EP0954559B1 - Pastelike detergent and cleaning agent - Google Patents

Abstract

A paste-form detergent and process of making the detergent is presented. The detergent is composed of: 5 to 30 percent by weight of an ethoxylated alcohol of the formula R1-(OC2H4)m-OH where R1 is an alkyl or alkenyl group containing 9 to 15 carbon atoms and the average degree of ethoxylation m is 1 to 8; 1 to 20 percent by weight of an ethoxylated alcohol of the formula R2-(OC2H4)nOH where R2 is an alkyl or alkenyl group containing 12 to 22 carbon atoms and the average degree of ethoxylation n is 3 to 14, and n is greater than m by at least 1.0; 1 to 20 percent by weight of an alcohol or alkyl ether corresponding to the formula R3-O-R4 where R3 is an alkyl or alkenyl group containing 6 to 22 carbon atoms and R4 is hydrogen or an alkyl group containing 1 to 6 carbon atoms; 20 to 80 percent by weight of an alkalizing agent, and 0 to 15 percent by weight of an organic builder. The paste-form detergent is useful in institutional laundries and results in a reduced tendency to foam at the rinsing and pressing stage.

Description

The present invention relates to pasty washing and cleaning agents for the Use in commercial laundry and a method for producing such Medium.

Detergents used in the household are tailored to the needs there; so they are usually powdery or sufficiently liquid to be themselves pour and dispense easily. Because such liquid detergents Additives are often intended to be stable in storage within relatively wide temperature ranges of organic solvents and / or hydrotropes, which, however, themselves not contribute to and from the washing or cleaning result Reason are undesirable. A way to avoid possible dosing problems with insufficiently liquid means in the European patent application EP 253 151 A2 proposed. From this document are fluid, partially highly viscous detergents based on non-ionic and anionic surfactants known, which contain polyethylene glycol as hydrotrope and which the user does not consider must be dosed in liquid form, but portioned into bags of water-soluble Material, for example polyvinyl alcohol, are packaged.

The paste-like detergent described in European patent EP 295 525 B1 consists of a liquid phase in the temperature range below 10 ° C nonionic surfactant is formed, and a solid phase dispersed therein Grain size, which consists of washing alkalis, sequestrants and optionally Anionic surfactants is formed. For this purpose surfactants or their mixtures used, the pour point (solidification point) must be below 5 ° C to solidify avoid the paste at low transport and storage temperatures. This Detergent paste is intended for commercial laundries and is so flowable that it can be conveyed via a suction line using a conventional feed pump. However, it has been found that such pastes are not during their manufacture always and satisfactorily ensure the homogeneity of their ingredients often tend to separate during storage. The segregation does not only concern the separation of the solid from the liquid components, but also the Phase separation of the liquid ingredients.

Another paste-like detergent, which is a nonionic surfactant 40 to 70 % By weight of ethoxylated fatty alcohol with 10 to 20 carbon atoms which is liquid at room temperature and an average degree of ethoxylation of 1 to 8 and 20 to 50% by weight at room temperature liquid ethoxylated and propoxylated fatty alcohol with 10 to 20 Carbon atoms and an average degree of ethoxylation of 2 to 8 and one contains average degree of propoxylation of 1 to 6 and 1 to 10 wt .-% soap is in the international patent application WO 95/09229. This pasty Detergent or cleaning agent is so pseudoplastic that it is below at room temperature The action of gravity is not flowable, but a significantly lower one when sheared Has viscosity and is then flowable under the influence of gravity. The Dosage of this pasty detergent or cleaning agent is preferably carried out in that the agent for lowering the viscosity is subjected to shear and the flowable agent can then be metered by means of feed pumps.

Especially in car washes, detergents often lead to foam problems make them unpleasantly noticeable especially in the washing and pressing area. attributable the occurrence of foams in this area should be due to the presence of surfactants, especially non-ionic surfactants, which adhere to the washed laundry have accumulated and from the rinse area to the washing and pressing area high mechanical stress. In addition to these disruptions in operations Excessive foaming can also cause skin irritation Do not leave larger amounts of surfactant on the washed laundry completely excluded.

In addition, in recent times, the demand for commercial laundry the waiver of detergent ingredients that are perceived as not being sufficiently biodegradable levied. This requirement is particularly difficult to comply with the cleaning performance of the detergents compared to the conditions at the Household linen has to meet much higher demands. this applies especially for the surfactants that make a significant contribution to cleaning performance Ingredients in which synthetic anionic surfactants, in particular of the type sulfonated alkylbenzenes play an outstanding role in this regard.

The present invention was therefore based on the object of a pasty To provide laundry detergents for use in commercial laundries shows a reduced tendency to foam in the rinsing and pressing area as well as lower Amounts of surfactant on the washed fabrics leads and with good storage stability has good washing performance.

Surprisingly, these problems were essentially solved by a Optimization of the non-ionic surfactant component and the use of long-chain Alcohols and / or long chain alkyl ethers.

The present invention relates to a pasty detergent for use in commercial laundering, containing alkylbenzenesulfonates, nonionic surfactant, organic and / or inorganic builders, alkalizing agents and optionally bleaching agent, enzyme, graying-inhibiting polymer and / or other conventional ingredients, which is characterized in that that it contains 5% by weight to 30% by weight, in particular 10% by weight to 25% by weight, of an ethoxylated alcohol of the general formula I, R ¹ - (OC ₂ H ₄ ) _m -OH in which R 'is an alkyl or alkenyl radical having 9 to 15 carbon atoms, in particular 12 to 14 carbon atoms and the average degree of ethoxylation m can assume values from 1 to 8, 1% by weight to 20% by weight, in particular 5% by weight to 15% by weight of an ethoxylated alcohol of the general formula II, R ² - (OC ₂ H ₄ ) _n -OH in which R ² denotes an alkyl or alkenyl radical having 12 to 22 carbon atoms and the average degree of ethoxylation n can assume values from 3 to 14, with the proviso that n is at least 1.0, preferably at least 2.0, larger as m, 20% by weight to 80% by weight of alkalizing agent, 1% by weight to 20% by weight, in particular 3% by weight to 15% by weight of medium to long-chain alcohol or alkyl ether of the general formula III, R ³ -OR ⁴ in which R ^{3 is} an alkyl or alkenyl radical having 6 to 22 carbon atoms, in particular 8 to 22 carbon atoms and R ^{4 is} hydrogen or an alkyl radical having 1 to 6 carbon atoms, and up to 15% by weight, preferably not more than 10% by weight, in particular not more than 8% by weight and particularly preferably not more than 5% by weight of organic builders of the polymeric polycarboxylate type and up to 25% by weight, preferably up to 7% Contains 5% by weight and in particular 0.5% by weight to 3% by weight of synthetic anionic surfactant selected from the alkylbenzenesulfonates. In the context of the invention, polymeric polycarboxylates are to be understood as meaning polymerization products of unsaturated mono- and / or dicarboxylic acids which, apart from carboxyl groups, have no further functionalities.

An agent according to the invention preferably contains up to 20% by weight, in particular up to 10% by weight, of an alkoxylated alcohol of the general formula IV as a further surfactant component in addition to the nonionic surfactants mentioned above R ⁵ - (OC ₂ H ₄ ) _x - (OC ₃ H ₆ ) _y -OH in which R ⁵ denotes an alkyl or alkenyl radical having 9 to 15 carbon atoms, in particular 12 to 15 carbon atoms, and the average degree of ethoxylation x can take on values from 3 to 7 and the average degree of propoxylation can take on values of 2 to 8.

The liquid phase of the paste-like composition according to the invention is essentially formed by the nonionic surfactants of the formulas I and II, which have different carbon chain lengths and different degrees of alkoxylation, and the alcohols or ethers of the formula III and, if appropriate, the additional surfactants according to formula IV. The viscosity of the agent according to the invention can be adjusted by combining ethoxylated alcohols with the formulas I and II. In the compounds of the formulas I, II and IV, the radicals R ¹ , R ² or R ^{5 can be} linear or branched, for example methyl-branched in the 2-position, linear radicals having primary etherified alcohol functions being preferred. The nonionic surfactant according to formula I preferably has a carbon chain length of 8 to 14, in particular 12 to 14, carbon atoms and an average degree of ethoxylation m of 1 to 8, in particular 1 to 5. The nonionic surfactant according to formula II has a broader carbon chain length distribution towards longer chains with 12 to 22, in particular 12 to 18 and particularly preferably 16 to 18 carbon atoms and a higher average degree of ethoxylation n of 3 to 14, in particular 6 to 12. The ethoxylated alcohols of the formula I and the ethoxylated alcohols of the formula II are preferably in weight ratios of 2: 1 to 1: 1.8. The agent according to the invention can contain further nonionic surfactants commonly used in washing and cleaning agents, such as, for example, alkyl polyglycosides and / or fatty acid polyhydroxyamides. However, the surfactant component is preferably free from exclusively propoxylated alcohols.

For the alcohols or ethers of the general formula III, which contribute to the particularly good low-temperature stability of the agents according to the invention, ensure low foam and reduce the surfactant deposit on the washed laundry and additionally contribute to the washing performance, the following applies essentially to the rest of R ³ the above for the radicals R ¹ and R ² . In addition to hydrogen, R ⁴ is preferably a methyl, ethyl, propyl or butyl group, hydrogen and the methyl group, in particular hydrogen, being particularly preferred. In a preferred embodiment of the invention, the agents contain up to 15% by weight, preferably 2% by weight to 10% by weight, of substances of the general formula III.

The agent contains up to 25% by weight, preferably up to 7.5% by weight and in particular 0.5% by weight to 3% by weight, of synthetic anionic surfactants selected from the alkylbenzenesulfonates as further surfactants. Suitable synthetic anionic surfactants, which can preferably be incorporated into the agent according to the invention in solid, finely divided, largely anhydrous form, include those of the sulfonate type which are normally present as alkali metal salts, preferably as sodium salts. However, the sulfonate-type surfactants mentioned can also be used in the form of their free acids. Suitable anionic surfactants of the sulfonate type are C _9-13 alkyl benzene sulfonates. The naturally occurring anionic surfactants include, in particular, the soaps, which can be present in the agents according to the invention preferably in amounts of up to 5% by weight, in particular from 0.5% by weight to 2% by weight. Suitable soaps are in particular the alkali metal salts of the saturated and / or unsaturated C _12-18 fatty acids, for example coconut, palm kernel or tallow fatty acid. The use of salts of a carboxylic acid mixture of, in each case based on the total carboxylic acid mixture, from 2% by weight to 8% by weight of C _14- , up to 1% by weight of C _15- , 18% by weight to 24 is particularly preferred % By weight C ₁₆ -, up to 3% by weight C ₁₇ -, 20% by weight to 42% by weight C ₁₈ - and 30% by weight to 44% by weight C _20-22 - carboxylic acid.

The solid phase of the agent according to the invention is essentially from the Alkalizing agents and builder substances are formed, optionally further particulate auxiliaries may be present. The solid phase should be in the liquid Be dispersed as homogeneously as possible. The contained as a solid phase Components of the paste-like agent should be finely divided and an average grain size have in the range of 5 microns to 200 microns, with at most 15% of the particles Have a grain size of more than 200 µm. Surprisingly, it is possible to be relative coarse-grained solids, for example those containing 20% to 50% particles Grain sizes over 100 microns included, without disadvantage in the pasty agents incorporate. The average grain size is preferably that of the solid phase Particles 10 microns to 80 microns and especially 10 microns to 60 microns, the maximum Grain size is less than 300 microns, especially less than 250 microns. Are preferred 90 wt .-% of the solid powdery components smaller than 200 microns, in particular smaller than 150 µm. The average grain size can be determined by known methods (for example using laser diffraction or a Coulter Counter).

The alkalizing agents contained as a further component are often also referred to as washing alkalis. They are mainly assigned to the fixed phase. Under the conditions of use of agents according to the invention, they ensure a pH in the alkaline range which is normally in the range from 9 to 13, in particular from 10 to 12 (in each case measured in a 1% strength by weight solution of the agent in ion-exchanged water). The preferred alkalizing agent is amorphous alkali silicate, in particular sodium metasilicate of the composition Na ₂ O: SiO ₂ from 1: 0.8 to 1: 1.3, preferably 1: 1, which is used in anhydrous form. In addition to the alkali silicate, anhydrous alkali carbonate or alkali hydrogen carbonate are also suitable, which, however, requires larger proportions of the liquid phase due to absorption processes and is therefore less preferred. The proportion of alkalizing agents in the agents is 20% by weight to 80% by weight, preferably 30% by weight to 70% by weight and in particular 40% by weight to 60% by weight. The alkalizing agent component of the agent according to the invention can consist solely of silicate. Alkali carbonate or alkali hydrogen carbonate is preferably present in amounts not exceeding 40% by weight, in particular up to 25% by weight, and in a preferred embodiment of the invention in amounts below 10% by weight. In particular, if a phosphate content is ecologically harmless when using agents according to the invention (for example in the case of wastewater treatment which eliminates the phosphates), polymeric alkali metal phosphates, such as sodium tripolyphosphate, may also be present in paste-like agents according to the invention. Their proportion is preferably up to 70% by weight, in particular 15% by weight to 40% by weight, based on the total composition, the proportion of the other solids, for example the alkali silicate and / or optionally contained aluminosilicate, accordingly can be reduced.

Suitable organic builder substances are, in particular, monomeric polycarboxylic acids or hydroxycarboxylic acids such as citric acid or gluconic acid or their salts and, in addition, those from the class of the aminopolycarboxylic acids and polyphosphonic acids. The aminopolycarboxylic acids include nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and their higher homologues, preference being given to using N, N-bis (carboxymethyl) aspartic acid. Suitable polyphosphonic acids are 1-hydroxyethane-1,1-diphosphonic acid, aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) and their higher homologs, such as, for example, diethylenetetraminetetra (methylenephosphonic acid). The aforementioned acids are usually used in the form of their alkali metal salts, in particular the sodium or potassium salts. The builders which can also be used include homopolymeric and / or copolymeric carboxylic acids or their alkali metal salts, the sodium or potassium salts also being particularly preferred here. Polymer carboxylates or polymer carboxylic acids with a relative molecular weight of at least 350, in the form of their water-soluble salts, in particular in the form of the sodium and / or potassium salts, have proven to be particularly suitable, such as oxidized polysaccharides according to international patent application WO 93/08251, polyacrylates , Polymethacrylates, polymaleinates and in particular copolymers of acrylic acid with maleic acid or maleic anhydride, preferably those of 50 to 70% acrylic acid and 50 to 10% maleic acid, as are characterized, for example, in European patent EP 022 551. The relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ dicarboxylic acid, maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical. Polymers of this type can be produced in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular weight of between 1,000 and 200,000. Further preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. Also useful are polyacetal carboxylic acids as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, which are obtained by polymerizing esters of glycolic acid, introducing stable terminal end groups and saponifying to give the sodium or potassium salts. Also suitable are polymeric acids which are obtained by polymerizing acrolein and disproportionating the polymer according to Canizzaro using strong alkalis. They are essentially made up of acrylic acid units and vinyl alcohol units or acrolein units.

If such substances at all in the paste-like compositions according to the invention are contained, the proportion of organic, carboxyl group-containing builder materials in the paste-like composition according to the invention up to 10% by weight, preferably 1 % By weight to 7.5% by weight and in particular 2% by weight to less than 5% by weight, the proportion of polymeric polycarboxylate is as low as possible and in one preferred embodiment of the invention is less than 5 wt .-%. These also mentioned Substances are used in an anhydrous form. The share of other organic Polymers, such as polyvinylpyrrolidone, are preferably also possible low and is preferably in the range from 0.5% by weight to 1% by weight; in a Another preferred embodiment of the invention is the proportion of the sum polymeric polycarboxylate and other organic polymers below 5 wt .-%.

In addition to the abovementioned phosphate, crystalline alkali silicates and finely divided alkali alumosilicates, in particular zeolites of the NaA, X and / or P type, are suitable as inorganic builders for use in agents according to the invention. Suitable zeolites normally have a calcium binding capacity in the range from 100 to 200 mg CaO / g, which can be determined according to the information in German patent DE 24 12 837. Their particle size is usually in the range from 1 µm to 10 µm. They are used in dry form. The water contained in bound form in the zeolites does not interfere in the present case. Crystalline sheet silicates of the formula NaMSi _x O _{2 + x} yH ₂ O, in which M represents hydrogen or sodium, x is a number from 1.9 to, are preferably used as crystalline silicates, which may be present alone or in a mixture with the aluminosilicates mentioned 4 and y is a number from 0 to 20. Preferred values for x are 2, 3 and 4. Such crystalline layered silicates are described, for example, in European patent application EP 164 514.

In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, it being possible, for example, to obtain β-sodium disilicate by the process described in international patent application WO 91/08171. Usable crystalline silicates are commercially available under the names SKS-6 (manufacturer Hoechst) and Nabion® 15 (manufacturer Rhone-Poulenc). The content of inorganic builder material in the paste can be up to 35% by weight, preferably up to 25% by weight and in particular 10% by weight to 25% by weight.

In a preferred embodiment of agents according to the invention, 5% by weight to 25 % By weight, in particular 10% by weight to 20% by weight, of builder substances, the Amount of polymeric polycarboxylates not more than 10 wt .-%, especially not more than 7% by weight, and the amount of phosphonates not more than 2% by weight, in particular not more than 1% by weight

In addition, a paste-like agent according to the invention can contain an oxygen-containing oxidizing agent and optionally a bleach activator. Inorganic peroxygen compounds in particular are used as the oxidizing agent, the sodium perborate tetrahydrate and the sodium perborate monohydrate being of particular importance in addition to sodium percarbonate. Other suitable oxidizing agents are, for example, persulfates, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperoxyazelaic acid or diperoxydodecanedioic acid. Sodium percarbonate, sodium persulfate and / or sodium perborate monohydrate are preferably used. Oxidizing agents can be present in the agents according to the invention preferably in amounts of up to 25% by weight and in particular from 10% by weight to 20% by weight.

The oxidizing power of such oxidizing agents can be achieved by using bleach activators be improved, which form peroxocarboxylic acids under perhydrolysis conditions. There are numerous proposals for such bleach activators, especially from the substance classes the N- or O-acyl compounds, for example multiple acylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, Sulfurylamides and cyanurates, also carboxylic anhydrides, in particular Phthalic anhydride, carboxylic acid esters, especially sodium nonanoyloxy-benzenesulfonate, Sodium isononanoyl oxybenzenesulfonate and triacetin (glycerol triacetate), and Acylated sugar derivatives, such as pentaacetyl glucose, have become known in the literature. Preferably a bleach activator is used, the peracetic acid under the washing conditions forms, with tetraacetylethylenediamine being particularly preferred. invention Agents preferably contain up to 10% by weight, in particular from 3% by weight to 8% by weight Bleach activator. By adding bleach activators, the bleaching effect can be more aqueous Peroxide liquors are increased so far that even at temperatures around 60 ° C in essentially the same effects as with the peroxide liquor only occur at 95 ° C. Especially at even lower temperatures, the use of Transition metal salts and complexes, such as in European patent applications EP 0 392 592, EP 0 443 651, EP 0 458 397, EP 0 544 490, EP 0 549 271, EP 0 630 964 or EP 0 693 550 proposed as additional so-called bleaching catalysts to or instead of conventional bleach activators, an increase in Result in bleaching performance. Those from the German patent applications are also particularly suitable DE 195 29 905, DE 195 36 082, DE 196 05 688, DE 196 20 411 and DE 196 20 267 known as bleach activating catalysts Transition metal complexes. Bleach-activating transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru are in the invention Agents in amounts of preferably not more than 1% by weight, in particular of Contain 0.0025 wt .-% to 0.25 wt .-%.

In addition, an agent according to the invention can contain further washing auxiliaries which normally in amounts up to about 15% by weight, based on the finished product, can be present. Enzymes, graying inhibitors, soil release agents, color transfer inhibitors such as homo- and / or copolymers of vinyl pyrrolidone and / or vinyl imidazole, optical brighteners, additional foam regulators and / or colors and fragrances are used. So far Fragrances are contained, which are generally liquid, these go into the liquid Phase of inventive agents over. Because of their small amount, however, they have no appreciable influence on the flow behavior of the pastes.

The paste-like detergents according to the invention are preferably essentially free of water. "Essentially free of water" means a condition where the content of free, that is not in the form of water of hydration and Constitutional water less than 3% by weight, preferably less than 2% by weight and in particular is less than 1% by weight. Higher water contents are disadvantageous because they are Increase the viscosity of the agent disproportionately and in particular its stability reduce. Organic solvents, which are commonly found in liquid concentrates used low molecular weight and low boiling alcohols and ether alcohols count, as well as hydrotropic compounds, optionally in amounts of up to 6% by weight be included, but are preferably not present.

Enzymes which may be present in the agents according to the invention are in particular those from the class of proteases, lipases, cutinases, amylases, pullulanases, Xylanases, hemicellulases, cellulases, peroxidases and oxidases or their Mixtures in question, the use of protease, amylase, lipase and / or Cellulase is particularly preferred. The proportion is preferably 0.2% by weight to 1.5 % By weight, in particular 0.5% by weight to 1% by weight. The enzymes can be used in the usual way adsorbed on carriers and / or embedded in coating substances or as concentrated, water-free liquid formulations incorporated into the pastes become. Proteases that can be used are, for example, from international patent applications WO 91/02792, WO 92/21760, WO 93/05134, WO 93/07276, WO 93/18140, WO 93/24623, WO 94/02618, WO 94/23053, WO 94/25579, WO 94/25583, WO 95/02044, WO 95/05477, WO 95/07350, WO 95/10592, WO 95/10615, WO 95/20039, WO 95/20663, WO 95/23211, WO 95/27049, WO 95/30010, WO 95/30011, WO 95/30743 and WO 95/34627 are known. Be preferred over enzymes stabilized by oxidative damage, for example those under the trade names Durazym® or Purafect® OxP or Duramyl® or Purafect® OxAm known Proteases or amylases used.

Suitable graying inhibitors or soil release agents are Cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed cellulose ethers, such as methylhydroxyethyl cellulose, Methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose. Preferably are sodium carboxymethyl cellulose and their mixtures with methyl cellulose used. Soil release agents commonly used include Copolyester, the dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units contain. Soil-removing copolyesters of the type mentioned as well their use in detergents has been known for a long time. For example, the German Offenlegungsschrift DT 16 17 141 a washing process using Polyethylene terephthalate polyoxyethylene glycol copolymers. The German published application DT 22 00 911 relates to detergents, the nonionic surfactant and a copolymer of polyoxyethylene glycol and contain polyethylene terephthalate. In the German patent application DT 22 53 063 are acidic textile finishing agents called, which are a copolymer a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally contain an alkylene or cycloalkylene glycol. The European patent EP 066 944 relates to textile treatment agents which contain a copolyester made of ethylene glycol, Polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid contained in certain molar ratios. From the European patent EP 185 427 are methyl or ethyl end-capped polyesters with ethylene and / or Propylene terephthalate and polyethylene oxide terephthalate units and Detergents containing such soil release polymer are known. The European patent EP 241 984 relates to a polyester which, in addition to oxyethylene groups and terephthalic acid units also contains substituted ethylene units and glycerol units. The Proportion of graying inhibitors and / or soil release active ingredients in Agents according to the invention are generally not more than 2% by weight and are preferably 0.5% to 1.5% by weight. In a preferred embodiment of the Invention is the agent free of such active ingredients.

The color transfer inhibitors that are suitable for use in agents according to the invention include in particular polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole, and mixtures thereof. The proportion of color transfer inhibitors in agents according to the invention is preferably 0.1% by weight to 2% by weight, in particular 0.2% by weight to 1% by weight. In a preferred embodiment of the Invention is the agent free of such active ingredients.

As an optical brightener for in particular textiles made of cellulose fibers (for example Cotton) can, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts may be included. For example, are suitable Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) stilbene-2,2'disulfonic acid or compounds of the same structure that replace the morpholino group a diethanolamino group, a methylamino group or a 2-methoxyethylamino group wear. Furthermore, brighteners of the type of optionally substituted dibenzofuranylbiphenyl or optionally substituted 4,4'-distyryl-diphenyl, for example 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of brighteners can also be used. For Polyamide fibers are particularly suitable for brighteners of the 1,3-diaryl-2-pyrazoline type, for example 1- (p-sulfoamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and the like established connections. The content of the agent in optical brighteners respectively Brightener mixtures are generally not more than 1% by weight, preferably 0.05% to 0.5% by weight. In a preferred embodiment of the Invention is the agent free of such active ingredients.

The usual foam regulators which can be used in the agents according to the invention in addition to the foam-regulating compounds of the general formula III include, for example, polysiloxane-silica mixtures, the fine-particle silica contained therein preferably being silanated. The polysiloxanes can consist of both linear compounds and crosslinked polysiloxane resins and mixtures thereof. Further defoamers are paraffin hydrocarbons, in particular microparaffins and paraffin waxes, the melting point of which is above 40 ° C, saturated fatty acids or soaps with in particular 20 to 22 C atoms, for example sodium behenate, and alkali metal salts of phosphoric acid mono- or dialkyl esters, in which the alkyl chains each have 12 have up to 22 carbon atoms. Among these, sodium monoalkyl phosphate and / or dialkyl phosphate with C ₁₆ to C ₁₈ alkyl groups is preferably used. The proportion of foam regulators can preferably be 0.2% by weight to 2% by weight. In many cases, the additional use of defoaming agents can be dispensed with entirely.

To increase the physical stability as well as the chemical stability, in particular of the bleach component and enzymes which may be present, dehydrating agents can also be used, for example in the form of salts which bind water of crystallization, such as anhydrous sodium acetate, calcium sulfate, calcium chloride, sodium hydroxide, magnesium silicate, or metal oxides such as CaO, MgO, P ₄ O ₁₀ or Al ₂ O ₃ can be used. Such dehydrating agents, with which the water content of agents according to the invention can be reduced to particularly low values, are present in the agents in amounts of preferably 1% by weight to 10% by weight and in particular 2% by weight to 8% by weight of the invention.

For the production of paste-like detergents and cleaning agents according to the invention it is preferred that the nonionic surfactants of the formulas I and II and optionally IV presents, the alcohol or ether of formula III admixed and if necessary with another foam regulator, soap or underlying fatty acid, polymeric polycarboxylate or other organic Polymer, synthetic anionic surfactant and optical brightener into one homogeneous premix mixed. Such a premix is largely stable on storage and flowable at temperatures ranging from room temperature to 40 ° C, even if at these temperatures the components of the premix are not always complete be liquid or dissolved. This premix is, preferably after heating Temperatures in the range from 40 ° C to 120 ° C, in particular 60 ° C to 90 ° C, the Mixture of the remaining solid components of the paste-like agent admixed, the be dispersed in the premix, in particular by stirring. When the When the powder mixture is added, the temperature should not be below 60 ° C. Subsequently the mixture thus obtained is preferably subjected to a wet grinding process. This gives the product the desired consistency and homogeneity. The Addition of other, especially temperature or shear sensitive Ingredients such as perfume oils and enzymes are then made, making them homogeneous Incorporation should be done as gently as possible so as not to damage the structure of the paste to destroy. The resulting washing or cleaning agents according to the invention are direct after production by the acting shear forces flowable and pumpable and can be filled into normal sales containers.

A paste-like agent according to the invention preferably has a viscosity at 25 ° C. in the range from 80,000 mPas to 250,000 mPas, in particular 100,000 mPas to 250,000 mPas, measured with a Brookfield rotary viscometer (spindle no. 7) at 5 revolutions per minute. Under otherwise identical conditions, the viscosity at 50 revolutions per minute is preferably 20,000 mPa · s to 80,000 mPa · s. In order to take into account any thixotropy effect of the paste, these numerical values for viscosity refer to the reading after a measuring time of 3 minutes. In a particular embodiment of the invention, the paste-like detergent and cleaning agent preferably has a viscosity at room temperature such that it is not flowable under the action of gravity. It is then preferably particularly pseudoplastic, that is to say it has a significantly lower viscosity when sheared and is flowable under the influence of gravity, it being particularly preferred to have a viscosity in the range from 3,000 mPas to 12,000 mPas at 25 ° C. and a shear rate of 0.01 s ^-1 , to be determined using a CS rheometer from Bohlin with a plate / plate measuring system, plate spacing 0.5 to 4 mm. When subjected to sufficient shear forces, for example a shear rate of 10 s ^-1 and otherwise the same measurement conditions, an agent according to the invention preferably has a viscosity which is substantially 100 to 1000 times lower. The reduction in viscosity during shear is largely reversible, that is to say after the shear has ended, the agent returns to its original physical state without segregation occurring. In this context, it should be noted that the viscosities mentioned do not refer to measurements directly after the paste has been made, but to stored pastes, which are, so to speak, in equilibrium, since the shear forces acting as part of the manufacturing process lead to a lower paste viscosity, which only occurs in the Increased over time to the definitive final viscosity. Storage times of 1 month are usually completely sufficient for this.

An agent according to the invention normally has a density in the range of 1.3 kg / l up to 1.6 kg / l. The agent according to the invention can be used with conventional devices Dosing of pastes can be dosed, as for example in the international Patent application WO 95/29282, German patent application DE 19605 906, the German patent specification DE 44 30 418 or the European patent specifications EP 0 295 525 and EP 0 356 707 have been described. One for them Dosage of structurally viscous pasty detergents is particularly suitable The device is, for example, from international patent application WO 95/09263 is known and is preferred for metering pseudoplastic pastes according to the invention used. The detergents and cleaning agents according to the invention can optionally can also be filled pre-portioned into water-soluble films in particular. Such films are, for example, in European patent application EP 253 151 described.

Examples

Tables 1 and 2 below give some examples of the composition of detergents according to the invention. The pasty detergents had very good storage stability and had excellent cleaning performance even in the absence of synthetic anionic surfactant. Composition of pasty detergents (% by weight) 1 2 3 4 5 6 7 8th Nonionic surfactant I 12.5 12.5 12.5 12.5 12.5 12.5 12.5 6.5 Nonionic surfactant II 10 10 10 10 10 10 - - Nonionic surfactant II - - - - - - 10 10 Nonionic surfactant IV - - - - - - - 6 alkylbenzenesulfonate 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 PVP - - - - - - 1 1 isotridecanol 4 - 4 4 - - 5 5 dodecanol - 4 - - 4 - - - Builder I 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 Builder II 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 NTA 4 4 4 4 4 4 4 4 Na metasilicate 53 53 53 33 33 20 47 47 Na tripolyphosphate - - - - 20 20 - - CMC / MC 1 1 1 1 1 1 1 1 foam inhibitor 1 1 1 1 1 1 1 1 opt. brighteners 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Na carbonate to 100 Composition of pasty detergents (% by weight) 9 10 11 12 13 Nonionic surfactant I 15 15 7 6 8th Nonionic surfactant II 7 7 7 - - Nonionic surfactant II - - - 8th 8th Nonionic surfactant IV - - 8th 8th 6 alkylbenzenesulfonate 2.5 2.5 2.5 2.5 2.5 PVP - - - - 1 isotridecanol - - 5 - 5 decanol 5 5 - 5 - Builder I 5.5 5.5 5.5 5.5 5.5 Builder II 1.5 1.5 1.5 1.5 1.5 NTA 4 4 4 4 4 Na metasilicate 45 45 45 20 44 Na tripolyphosphate - - - 20 - CMC / MC 1 1 1 1 1 foam inhibitor 1 1 1 1 1 opt. brighteners 0.3 0.3 0.3 0.3 0.3 Na carbonate to 100

Claims (15)

1. A paste-form detergent for use in institutional laundries containing alkyl benzenesulfonates, nonionic surfactant, organic and/or inorganic builders, alkalizing agents and optionally bleaching agent, enzyme, redeposition-inhibiting polymer and/or other typical ingredients, characterized in that it contains 5% by weight to 30% by weight of an ethoxylated alcohol corresponding to general formula (I): R¹-(OC₂H₄)_m-OH in which R¹ is an alkyl or alkenyl group containing 9 to 15 carbon atoms and the average degree of ethoxylation m can assume values of 1 to 8,
   1% by weight to 20% by weight of an ethoxylated alcohol corresponding to general formula (II): R²-(OC₂H₄)_nOH in which R² is an alkyl or alkenyl group containing 12 to 22 carbon atoms and the average degree of ethoxylation n can assume values of 3 to 14, with the proviso that n is greater than m by at least 1.0,
   20% by weight to 80% by weight of alkalizing agent, 1% by weight to 20% by weight of medium-chain to long-chain alcohol or alkyl ether corresponding to general formula (III): R³-O-R⁴ in which R³ is an alkyl or alkenyl group containing 6 to 22 carbon atoms and R⁴ is hydrogen or an alkyl group containing 1 to 6 carbon atoms,
   up to 15% by weight of organic builder of the polymeric polycarboxylate type and up to 25% by weight, preferably up to 7.5% by weight and more particularly 0.5% by weight to 3% by weight of synthetic anionic surfactant selected from the alkyl benzenesulfonates.
2. A detergent as claimed in claim 1, characterized in that it contains 10% by weight to 25% by weight of the ethoxylated alcohol corresponding to general formula I.
3. A detergent as claimed in claim 1 or 2, characterized in that it contains 5% by weight to 15% by weight of the ethoxylated alcohol corresponding to general formula II.
4. A detergent as claimed in claim 3, characterized in that the average degree of ethoxylation n of the surfactant of formula II is higher by at least 2.0 than the average degree of ethoxylation m of the surfactant of general formula I.
5. A detergent as claimed in any of claims 1 to 4, characterized in that it contains 3% by weight to 15% by weight of compounds corresponding to general formula III, particularly those in which R⁴ is hydrogen.
6. A detergent as claimed in any of claims 1 to 5, characterized in that it additionally contains up to 20% by weight and, more particularly, up to 10% by weight of an alkoxylated alcohol corresponding to general formula IV: R⁵-(OC₂H₄)_x-(OC₃H₆)_y-OH in which R⁵ is an alkyl or alkenyl group containing 9 to 15 carbon atoms and the average degree of ethoxylation x can assume a value of 3 to 7 and the average degree of propoxylation y a value of 2 to 8.
7. A detergent as claimed in any of claims 1 to 6, characterized in that it contains up to 5% by weight and, more particularly, 0.5% by weight to 2% by weight of soap and/or 0.5% by weight to 1% by weight of polyvinyl pyrrolidone.
8. A detergent as claimed in any of claims 1 to 6, characterized in that it contains 30% by weight to 70% by weight and, more particularly, 40% by weight to 60% by weight of alkalizing agent.
9. A detergent as claimed in any of claims 1 to 8, characterized in that it contains 5% by weight to 25% by weight and, more particularly, 10% by weight to 20% by weight of builders.
10. A detergent as claimed in any of claims 1 to 9, characterized in that the ingredients of the paste-form detergent present as solid phase are fine-particle materials and have a mean particle size of 5 µm to 200 µm and, more particularly, 10 µm to 80 µm.
11. A detergent as claimed in any of claims 1 to 10, characterized in that at most 15% of the particles of the ingredients present as solid phase have a particle size of more than 200 µm.
12. A detergent as claimed in any of claims 1 to 11, characterized in that it contains 0.2% by weight to 1.5% by weight and, more particularly, 0.5% by weight to 1% by weight of enzyme, more particularly protease, amylase, lipase and/or cellulase.
13. A detergent as claimed in any of claims 1 to 12, characterized in that it contains 1% by weight to 10% by weight and, more particularly, 2% by weight to 8% by weight of dehydrating agent.
14. A detergent as claimed in any of claims 1 to 13, characterized in that it has a viscosity at 25°C of 80.000 mPa·s to 250,000 mPa·s, as measured with a Brookfield rotational viscosimeter (spindle No. 7) at 5 revolutions per minute, and a viscosity under otherwise the same conditions of 20,000 mPa·s to 80,000 mPa·s at 50 revolutions per minute.
15. A process for producing the paste-form detergent claimed in any of claims 1 to 14, characterized in that the nonionic surfactants of formulae I and II and optionally IV are initially introduced, the alcohol or ether corresponding to formula III is added and the whole is optionally mixed with more foam regulator, soap or the basic fatty acid, polymeric polycarboxylate or other organic polymer, synthetic anionic surfactant and optical brightener to form a homogeneous premix, the mixture of the remaining solid ingredients of the paste-form detergent is added to the premix thus formed, preferably after heating to temperatures of 40°C to 120°C and, more particularly, in the range from 60°C to 90°C and are dispersed in the premix, more particularly by stirring, the mixture thus obtained is then subjected to wet grinding which gives the product the required consistency and homogeneity, after which other ingredients, more particularly temperature-sensitive or shearing-sensitive ingredients, are uniformly incorporated as carefully possible.