EP0954559B1 - Produit detergent et nettoyant a l'etat pateux - Google Patents

Produit detergent et nettoyant a l'etat pateux Download PDF

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Publication number
EP0954559B1
EP0954559B1 EP98907965A EP98907965A EP0954559B1 EP 0954559 B1 EP0954559 B1 EP 0954559B1 EP 98907965 A EP98907965 A EP 98907965A EP 98907965 A EP98907965 A EP 98907965A EP 0954559 B1 EP0954559 B1 EP 0954559B1
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EP
European Patent Office
Prior art keywords
weight
detergent
alkyl
carbon atoms
general formula
Prior art date
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Expired - Lifetime
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EP98907965A
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German (de)
English (en)
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EP0954559A1 (fr
Inventor
Thomas Merz
Khalil Shamayeli
Edgar Köppelmann
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Ecolab GmbH and Co OHG
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Ecolab GmbH and Co OHG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C11D1/8305—Mixtures of non-ionic with anionic compounds containing a combination of non-ionic compounds differently alcoxylised or with different alkylated chains
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • 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.
  • 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.
  • the pour point solidification point
  • 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.
  • Another paste-like detergent which is a nonionic surfactant 40 to 70 %
  • 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.
  • 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.
  • 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 alkeny
  • 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.
  • 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.
  • the surfactant component is preferably free from exclusively propoxylated alcohols.
  • R 4 is preferably a methyl, ethyl, propyl or butyl group, hydrogen and the methyl group, in particular hydrogen, being particularly preferred.
  • 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.
  • 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 %
  • 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 ⁇ m.
  • 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 ⁇ m.
  • 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.
  • 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.
  • polymeric alkali metal phosphates such as sodium tripolyphosphate
  • 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.
  • 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.
  • 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.
  • 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 .-%.
  • organic Polymers such as polyvinylpyrrolidone
  • 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 .-%.
  • crystalline alkali silicates and finely divided alkali alumosilicates 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 ⁇ m to 10 ⁇ m. They are used in dry form. The water contained in bound form in the zeolites does not interfere in the present case.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, it being possible, for example, to obtain ⁇ -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.
  • 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
  • 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.
  • 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
  • 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.
  • 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 .-%.
  • 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.
  • 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.
  • 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.
  • the agent free of such active ingredients is preferred embodiment of the Invention.
  • 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.
  • diaminostilbenedisulfonic acid 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the temperature should not be below 60 ° C.
  • 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.
  • 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.
  • 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.
  • an agent according to the invention 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.
  • 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.
  • 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 12.5 6.5

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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Claims (15)

  1. Produit de lavage à l'état pâteux pour l'utilisation dans les laveries industrielles, contenant un alkyl benzène sulfonate, un agent tensioactif non ionique, des agents de structuration organiques et/ou minéraux, des agents d'alcalinisation, ainsi que le cas échéant des agents de blanchiment, un enzyme, un polymère inhibiteur de grisaillement et/ou d'autres ingrédients usuels,
    caractérisé en ce qu'
    il contient de 5 % en poids à 30 % en poids d'un alcool éthoxylé de formule générale I : R1 - (OC2H4)m - OH dans laquelle R1 signifie un reste alkyle ou alkényle ayant de 9 à 15 atomes de carbone, et le degré moyen d'éthoxylation m peut prendre des valeurs allant de 1 à 8,
    de 1 % en poids à 20 % en poids d'un alcool éthoxylé de formule générale II : R2 - (OC2H4)n - OH dans laquelle R2 signifie un reste alkyle ou alkényle ayant de 12 à 22 atomes de carbone, et le degré moyen d'éthoxylation n peut prendre des valeurs allant de 3 à 14, avec la restriction que n est au moins plus grand de 1 que m; de 20 % en poids à 80 % en poids d'agent d'alcalinisation, de 1 % en poids à 20 % en poids d'alcool à chaíne moyenne à longue ou un éther d'alkyle de formule générale III R3-O-R4 dans laquelle R3 signifie un reste alkyle ou alkényle ayant de 6 à 22 atomes de carbone, et R4 signifie de l'hydrogène ou un reste alkyle ayant de 1 à 6 atomes de carbone, et jusqu'à 15 % en poids d'un agent de structuration organique du type des polycarboxylates polymères ainsi que jusqu'à 25 % en poids - de préférence jusqu'à 7,5 % en poids - et en particulier de 0,5 % en poids à 3 % en poids d'un agent tensioactif anionique synthétique choisi parmi les alkyl benzène sulfonates.
  2. Produit selon la revendication 1,
    caractérisé en ce qu'
    il contient de 10 % en poids à 25 % en poids, d'alcool éthoxylé de formule générale I.
  3. Produit selon la revendication 1 ou la revendication 2,
    caractérisé en ce qu'
    il contient de 5 % en poids à 15 % en poids, d'alcool éthoxylé de formule générale II.
  4. Produit selon la revendication 3,
    caractérisé en ce que
    le degré moyen d'éthoxylation n de l'agent tensioactif conformément à la formule II est plus grand d'au moins 2,0 que le degré moyen d'éthoxylation de l'agent tensioactif conformément à la formule I.
  5. Produit selon l'une des revendications 1 à 4,
    caractérisé en ce qu'
    il contient de 3 % en poids à 15 % en poids en composés de formule générale III, en particulier ceux dans lesquels R4 est de l'hydrogène.
  6. Produit selon l'une des revendications 1 à 5,
    caractérisé en ce qu'
    il contient en supplément jusqu'à 20 % en poids en particulier jusqu'à 10 % en poids d'un alcool éthoxylé de formule générale IV : R5-(OC2H4)x-(OC3H6)y-OH dans laquelle R5 signifie un reste alkyle ou alkényle ayant de 9 à 15 atomes de carbone, et où le degré moyen d'éthoxylation ne peut prendre des valeurs allant de 3 à 7, et le degré de propoxylation moyen y des valeurs allant de 2 à 8.
  7. Produit selon l'une des revendications 1 à 6,
    caractérisé en ce qu'
    il contient jusqu'à 5 % en poids, en particulier de 0,5 % en poids à 2 % en poids de savon et/ou de 0,5 % en poids à 1 % en poids de polyvinyl-pyrolidone.
  8. Produit selon l'une des revendications 1 à 7,
    caractérisé en ce qu'
    il contient de 30 % en poids à 70 % en poids en particulier de 40 % en poids à 60 % en poids d'agent d'alcalinisation.
  9. Produit selon l'une des revendications 1 à 8,
    caractérisé en ce qu'
    il contient de 5 % en poids à 25 % en poids en particulier de 10 % en poids à 20 % en poids de substances d'agent de structuration.
  10. Produit selon l'une des revendications 1 à 9,
    caractérisé en ce que
    les constituants contenus sous forme de phase solide du produit à l'état pâteux sont finement divisés et possèdent une taille moyenne de grains dans la zone de 5 µm à 200 µm, en particulier de 10 µm à 80 µm.
  11. Produit selon l'une des revendications 1 à 10,
    caractérisé en ce qu'
    au maximum 15 % des particules des constituants contenus sous forme de phase solide, possèdent une taille de grains supérieure à 200 µm.
  12. Produit selon l'une des revendications 1 à 12,
    caractérisé en ce qu'
    il contient de 0,2 % en poids à 1,5 % en poids - en particulier de 0,5 % en poids à 1 % en poids - d'enzymes en particulier de protéase, d'amylasc, de lipase et/ou de cellulase.
  13. Produit selon l'une des revendications 1 à 12,
    caractérisé en ce qu'
    il contient de 1 % en poids à 10 % en poids - en particulier de 2 % en poids à 8 % en poids - d'agent déshydratant.
  14. Produit selon l'une des revendications 1 à 13,
    caractérisé en ce qu'
    il possède à 25°C une viscosité allant de 80 000 mPas à 250 000 mPas - mesurée avec un viscosimètre à rotation Brookfield (tige n° 7) à 5 tours par minute et dans des conditions par ailleurs identiques à 50 tours par minute une viscosité allant de 20 000 mPas à 80 000 mPas.
  15. Procédé de production d'un produit à l'état pâteux conformément à l'une des revendications 1 à 14,
    caractérisé en ce qu'
    on introduit les agents tensioactifs non ioniques de formules I et II ainsi qu'éventuellement IV, on mélange l'alcool ou l'éther de formule III ainsi qu'éventuellement avec un autre régulateur de mousse, des savons ou des acides gras sous jacents, un polycarboxylate polymère et un autre polymère organique, un agent tensioactif anionique synthétique et un azurant optique en un prémélange homogène, on mélange à cc prémélange après chauffage à des températures dans la zone de 40°C à 120°C, en particulier de 60°C à 90°C le mélange des constituants solides restants du produit en particulier dispersés par agitation en prémélange à l'état pâteux, ensuite on soumet le mélange ainsi obtenu à un processus de broyage à l'état humide, grâce à quoi le produit obtient la consistance désirée ainsi que l'homogénéité voulue, et à la suite de cela on incorpore d'autres ingrédients - en particulier sensibles à la température ou sensibles au cisaillement d'une manière homogène la plus modérée possible.
EP98907965A 1997-01-30 1998-01-21 Produit detergent et nettoyant a l'etat pateux Expired - Lifetime EP0954559B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19703364A DE19703364A1 (de) 1997-01-30 1997-01-30 Pastenförmiges Wasch- und Reinigungsmittel
DE19703364 1997-01-30
PCT/EP1998/000299 WO1998033881A1 (fr) 1997-01-30 1998-01-21 Produit detergent et nettoyant a l'etat pateux

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EP0954559A1 EP0954559A1 (fr) 1999-11-10
EP0954559B1 true EP0954559B1 (fr) 2002-10-23

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AT (1) ATE226627T1 (fr)
CA (1) CA2278743C (fr)
DE (2) DE19703364A1 (fr)
ES (1) ES2185149T3 (fr)
HU (1) HUP0001025A3 (fr)
PL (1) PL186322B1 (fr)
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HUP0001025A3 (en) 2003-02-28
DE19703364A1 (de) 1998-08-06
EP0954559A1 (fr) 1999-11-10
HUP0001025A2 (hu) 2000-09-28
WO1998033881A1 (fr) 1998-08-06
ES2185149T3 (es) 2003-04-16
US6329333B1 (en) 2001-12-11
CA2278743C (fr) 2007-05-15
CA2278743A1 (fr) 1998-08-06
SK101799A3 (en) 2000-05-16
PL186322B1 (pl) 2003-12-31
DE59806048D1 (de) 2002-11-28
ATE226627T1 (de) 2002-11-15
PL334944A1 (en) 2000-03-27

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