymeric polycarboxylic acids and the substituted and unsubstituted alkanedi- and polyphosphonic acids. Typical examples of these classes of compounds are citric acid, nitrilotriacetic acid, mellitic acid, carboxymethyloxysuccinic 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 recent years, the fine-particle, cation-exchanging, crystalline sodium aluminosilicates described in German Offenlegungsschrift 2412837 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.

Zeolite NaA is mainly used on a large scale as a substitute for sodium tripolyphosphate in low-phosphate and phosphate-free detergents.

The framework substance in the agents according to the invention is preferably selected from the group sodium triphosphate, sodium aluminum silicate, sodium nitrilotriacetate, sodium alkane polyphosphonate and mixtures thereof.

The builder component is generally present in the detergent according to the invention in an amount of 3 to 70% by weight, preferably in an amount of 20 to 50% by weight; individual builder substances, for example the alkane polyphosphonates, can also be used in much smaller amounts, i.e. present in amounts of 0.1 to 3% by weight.

The detergents and cleaning agents according to the invention, in addition to the already mentioned high cleaning power, show a surprisingly high dirt-carrying capacity as a further special property. With these agents, graying values can be achieved, for example, in textile washing, which are otherwise only observed in the presence of special graying inhibitors, which are generally high molecular weight polyionic compounds. This means that the use of graying inhibitors can be dispensed with entirely, thus considerably simplifying the detergent formulation. However, the agents can also contain additional graying inhibitors and then achieve a higher dirt-carrying capacity in the liquor than conventional agents.

As graying inhibitors, water-soluble colloids, usually of an 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 its sodium salts, methyl celluloses and polymers and copolymers of (meth) acrylic acid and maleic acid are preferred. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Also polyvinylpyrrolidone-type coloring inhibitors are useful.

Another surprising property of the detergents according to the invention is that they give the washed cotton textiles a significantly softer feel than conventional modern detergents. This can go so far that the incorporation of special softening agents, so-called finish substances, into the detergents, as is occasionally done today, and also a subsequent finish in the rinsing bath can be dispensed with. This effect is particularly evident in detergents in which the proportion of acylcyanamides is above 6% by weight, in particular above 12% by weight.

Bleaching agents can be contained in the washing and cleaning agents according to the invention in order to remove certain plant stains. Known peroxide-type bleaching agents such as sodium perborate, sodium carbonate perhydrate, potassium peroxomonosulfate and organic percarboxylic acids are particularly suitable. These bleaches 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 0.1-1 equivalent, based on the amount of per-compound present. The per compounds themselves are present in amounts of up to 40% by weight, preferably 1-30% by weight, the stabilizers containing 0.01-5% by weight.

In addition to the constituents already mentioned, the washing and cleaning agents according to the invention can also contain other customary additives, in particular foam-regulating agents, enzymes, perfume oils, electrolytes, microbicidal agents and optical brighteners.

The following substances are considered as foam-inhibiting additives: soaps with 20-24 carbon atoms, long-chain alkyl melamines, low-foam nonionic surfactants, paraffinic 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 .

For effective foam regulation, 20% by weight of additive is always sufficient; 0.05-10% by weight are preferably used.

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 action even at elevated temperatures are preferred.

Electrolytes can be contained in the agents for increasing the ionic strength in the application solutions, for pH regulation, as carriers or envelopes, for the desensitization of per compounds or even only as fillers. These are preferably salts of sodium and potassium, for example sodium borate, sodium sulfate and potassium hydrogen phosphate, but can weak acids such as boric acid or bases such as ammonia can also be used.

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 if they are compatible with the other components of the agents.

Optical brighteners are used in the agents according to the invention when it is a question of using these agents to increase the whiteness of the treated objects optically as well. Numerous compounds have been described in the literature as being useful for this purpose. The derivatives of diaminostilbenedisulfonic acid or its salts are particularly suitable for textile detergents, for example 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2, 2'-disulfonic acid, and brighteners 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. In addition, the good temperature stability of the acycyanamide salts has a positive effect in the spray drying process. The production of pasty and 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. The addition of water-miscible organic solvents, such as ethanol or isopropanol, and the addition of hydrotropes, such as NaCl or triethanolamine, can be useful for dissolving other organic constituents.

Examples

• AMS-K, AMS-T, AMS-St: Acylcyanamid-Natriumsalze nach Formel auf Basis von Kokosfettsäure, Talgfettsäure bzw. raffinierter, hydrierter Talgfettsäure. Das Maximum in der Kettenlängenverteilung des Alkyl- bzw. Alkenylrestes R in Formel I liegt bei C₁₁, C₁₇ bzw. C_15/17.
• ABS: Im wesentlichen lineares Alkylbenzolsulfonat mit im wesentlichen 11-13 C-Atomen in der Alkylkette
• TSE: Aus hydriertem Talgfettsäuremethylester mit S0₃ hergestelltes Sulfonat (Estersulfonat)
• FAS: Monoalkylsulfat aus hydriertem Fettalkohol mit einem Maximum der Kettenlängenverteilung bei C_16/18 (Fettalkoholsulfat)
• SAS: Salz einer aus Paraffinen mit 12-16 C-Atomen mittels Sulfoxiodation gewonnenen Sulfonsäure (Alkansulfonat)
• FAES: Monoalkylsulfat aus dem Anlagerungsprodukt von 3 Mol Ethylenoxid an hydriertem Talgfettalkohol (Fettalkoholethersulfat)
• SOS: Olefinsulfonat, das aus einem Gemisch von im wesentlichen geradkettigen Olefinen mit 15-18 C-Atomen durch Sulfonieren mit S0₃ und Hydrolyse hergestellt wurde
• TA 5: Additionsprodukt aus hydriertem Talgalkohol und 5 Mol Ethylenoxid
• TA 10: Additionsprodukt aus einem technischen Oleylalkohol der Jodzahl 45 und 10 Mol Ethylenoxid
• TA 14: Additionsprodukt aus hydriertem Talgalkohol und 14 Mol Ethylenoxid
• NP 9,5: Additionsprodukt aus Nonylphenol und 9,5 Mol Ethylenoxid
• SASIL^O: NatriumaluminiumsilikatvomTypZeolith A mit der Zusammensetzung 1,07 Na₂O·1,00 Al₂O₃·1,90 SiO₂·H₂O, mit einem Calciumbindevermögen von 160 mg CaO pro Gramm wasserfreie Substanz. Die Zahlenwerte in den Beispielen beziehen sich ebenfalls auf die wasserfreie Substanz.
• NTA: Trinatriumsalz der Nitrilotriessigsäure
• HEDP: Dinatriumsalz der 1-Hydroxyethan-1,1- diphosphonsäure
• Silikat: Natriumsilikat der Zusammensetzung NaZOx3,3 Si0₂
• Perborat: Technisches Natriumperborat-Tetrahydrat mit 10,1 Gew.% Aktivsauerstoff
• Seife: Gemisch von Salzen langkettiger Fettsäuren mit 16-22 C-Atomen
• SiE: Schauminhibitor auf Basis von aerosilgebundenem Polysiloxan.
• CMC: Vergrauungsinhibitor auf Basis Carboxymethylcellulose und Methylcellulose
  
  

The following examples describe compositions of several agents according to the invention, for reasons of space the list of some constituents not essential to the invention, such as perfume, enzymes, stabilizers, Na ₂ SO ₄ and water, has been dispensed with. Unless otherwise stated, ionic components, such as anionic surfactants and salts, are in the form of the sodium salts. The names and abbreviations used in the table have the following meaning:

• AMS-K, AMS-T, AMS-St: Acylcyanamide sodium salts according to the formula based on coconut fatty acid, tallow fatty acid or refined, hydrogenated tallow fatty acid. The maximum in the chain length distribution of the alkyl or alkenyl radical R in formula I is C ₁₁ , C ₁₇ or C _15/17 .
• ABS: Essentially linear alkylbenzenesulfonate with essentially 11-13 carbon atoms in the alkyl chain
• TSE: Sulfonate (ester sulfonate) made from hydrogenated tallow fatty acid methyl ester with S0 ₃
• FAS: Monoalkyl sulfate from hydrogenated fatty alcohol with a maximum chain length distribution at C _16/18 (fatty alcohol sulfate)
• SAS: Salt of a sulfonic acid (alkanesulfonate) obtained from paraffins with 12-16 C atoms by sulfoxiodation
• FAES: Monoalkyl sulfate from the adduct of 3 moles of ethylene oxide with hydrogenated tallow fatty alcohol (fatty alcohol ether sulfate)
• SOS: olefin sulfonate, which was prepared from a mixture of essentially straight-chain olefins with 15-18 C atoms by sulfonation with SO ₃ and hydrolysis
• TA 5: addition product of hydrogenated tallow alcohol and 5 moles of ethylene oxide
• TA 10: addition product from a technical oleyl alcohol with an iodine number of 45 and 10 moles of ethylene oxide
• TA 14: Addition product from hydrogenated tallow alcohol and 14 moles of ethylene oxide
• NP 9.5: addition product of nonylphenol and 9.5 mol ethylene oxide
• SASIL ^O : Zeolite A sodium aluminum silicate with the composition 1.07 Na ₂ O · 1.00 Al ₂ O ₃ · 1.90 SiO ₂ · H ₂ O, with a calcium binding capacity of 160 mg CaO per gram of anhydrous substance. The numerical values in the examples also relate to the anhydrous substance.
• NTA: trisodium salt of nitrilotriacetic acid
• HEDP: disodium salt of 1-hydroxyethane-1,1-diphosphonic acid
• Silicate: sodium silicate with the composition NaZOx3.3 Si0 ₂
• Perborate: Technical sodium perborate tetrahydrate with 10.1% by weight active oxygen
• Soap: Mixture of salts of long-chain fatty acids with 16-22 carbon atoms
• SiE: foam inhibitor based on aerosil-bound polysiloxane.
• CMC: graying inhibitor based on carboxymethyl cellulose and methyl cellulose
  
  

Examples 1-7

These are heavy duty textile detergents that contain bleach and are suitable for a wide temperature range up to the boil.

In addition to the ingredients listed in Table 1, the agent according to Example 3 contains 6.2% by weight of tetraacetylethylene diamine, a bleach activator, and 2.0% by weight of Sokalan® CP5, a partially neutralized modified poly acrylic acid, remarkable. The agent according to Example 6 contains 1.1% by weight of the hexasodium salt of ethylenediaminetetrakismethylenephosphonic acid as a further builder component; on average according to Example 7, 2.2% Dobanol® 45-7, an adduct of C _14/15 oxo alcohol and 7 mol ethylene oxide and 2.5% by weight aminotrismethylene phosphonic acid pentasodium salt are contained as nonionic surfactant.

Examples 8 and 9

Both agents are mild detergents.

Examples 10 and 11

It is a bleach-free heavy-duty detergent

Examples 12-14

These heavy-duty detergents have no bleach and are suitable for the medium and low temperature range. The agent according to Example 12 contains 0.8% sodium citrate as a further builder component.

Example 15

Soaking and prewash

Example 16

Paste-like laundry pretreatment agent

Example 17

Liquid detergent, especially for textiles. As a further nonionic surfactant, it contains 17.0% by weight of an addition product of 7 mol of ethylene oxide to a mixture of secondary alcohols with 12-14 C atoms and 3.0% by weight of ethylenediaminetetraacetate as calcium complexing agent.

Example 18

Cleaning paste for household use on hard surfaces. The soap used here is the potassium salts of tallow fatty acids.

Example 19

Germ-inhibiting cleaner in concentrated form, which contains 2.6% by weight sodium citrate and 14.5% by weight a mixture of chlorinated and non-chlorinated phenols as disinfectant in addition to the surfactants.

Example 20

Concentrated technical cleaner with anti-corrosion effect.

Example 21

Aqueous-alcoholic, almost salt-free agent for cleaning hard surfaces, especially glass and ceramics. The solution contains 8.0% by weight of ethanol.

Example 22

Bleaching and germ-inhibiting abrasive containing 1.8% by weight magnesium monoperphthalate and 88.5% quartz powder.

Claims (9)

1. Detergents for solid materials, particularly fabrics, containing at least one synthetic anionic surfactant and at least one builder from the group comprising condensed phosphates and phosphate substitutes, and optionally a nonionic surfactant, characterized in that the anionic surfactant component consists completely or partly of an acylcyanamide salt corresponding to the following general formula

in which Me represents sodium or potassium and R represents an alkyl or alkenyl radical containing from 9 to 23 carbon atoms which may be substituted by hydroxyl or alkoxyl groups.

2. A detergent as claimed in Claim 1, characterized in that the acylcyanamide salt of formula I is the sodium salt in which the alkyl or alkenyl radical contains from 11 to 17 carbon atoms and is unsubstituted.

3. A detergent as claimed in Claim 1 or 2, characterized in that the acylcyanamide salt is present in combination with at least one synthetic anionic surfactant from the group comprising alkylbenzene sulfonates, ester sulfonates, alkane sulfonates, olefin sulfonates, alcohol sulfates and alkyl polyglycol ether sulfates.

4. A detergent as claimed in Claim 1 or 2, characterized in that the acylcyanamide salt is present in combination with at least one synthetic nonionic surfactant from the group comprising alcohol ethoxylates and alkylphenol ethoxylates.

5. A detergent as claimed in Claim 3, characterized in that it contains from 1 to 30% by weight and preferably from 3 to 15% by weight of the acylcyanamide salt corresponding to formula I, from 1 to 30% by weight and preferably from 3 to 15% by weight of a synthetic anionic surfactant from the group comprising alkylbenzene sulfonates, ester sulfonates, alcohol sulfates and mixtures thereof and from 40 to 98% by weight of other standard detergent ingredients.

6. A detergent as claimed in Claim 4, characterized in that it contains from 1 to 30% by weight and preferably from 3 to 15% by weight of the acylcyanamide salt corresponding to formula I, from 1 to 30% by weight and preferably from 2 to 15% by weight of a synthetic nonionic surfactant from the group comprising alcohol ethoxylates, alkyl phenol ethoxylates and mixtures thereof and from 40 to 98% by weight of other standard detergent ingredients.

7. A detergent as claimed in Claims 1 to 6, characterized in that it contains from 2 to 50% by weight and preferably from 5 to 30% by weight of a combination of the acylcyanamide salt of formula I and a nonionic surfactant of the general formula R-O{CH₂-CH₂-O}_mH, in which R is an n-alkyl or n-alkenyl radical containing form 12 to 18 carbon atoms and m has an average value of from 4 to 15, in a ratio by weight of acylcyanamide salt to nonionic surfactant of from 1:4 to 4:1 and preferably from 2:3 to 4:1.

8. A detergent as claimed in Claims 1 to 7, characterized in that it contains from 1 to 30% by weight and preferably from 3 to 15% by weight of the acylcyanamide salt corresponding to formula 1, from 1 to 30% by weight and preferably from 3 to 15% by weight of a synthetic anionic surfactant from the group comprising alkyl benzene sulfonates, ester sulfonates, alcohol sulfates and mixtures thereof, from 1 to 30% by weight and preferably from 2 to 15% by weight of a synthetic nonionic surfactant from the group comprising alcohol ethoxylates, alkyl phenol ethoxylates and mixtures thereof and from 10 to 97% by weight of other standard detergept ingredients.

9. A detergent as claimed in Claims 1 to 8, characterized in that it contains from 1 to 30% by weight and preferably from 3 to 15% by weight of the acylcyanamide salt of formula 1, from 1 to 30% by weight and preferably from 3 to 15% by weight of a synthetic anionic surfactant from the group comprising alkylbenzene sulfonates, ester sulfonates, alcohol sulfates and mixtures thereof, from 1 to 30% by weight and preferably from 2 to 15% by weight of a synthetic nonionic surfactant from the group comprising alcohol ethoxylates, alkyl phenol ethoxylates and mixtures thereof, from 3 to 70% by weight and preferably from 20 to 50% by weight of a builder, more particularly from the group comprising sodium triphosphate, sodium aluminium silicate, sodium nitrilotriacetate, sodium alkane polyphosphonate and mixtures thereof, from 0 to 40% by weight and preferably from 1 to 30% by weight of a peroxide bleach, optionally together with stabilizers and activators, from 0 to 20% by weight and preferably from 0.05 to 10% by weight of foam regulators and from 0 to 94% by weight of other standard detergent ingredients.