EP0163910B1 - Washing materials containing softening agent - Google Patents

Abstract

Softener-containing washing agents which, in addition to the customary components of washing agents, contain 0 to 10% by weight of a quaternary ammonium compound and 1 to 30% by weight of a softener system which comprises 10 to 90% by weight of a tertiary amine and 90 to 10% by weight of a crystalline sheet-silicate of the formula Me2SixO2x+1x yH2O in which Me denotes an alkali metal ion or a proton, x denotes a number greater than 7, in particular from 7.5 to 23, and y denotes a number smaller than 7 x, in particular smaller than x. In the softener system, the tertiary amine is in a state of adsorption on the alkali metal silicate. The ammonium compounds, which are adsorbed on said silicate, produce a softening effect in the washing agent but on the other hand are compatible with anionic surfactants in the washing agent. produce a softening effect in the washing agent but on the other hand are compatible with anionic surfactants in the washing agent.

Description

Washed textiles, especially those made from cellulose fibers, are known to have an unpleasant hardening of the handle after drying. This is particularly the case when washing is done in the washing machine. It is also known that this undesirable hardening of the handle can be eliminated by treating textiles after washing in the washing machine in the last rinse cycle with quaternary ammonium compounds which contain at least two long-chain, all-phatic residues in the molecule. In practice, the dialkyldimethylammonium salts suspendable in water have been introduced for this purpose.

The disadvantage is that these softening substances must be applied separately from the main wash in the household washing machine, since the cationic compounds are not compatible with the anionic detergents in the detergent. When used together, the cationic products are removed from the washing system in the form of neutral salts and can therefore no longer be absorbed onto the fiber.

If you work with detergent based on non-ionic detergents that are compatible with cationic plasticizers, the dirt is repositioned on the fiber so that the washed pieces have a pleasantly soft feel, but the dirt particles are not detached by the laundry.

EP-A-26 529 already discloses surfactant mixtures which, in addition to an anionic surfactant and a tertiary amine or the corresponding quaternary ammonium compound, also contain a clay mineral of the smectite type. These mixtures are used as detergents, they also have a softening effect. It has now been found that the above-described difficulties are avoided and the hardening of the washed laundry is prevented or, by washing already hardened fabric, is given a soft feel again if textile softening systems based on certain crystalline alkali silicates are used in the washing agent used for the laundry.

wobei

• R₁ und R₂ gleich oder verschieden sein können und Wasserstoff, C₁-C₄-Alkyl, C₂-C₃-Hydroxyalkyl oder Benzyl,
• R₃ Wasserstoff, C1-C22-, vorzugsweise C₁₂-C₂₂-Alkyl, C₂-C₄-Hydroxyalkyl oder Benzyl,
• R₄ C₁-C₂₂-, vorzugsweise Cs-C22-Alkyl, C₄-C₂₂-Alkoxyethyl oder C₄-C₂₂-Alkylphenoxyethyl und
• X ein Anion bedeuten,

sowie 1 bis 30, vorzugsweise 10 bis 15 Gew.-% eines pulverförmigen Weichmachersystems enthalten, bestehend aus

• a) 10 bis 90, vorzugsweise 30 bis 70 Gew.-% einer Verbindung der Formel
  
  oder
  
  
  wobei
  • R₅ C₆-C₂₂-Alkyl, C₄-C₂₂-Alkoxyethyl oder C₄-C₂₂-Alkylphenoxyethyl,
  • n eine Zahl von 1 bis 12, vorzugsweise von 1 bis 3,
  • m 1 oder 2 und
  • X NH oder O bedeuten
  
  und
  • 
    R, die oben genannte Bedeutung hat, und
• b) 90 bis 10, vorzugsweise 70 bis 30 Gew.-% eines kristallinen Alkalisilikats aus der Gruppe der Phyllosilikate der Formel
  • Me₂Si_xO_2×+1 ^yH₂0
  
  wobei
  • Me ein Alkalimetall-lon oder ein Proton,
  • x eine Zahl größer 7, insbesondere von 7,5 bis 23 und
  • y eine Zahl kleiner 7 x, insbesondere kleiner x bedeutet,

wobei diese Alkalisilikate ein lonen-austauschvermögen von 130 - 400 mmol Me⁺/100 g wasserfreies Silikat besitzen, im Röntgenbeugungsdiagramm einen oder mehrere Reflexe im Bereich der d-Werte von 3,0 bis 4,0 x 10-8 cm aufweisen, die nicht Quarz, Tridymit und Cristobalit zugeordnet werden können und ihrer Gehalt an MgO und A1₂0₃ zusammen weniger als 15 Gew % beträgt.The invention relates to detergents containing plasticizers which contain 0 to 10, preferably 1 to 5% by weight of a compound of the formula

in which

• R ₁ and R _{2 may be the} same or different and are hydrogen, C ₁ -C ₄ -alkyl, C ₂ -C ₃ -hydroxyalkyl or benzyl,
• R _{3 is} hydrogen, C1-C22, preferably C ₁₂ -C ₂₂ alkyl, C ₂ -C ₄ hydroxyalkyl or benzyl,
• R _{4 is} C ₁ -C ₂₂ -, preferably Cs-C22-alkyl, C ₄ -C ₂₂ -alkoxyethyl or C ₄ -C ₂₂ -alkylphenoxyethyl and
• X is an anion,

and 1 to 30, preferably 10 to 15 wt .-% of a powdered plasticizer system, consisting of

• a) 10 to 90, preferably 30 to 70 wt .-% of a compound of the formula
  
  or
  
  
  in which
  • R _{5 is} C ₆ -C ₂₂ alkyl, C ₄ -C ₂₂ alkoxyethyl or C ₄ -C ₂₂ alkylphenoxyethyl,
  • n is a number from 1 to 12, preferably from 1 to 3,
  • m 1 or 2 and
  • X is NH or O
  
  and
  • 
    R, which has the meaning given above, and
• b) 90 to 10, preferably 70 to 30% by weight of a crystalline alkali silicate from the group of the phyllosilicates of the formula
  • Me ₂ Si _x O _{2 × + 1} ^y H ₂ 0
  
  in which
  • Me an alkali metal ion or a proton,
  • x is a number greater than 7, in particular from 7.5 to 23 and
  • y is a number less than 7 x, in particular less than x,

these alkali silicates have an ion exchange capacity of 130 - 400 mmol Me ⁺ / 100 g anhydrous silicate, in the X-ray diffraction pattern one or more reflections in the range of the d values from 3.0 to 4.0 x 10-8 cm, which do not Quartz, tridymite and cristobalite can be assigned and their MgO and A1 ₂ 0 ₃ content together is less than 15% by weight.

The crystalline alkali silicates (layered silicates) mentioned above have a fundamentally different molecular structure from the smectites mentioned in many patents, which also include montmorillonites and hectorites, since they contain no magnesium or aluminum, apart from possible impurities in small amounts. In contrast to the smectites, the total amount of MgO and A1 ₂ 0 ₃ in the silicate is in each case less than 15% by weight, but usually less than 5% and preferably less than 2%. The alkali silicates used in the present invention or the corresponding free silicas can be assigned to the group of phyllosilicates. Their anhydrous composition can be described in explanatory terms using the formula given. All or part of the alkali metal ions can be exchanged for protons, so that in this case Me can stand for protons or various alkali metals. Accordingly, the term alkali silicates also includes the corresponding free silicas in all cases. It is preferred that Me is sodium. The ion exchange capacity of the crystalline alkali silicates used in the invention is 130-400 mmol Me + / 100 g anhydrous silicate. The silicates have cm one or more reflections in the range of d values from 3.0 to 4.0 x 10 ⁸ in the X-ray diffraction diagram, the quartz, tridymite and cristobalite can not be assigned.

Both natural and synthetic crystalline alkali silicates can be used for the invention, such as, for example, the naturally occurring magadiite, Na ₂ Si _t 4 0 ₂₉ x 11 H ₂ 0 and the kenyaite, Na ₂ Si ₂₂ 0 ₄₅ x 10 H ₂ 0 (HF Eugster, Science, 157, 1177-1180 (1967)) and synthetic products of the composition Na ₂ Si ₈ O ₁₇ , K ₂ Si ₈ O ₁₇ and N _a 2Si ₁₄ O ₂₉ (RK Iler, J. Colloid Sci., 29, 648-657 (1964); DE-PS-2 742 912; G. Lagaly, K.Beneke and A. Weiss, Am. Mineral., 60, 642-649 (1975)). The grain size of the silicates to be used according to the invention is preferably 0.1 to 50 μm.

The layered alkali silicates, in particular the sodium and potassium salts, are usually synthesized from silica gel, silica sol or precipitated silica with the addition of alkali metal hydroxide under hydrothermal conditions. An appropriate carbonate solution is sometimes used instead of an alkali hydroxide solution. The amount of alkali depends on the desired product.

Particularly preferred in the context of the present application, however, are such crystalline alkali layer silicates, the preparation of which is described in EP-A-151 295, published Aug. 14, 1985. In this process, a solution of water or an amorphous alkali silicate with a molar ratio M ₂ 0 / Si0 ₂ of 0.24 to 2.0, where M stands for an alkali metal, is mixed with so much of an acidic compound that a molar ratio M ₂ 0 (not neutralized) / Si0 ₂ of 0.05 to 0.239 is reached, if necessary a molar ratio Si0 _{2 /} H ₂ 0 of 1: 5 to 1: 100 is established by dilution and the reaction mixture is at a reaction temperature for so long kept from 70 to 250 ° C until the alkali layer silicate has crystallized. M is preferably sodium and potassium.

A preferred, very reactive starting compound is soda water glass with an Si0 ₂ content of approximately 22 to 37% and an Na ₂ 0 content of 5 to 18% and an A1 ₂ 0 ₃ content of less than 0.5%. A sodium water glass with 22-30% by weight Si0 ₂ and 5-9% by weight Na ₂ 0 is particularly preferred. But also amorphous alkali silicates, in particular solid sodium and potassium silicates, which can also be anhydrous, but at least in water soluble at the reaction temperature can be used.

The acidic compound added can be an acid anhydride or an acidic salt such as sodium bisulfate. However, free organic or inorganic acids are preferred. Inorganic acids such as phosphoric acid or sulfuric acid are particularly preferred.

The amount of acidic compound to be added depends on the starting silicate and the desired end product.

The end product formed almost always has a lower M ₂ 0 / Si0 ₂ ratio than the reaction mixture from which it is formed. In the end products, the alkali metal / silicon atomic ratio is approximately between 1: 4 and 1: 11. The pH of the product mixture after the acidic compound has been added is generally above 9. A pH of between 10 and 12 is preferably set. The reaction system is buffered by the addition of the acidic compound.

Pure products or mixtures of crystalline alkali layer silicates can be obtained by this process. The alkali layer silicates obtained show ion exchange capacity. Their X-ray diffraction diagrams are similar to those of known alkali layer silicates.

In addition to the alkali metal ions, other metal ions can also be present in the synthesis, for example germanium, aluminum, indium, arsenic and antimony, and the non-metals boron and phosphorus. If the amount of these constituents, based on the alkali content, is less than 10%, the synthesis is influenced only insignificantly. To produce a pure alkali layer silicate, or the free acid, it is advantageous to dispense with the addition of foreign metals in the synthesis. Pure sheet silicates with a cation other than alkali can easily be obtained in a further step from the alkali salt by ion exchange or from the corresponding free acid by neutralization. The process described can also be carried out in the presence of small amounts of organic compounds; however, preference is given to working without any organic compounds.

For the process described, a molar ratio of the starting products of H ₂ 0 / Si0 ₂ from 8: 1 to 40: 1 is preferred. For the production of low-alkali layered silicates (atomic ratio M / Si from 1: 7 to 1:11), a greater dilution with water is often advantageous than for the production of the higher-alkali layered silicates (atomic ratio M / Si approximately 1: 4 to 1: 7). The reaction temperature is preferably 130-230 ° C, in particular 160-210 ° C. Longer reaction times, high reaction temperatures and low ratios of alkali (not neutralized) / Si0 ₂ favor the formation of low-alkali layer silicates. Short reaction times, low reaction temperatures and high alkali / Si ratios favor the formation of layer silicates rich in alkali.

The reaction time strongly depends on the reaction temperature. It can be less than 1 hour or several months. The optimal reaction time can be determined for the selected reaction temperature by taking samples at different times during the reaction, which are examined by X-ray analysis.

The reaction is preferably carried out in a pressure vessel with thorough stirring. The addition of seed crystals is very advantageous since the purity of the product is improved and the reaction time is shortened. However, you can also work without seed crystals. Any admixtures of amorphous silicates or in this type of production with resulting amorphous silicates do not interfere, since they can take on the function of builders in the detergent. The phyllosilicates themselves can also act as builders.

The amount of seed crystals can be up to 30 wt .-%, based on the Si0 ₂ portion of the added, dissolved in water or amorphous alkali silicate in batch reaction. Seed crystal additives below 0.01% by weight no longer have any noticeable effect. Instead of adding seed crystals, it may also be sufficient if small residues from an earlier batch remain in the reaction vessel. When the reaction is carried out continuously, significantly higher concentrations of crystal nuclei (in stationary equilibrium) have proven to be advantageous.

The process can be carried out batchwise, semi-continuously and continuously in apparatus with flow tube, stirred tank or cascade characteristics.

Various alkali layer silicates can be produced using this process, including also the silicate Na-SKS-1, which is used in the examples and which has an ion exchange capacity of about 140 to 157 mmol of Na + / 100 g of dry product (calculated on the basis of the annealed product).

The use of the synthetic alkali layer silicates is particularly advantageous because they normally do not contain any heavy metal ions that decompose the perborate.

The tertiary organic amines and quaternary ammonium compounds which are used in addition to the layered silicates are compounds which are known per se. The anion in the quaternary ammonium compounds is preferably a chloride, bromide, CH ₃ SO ₄ , iodide, CH ₃ PO ₄ ion or an acetate, propionate or lactate ion.

The production of the plasticizer system from crystalline alkali layer silicates and tertiary amines can be carried out by keeping these silicates in an aqueous or aqueous-alcoholic one at approx. 20-65 ° for some time Solution of the listed tertiary amines is stirred. After a reaction time of about 0.5 to 1 hour, the suspension obtained is filtered and dried. Detailed descriptions of this reaction can be found in the literature (Lagaly et al., Organic Complexes of Synthetic Magadiite; Proc. Int. Clay Conf., Madrid 1972, p. 663-673, Madrid 1973). The powders obtained in this way are then mixed with the usual constituents of the washing powder.

Of the quaternary ammonium compounds, which are usually sold as aqueous solutions, a powdery derivative is preferably also prepared beforehand by adding silica powder to the aqueous solutions of these products. Silica powder for this purpose is commercially available under the names ^e Sipernat 22 and ^O Sipernat 50 (Degussa). The powdered preparations of the quaternary ammonium compounds thus obtained can also be mixed with the other detergent components in a simple manner.

In addition to the quaternary ammonium compounds and the plasticizer system described above, the detergents also contain the usual constituents in the customary amounts, in particular anionic, zwitterionic and nonionic surfactants, alone or in a mixture in a total amount of 4 to 70, preferably 6 to 60,% by weight, the nonionic surfactants should only amount to up to 70% by weight, in particular up to 10% by weight, of the total amount of surfactant.

The usual detergent ingredients continue to include z. B. neutral to alkaline framework substances, complexing agents, bleaching components, perborate activators, foam stabilizers, foam inhibitors, dirt carriers, enzymes and the like.

• Etwa 6 bis 60 Gew.-% einer im wesentlichen aus anionischen Tensiden vom Sulfonat- und/oder Sulfat-Typ mit bevorzugt 8 bis 18 Kohlenstoffatomen im hydrophoben Rest, Seifen und gegebenenfalls nichtionischen Tensiden bestehenden Tensidkomponente, wobei gegebenenfalls vorhandene nichtionische Tenside bis zu etwa 70 Gew.-% und vorzugsweise nicht mehr als 10 Gew.-% dieser Tensidkomponente ausmachen, 0,5 - -15 % des oben beschriebenen Weichmachersystems und 0 - 5 % der quartären Ammoniumverbindung in Pulverform und ein der Differenz bis zu 100 Gew.-% entsprechender Anteil an sonstigen Waschmittelbestandteilen, insbesondere an alkalisch bis neutral reagierenden Gerüstsubstanzen und anderen Hilfsstoffen wie z. B. Bleichmittel, Perborataktivatoren, Schmutzträger, Enzyme, Aufheller, Parfüme, Farbstoff, Wasser.

The composition of detergents of practical interest which are of particular interest in general lies in the range of the following recipe:

• About 6 to 60% by weight of a surfactant component consisting essentially of anionic surfactants of the sulfonate and / or sulfate type with preferably 8 to 18 carbon atoms in the hydrophobic residue, soaps and optionally nonionic surfactants, with any nonionic surfactants present up to about 70 % By weight and preferably not more than 10% by weight of this surfactant component, 0.5-15% of the plasticizer system described above and 0-5% of the quaternary ammonium compound in powder form and a difference of up to 100% by weight Corresponding proportion of other detergent components, in particular alkaline to neutral reacting framework substances and other auxiliaries such as. B. bleach, perborate activators, dirt carriers, enzymes, brighteners, perfumes, dye, water.

In the detergents containing soaps, the quantitative ratio of the anionic surfactants of the sulfonate and / or sulfate type to the soap is in the range from about 10: 1 to 1: 5, preferably 7: 1 to 1: 2. The detergents can also contain a bleaching component , which is considered part of the other detergent ingredients in the above recipe. If a bleaching component is present, it is preferably perborate, optionally in combination with activators.

The detergent according to the invention is suitable for washing cotton fabrics, delicates and easy-care textiles, in particular those made of cotton, polyester, polyacrylonitrile and polyamide, especially when processed as fabrics and knitted fabrics. A temperature in the range of 30-60 ° C is selected as the washing temperature. But it is also possible to wash at temperatures up to cooking temperatures.

The components of the mild detergent, easy-care and heavy-duty detergent are the already known components, as have already been extensively described in the literature (see, for example, Schwartz, Perry, Berch, "Surface Active Agents and Detergents" Vol. 11 ( 1958), pages 25-93, 120-130 and 238-317; Lindner, "Tenside, Textilhilhilmittel, Waschrohstoffe" Vol. I, (1964), pages 561-921 and 1035-1041; P. Bert, "Chemistry and Technology of Modern Detergents ", Chemikerzeitung 94, 1970, No. 23/24, p. 974 ff).

• Die anionischen, zwitterionischen oder nichtionischen Tenside enthalten im Molekül wenigstens einen hydrophoben Rest von meist 8 bis 26, insbesondere 10 bis 18 C-Atomen und wenigstens eine anionische, nichtionische oder zwitterionische wasserlöslichmachende Gruppe. Der vorzugsweise gesättigte hydrophobe Rest ist meist aliphatischer, gegebenenfalls auch alicyclischer Natur; er kann mit den wasserlöslichmachenden Gruppen direkt oder über Zwischenglieder verbunden sein. Als Zwischenglieder kommen z. B. Benzolringe, Carbonsäureester- oder Carbonamidgruppen infrage. Als anionische Waschaktivsubstanz sind auch Seifen aus natürlichen oder synthetischen Fettsäuren, gegebenenfalls auch aus Harz- oder Naphthensäuren brauchbar insbesondere wenn diese Säuren Jodzahlen von höchstens 30 und vorzugsweise von weniger als 10 aufweisen.

The anionic, zwitterionic and nonionic detergent active substances of the detergents according to the invention are in particular the products listed below:

• The anionic, zwitterionic or nonionic surfactants contain at least one hydrophobic radical of mostly 8 to 26, in particular 10 to 18, carbon atoms and at least one anionic, nonionic or zwitterionic water-solubilizing group in the molecule. The preferably saturated hydrophobic residue is usually aliphatic, possibly also alicyclic in nature; it can be connected to the water-solubilizing groups directly or via intermediate links. As intermediate links come z. B. benzene rings, carboxylic acid ester or carbonamide groups in question. Soaps from natural or synthetic fatty acids, optionally also from resin or naphthenic acids, can also be used as the anionic detergent active substance, in particular if these acids have iodine numbers of at most 30 and preferably less than 10.

Of the synthetic anionic surfactants, the sulfonates and sulfates are of particular practical importance. The sulfonates include, for example, the alkylarylsulfonates, in particular the alkylbenzenesulfonates, which are obtained, inter alia, from preferably straight-chain aliphatic hydrocarbons having 9 to 15, in particular 10 to 14, carbon atoms by chlorinating and alkylating benzene or from corresponding terminal or internal olefins by alkylating benzene and sulfonating the alkylbenzenes obtained. Also of interest are aliphatic sulfonates, such as those found in e.g. B. from preferably saturated, about 8 to 18 and preferably 12 to 18 carbon atoms in a straight chain in the molecule containing hydrocarbons by sulfochlorination with sulfur dioxide and chlorine or sulfoxidation with sulfur dioxide and oxygen and converting the products obtained in the sulfonates are accessible. As aliphatic sulfonates, alkene sulfonates, hydroxyalkanesulfonate and disulfonate-containing mixtures which can be used, for. B. from terminal or medium-sized olefins with about 8 to 18 carbon atoms by sulfonation with sulfur trioxide and acidic or alkaline hydrolysis of the sulfonation products. In the aliphatic sulfonates produced in this way, the sulfonate group is often located on a secondary one Carbon atom; but it is also possible to use sulfonates having a terminal sulfonate group obtained by reacting terminal olefins with bisulfite.

The sulfonates to be used according to the invention also include salts, preferably dialkali salts of alpha-sulfo fatty acids and salts of esters of these acids with mono- or polyhydric alcohols containing 1 to 4 and preferably 1 to 2 carbon atoms. Further useful sulfonates are salts of fatty acid esters of oxethanesulfonic acid or dioxypropanesulfonic acid, the salts of fatty alcohol esters of lower, 1 to 8 carbon atoms containing aliphatic or aromatic sulfomono- or dicarboxylic acids, the alkylglyceryl ether sulfonates and the salts of the amide-like condensation products of fatty acids or sulfonic acids with aminoethanesulfonic acids .

Fatty alcohol sulfates are to be mentioned as surfactants of the sulfate type, in particular those made from coconut fatty alcohols, tallow fatty alcohols or from oleyl alcohol. Useful sulfonation products of the sulfate type can also be obtained from terminal or internal olefins having about 8 to 16 carbon atoms. This group of surfactants also includes sulfated fatty acid alkylolamides or fatty acid monoglycerides and sulfated alkoxylation products of alkylphenols (C _8-15 -alkyl), fatty alcohols, fatty acid amides or fatty acid alkylolamides, which contain about 1 to 20, in particular 2 to 4, ethylene and / or propylene glycol residues in the molecule can.

Suitable anionic surfactants of the carboxylate type are also the fatty acid esters or fatty alcohol ethers of hydroxycarboxylic acids and the amide-like condensation products of fatty acids or sulfonic acids with aminocarboxylic acids, e.g. B. with glycol, sarcosine and the like.

Nonionic surfactants include products that owe their water solubility to the presence of polyether chains, amine oxide, sulfoxide or phosphine oxide groups, alkylolamide groups and, quite generally, an accumulation of hydroxyl groups. Of particular practical interest here are the products obtainable by addition of ethylene oxide and / or propylene glycol onto fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid or sulfonic acid amides, which can contain about 4 to 60, in particular 8 to 20, ether residues, especially ethylene glycol ether residues per molecule .

Nonionic surfactants also include fatty acid or sulfonic acid alkylolamides, which are e.g. B. of mono- or diethanolamine, of dihydroxypropylamine or other polyhydroxyalkylamines, e.g. B. derive the Glycaminen. They can be replaced by amides from higher primary or secondary alkylamines and polyhydroxycarboxylic acids.

Capillary-active amine oxides are also suitable as surfactants; these include e.g. B. the products derived from higher tertiary amines containing a hydrophobic alkyl radical and two shorter alkyl and / or alkylol radicals each containing up to 4 carbon atoms.

Zwitterionic surfactants contain both acidic and basic hydrophilic groups in the molecule. The acidic groups include carboxyl, sulfonic acid, sulfuric acid half-ester, phosphonic acid and phosphoric acid partial ester groups. Primary, secondary, tertiary amine and quaternary ammonium groups are possible as basic groups. Zwitterionic compounds with quaternary ammonium groups belong to the type of betaines.

The foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants, just as it can be changed by adding non-surfactant-like organic substances. Capillary-active carboxy- or sulfobetaines and the above-mentioned nonionics of the alkylolamide type are particularly suitable as foam stabilizers in the case of surfactants of the sulfonate or sulfate type; in addition, fatty alcohols or higher terminal diols have been proposed for this purpose.

Products with reduced foaming power are primarily intended for use in washing machines, sometimes with limited foam attenuation, while in other cases more foam attenuation may be desirable. Of particular practical importance are products that still foam in the medium temperature range up to about 65 ° C, but develop less and less foam when transitioning to higher temperatures up to 100 ° C.

A reduced foaming power is often obtained with combinations of different types of surfactants, especially with combinations of synthetic anionic surfactants, especially sulfates and / or sulfonates or nonionic surfactants on the one hand and soaps on the other.

However, the foaming power of the surfactants can also be reduced by adding non-surfactant foam inhibitors known per se.

Suitable builders for the detergents according to the invention are weakly acidic, neutral and alkaline inorganic or organic salts, in particular inorganic or organic complexing agents.

Useful, weakly acidic, neutral or alkaline-reacting salts are, for example, the bicarbonates, carbonates or silicates of the alkalis, furthermore mono-, di- or trialkali orthophosphates, di- or tetraalkali-pyrophosphates, metaphosphates, alkali sulfates known as complexing agents and the alkali salts of organic, non-capillary-active, Sulfonic acids, carboxylic acids and sulfocarboxylic acids containing 1 to 8 carbon atoms. These include, for example, water-soluble salts of benzene, toluene or xylene sulfonic acid, water-soluble salts of sulfoacetic acid, sulfobenzoic acid or salts of sulfodicarboxylic acids and the salts of acetic acid, lactic acid, citric acid and tartaric acid.

The weakly acidic metaphosphates and the alkaline polyphosphates, in particular tripolyphosphate, are also suitable as complex-forming framework substances. They can be replaced in whole or in part by organic complexing agents. Organic complexing agents include for example nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediamine triacetic acid, polyalkylene-polyamine-N-polycarboxylic acids and other known organic complexing agents, it also being possible to use combinations of different complexing agents.

Suitable perborate activators are customary products from the group N-acetyl, O-acetyl derivatives, such as. B. tetraacetylethylenediamine, tetraacetylglycoluryl or z. B. Glucose pentaacetate.

Examples

In the following examples, three types of detergent were selected to represent the numerous possible variations of detergent formulations.

The composition of the detergents described in the examples can be found in the tables below. The salt-like components contained in the detergents - salt-like surfactants, other organic salts and inorganic salts - are present as sodium salt, unless expressly stated otherwise; the percentages mean percentages by weight, unless stated otherwise.

• SAS - Alkansulfonat, ein aus Paraffin mit 13 bis 18 C-Atomen durch Sulfoxidation erhaltenes Sulfonat.
• ABS - Alkylbenzolsulfonat, das Salz einer durch Kondensation von geradkettigen Olefinen mit Benzol und Sulfonierung des so entstandenen Alkylbenzols erhaltenen Alkylbenzolsulfonsäure mit 12 bis 14 Kohlenstoffatomen in der Alkylkette.
• AOS - Olefinsulfonat, ein aus Olefingemischen mit 12 bis 18 C-Atomen durch Sulfonieren mit S0₃ und Hydrolysieren des Sulfonierungsproduktes mit Lauge erhaltenes Sulfonat, das im wesentlichen aus Alkansulfon und Oxyalkansulfonat besteht, daneben aber auch geringe Mengen Disulfonate enthält.
• FAAS - Fettalkohol-Ethersulfat, hergestellt durch Anlagerung von 3 Mol Ethylenoxid an 1 Mol eines C₁₂ bis C₁₄-Alkohols und anschließendes Sulfonieren mit S0₃ und Neutralisieren mit NaOH.

The related names or abbreviations mean:

• SAS - alkane sulfonate, a sulfonate obtained from paraffin with 13 to 18 carbon atoms by sulfoxidation.
• ABS - alkylbenzenesulfonate, the salt of an alkylbenzenesulfonic acid with 12 to 14 carbon atoms in the alkyl chain obtained by condensation of straight-chain olefins with benzene and sulfonation of the resulting alkylbenzene.
• AOS - olefin sulfonate, a sulfonate obtained from olefin mixtures with 12 to 18 carbon atoms by sulfonation with SO ₃ and hydrolyzing the sulfonation product with alkali, which consists essentially of alkanesulfone and oxyalkanesulfonate, but also contains small amounts of disulfonates.
• FAAS - fatty alcohol ether sulfate, produced by addition of 3 moles of ethylene oxide to 1 mole of a C ₁₂ to C ₁₄ alcohol and subsequent sulfonation with S0 ₃ and neutralization with NaOH.

N - Nonionic surfactant, produced from a 1 mole of a fatty alcohol with a specified number of carbon atoms by reaction with a specified number of moles of alkylene oxide (EO - ethylene oxide).

• CMC - Carboxymethylcellulose, Natriumsalz
• NaTPP - Natriumtripolyphosphat

Soap made from a mixture of fatty acids with 16 to 22 carbon atoms.

• CMC - carboxymethyl cellulose, sodium salt
• NaTPP - sodium tripolyphosphate

The plasticizer systems S 1 to S 3 used in the examples contain tertiary amines as indicated as textile softeners, crystalline alkali silicate SKS-1 and quaternary ammonium compounds as indicated.

• Man stellt zunächst eine Reaktionsmischung der molaren Zusammensetzung
  • 0,303 Na₂0 : 0,0052 Al₂O₃: Si0₂ : 30 H₂0

dadurch her, daß man 83,5 Gewichtsteile Natronwasserglas (27 % SiO₂, 8,43 % Na₂0, 0,24 % Al₂O₃) zu 149 Teilen Wasser gibt. Danach wird ein Teil eines filterfeuchten kristallinen Natriumsilikats aus einem früheren Versuch (71 % Gewichtsverlust durch Erhitzen auf 1200°C; für die Berechnung der molaren Zusammensetzung wurde nur der Wasseranteil berücksichtigt) zugegeben. Man setzt anschließend langsam unter Rühren 4,93 Teile 96 %ige Schwefelsäure zu. Danach hat die Reaktionsmischung folgende molare Zusammensetzung:

• 0,174 Na₂0 : 0,0052 A1₂0₃: Si0₂ : 0,129 Na₂S0₄ : 30 H₂0.

The sodium silicate Na-SKS-1 was produced in the following way:

• A reaction mixture of molar composition is first prepared
  • 0.303 Na ₂ 0: 0.0052 Al ₂ O ₃ : Si0 ₂ : 30 H ₂ 0

by giving 83.5 parts by weight of sodium water glass (27% SiO ₂ , 8.43% Na ₂ 0, 0.24% Al ₂ O ₃ ) to 149 parts of water. Then a part of a filter-moist crystalline sodium silicate from a previous experiment (71% weight loss by heating to 1200 ° C; only the water content was taken into account for the calculation of the molar composition) is added. 4.93 parts of 96% sulfuric acid are then slowly added with stirring. The reaction mixture then has the following molar composition:

• 0.174 Na ₂ 0: 0.0052 A1 ₂ 0 ₃ : Si0 ₂ : 0.129 Na ₂ S0 ₄ : 30 H ₂ 0.

The reaction mixture is heated in a stainless steel autoclave to 205 ° C. in the course of 1.5 hours, held at this temperature for 2.5 hours and then slowly cooled. After cooling, the reaction mixture is filtered, washed with water and sucked dry on a suction filter. The filter-moist product has a loss on ignition of 55%. The product, briefly dried in air, is examined thermogravimetrically. A weight loss of 43% has occurred up to a temperature of around 140 ° C. No further significant weight loss is observed up to approx. 1000 ° C. The product, Na-SKS-1, dried at 120 ° C to constant weight, shows the following elementary analytical composition: 3.8% Na, 0.24% Al, 41.5% Si and 0.003% Fe. A molar Si0 _{2 /} Na ₂ 0 ratio of 17.9 can be calculated from this. The X-ray diffraction chart of the air-dried sodium silicate (Na-SKS-1) is shown in the following table.

(R = hydrogenated tallow fatty alkyl)

These plasticizer systems, along with the quaternary ammonium compounds, were incorporated into three different types of detergents as indicated below. The quaternary ammonium compounds were previously absorbed on finely divided silica ® (Sipernat 50) and thus converted into powder form. The type and amount of the quaternary ammonium compounds are shown in Table 2 below. The absorption on the silica was carried out as described above by briefly heating the solution of the quaternary ammonium compound with the silica. These powdered preparations of the quaternary ammonium compounds are referred to below as QAC.

Composition of the detergent (WAMI) = heavy duty detergent 60 - 95 ° C

Composition of detergents (synthetic detergents) 60 ° C

Composition of the detergent (mild detergent)

Depending on the intended use of the detergents, cotton brighteners, polyamide brighteners, polyester brighteners or a combination thereof are used as brighteners.

• In einer Waschflotte mit jeweils 7,5 g/I der oben beschriebenen Waschmittel mit einem Gehalt des zu prüfenden Textilweichmachers werden in einer Trommelwaschmaschine (AEG Lavamat Regina de Lux) Proben von neuem Baumwollfrotteegewebe bei 60° C mit Ballaststoff (Flottenverhältnis 1 : 5 bis 1 : 8) jeweils dreimal gewaschen. Zur Kontrolle werden 7,5 g/I der oben beschriebenen textilweichmacherfreien Waschmittel verwendet.

The textile softening effect of the detergents WAMI 1-9 was demonstrated as follows in comparison to the corresponding control detergents which did not contain any plasticizer systems:

• In a washing liquor with 7.5 g / l each of the above-described detergents containing the textile softener to be tested, samples of new cotton terry fabric at 60 ° C with fiber are used in a drum washing machine (AEG Lavamat Regina de Lux) (liquor ratio 1: 5 to 1 : 8) Washed three times each. 7.5 g / l of the detergent-free detergent described above are used as a control.

After each wash, the fabric is rinsed and dried hanging and then left in the climate room for 24 hours at 20 ° C 60% relative humidity. The softening effect achieved in the washing tests is determined by evaluating the handle independently by 7 trained persons.

• 100 voller und sehr weicher Griff
• 0 sehr harter Griff bedeuten.

The grip rating is expressed in grades from 0 to 100, where

• 100 full and very soft handle
• 0 means very hard grip.

• Proben von neuem Baumwollfrotteestoff werden 10 mal im Waschautomaten unter Kochwaschbedingungen in Wasser mit einem handelsüblichen Vollwaschmittel behandelt. Nach dem Trocknen wird dem derartig vorgehärteten Gewebe die Griffnote 0 gegeben.

The limit values 0 and 100 are defined as follows:

• Samples of new cotton terry cloth are treated 10 times in the washing machine under boil-washing conditions in water with a commercial heavy-duty detergent. After drying, the pre-hardened fabric is given a touch rating of 0.

Samples of a new cotton terry cloth fabric are unsealed and treated with a solution of distearyldimethylammonium chloride (1.5 g active substance plasticizer per kg substance). The touch 100 is given to the fabric softened in this way.

Result

When using detergents according to the invention with plasticizer systems (example WAMI 1-3), a handle improvement of 30-50% is achieved compared to the washing powder of the same composition, but without a plasticizer system.

Claims (4)

1. A softener-containing washing agent which contains 0 to 10 % by weight of a quaternary ammonium compound of the formula

where

R₁ and R₂ can be identical or different and denote hydrogen, C₁-C₄-alkyl, C₂-C₃-hydroxyalkyl or benzyl,

R₃ denotes hydrogen, C₁-C₂₂-alkyl, preferably C₁₂-C₂₂-alkyl, C₂-C₄-hydroxyalkyl or benzyl,

.R₄ denotes C₁-C₂₂-alkyl, preferably C₆-C₂₂-alkyl, C₄-C₂₂-alkoxyethyl or C₄-C₂₂-alkylphenoxyethyl, and

X denotes an anion, and 1 to 30, preferably 10 to 15 % by weight of a pulverulent softener system comprising

a) 10 to 90, preferably 30 to 70 % by weight of a compound of the formula

where

R₅ denotes C₆-C₂₂-alkyl, C₄-C₂₂-alkoxyethyl or C₄-C₂₂-alkylphenoxyethyl,

n denotes a number from 1 to 12, preferably from 1 to 3,

m denotes 1 or 2, and

X denotes NH or 0

and R₁ has the abovementioned meaning, and

b) 90 to 10, preferably 70 to 30 % by weight of a crystalline alkali metal silicate from the group of the phyllosilicates of the formula

Me₂Si_xO_2x+1 . yH₂0

where

Me denotes an alkali metal ion or a proton,

x denotes a number greater than 7, in particular 7.5 to 23, and

y denotes a number smaller than 7 x, in particular smaller than x,

these alkali metal silicates having an ion exchange capacity of 130 - 400 mmol of Me+/100 g of water-free silicate, one or more reflections in the X-ray diffraction diagram within the range of d values from 3.0 to 4.0 x 10-s cm which cannot be assigned to quartz, tridymite and cristobalite and their content of MgO and Al₂O₃ together is less than 15 % by weight.

2. The softener-containing washing agent as claimed in claim 1, which contains 1 to 5 % by weight of the quaternary ammonium compounds and 10 to 15 % by weight of the softener system which comprises 30 to 70 % by weight of tertiary amine and 70 to 30 % by weight of crystalline alkali metal silicate.

3. The softener-containing washing agent as claimed in claim 1, in which the softener system contains a crystalline alkali metal silicate of the indicated formula in which Me denotes sodium, x is a number from 7.5 to 23, and y is a number from 0 to 25.

4. The softener-containing washing agent as claimed in claim 1, which contains the quaternary ammonium compounds adsorbed onto finely divided silica.