EP0876456A1 - Procede pour la preparation de granules antisouillure a support de dextrine, et agents les contenant - Google Patents

Procede pour la preparation de granules antisouillure a support de dextrine, et agents les contenant

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Publication number
EP0876456A1
EP0876456A1 EP96941046A EP96941046A EP0876456A1 EP 0876456 A1 EP0876456 A1 EP 0876456A1 EP 96941046 A EP96941046 A EP 96941046A EP 96941046 A EP96941046 A EP 96941046A EP 0876456 A1 EP0876456 A1 EP 0876456A1
Authority
EP
European Patent Office
Prior art keywords
weight
polymer
dirt
dextrin
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96941046A
Other languages
German (de)
English (en)
Inventor
Manfred Greger
Thomas Möller
Beatrix Kottwitz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0876456A1 publication Critical patent/EP0876456A1/fr
Withdrawn legal-status Critical Current

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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin

Definitions

  • the present invention relates to a process for the preparation of granular detergent components which can be scooped and poured and which contain a dirt-releasing polymer and dextrin as finely divided carrier material for this polymer, the use of such granules for the production of solid detergents and cleaning agents, and detergents and cleaning agents, which contain a combination of soil release polymer and dextrin.
  • detergents and cleaning agents In addition to the surfactants which are indispensable for the washing or cleaning performance, detergents and cleaning agents normally also contain so-called builder substances, which have the task of supporting the performance of the surfactants by hardening agents, that is to say essentially calcium and magnesium ions to eliminate from the wash liquor that they do not interact in a negative way with the surfactants.
  • builder substances which improve the primary washing power is zeolite Na-A, which is known to be able to form complexes, in particular with calcium ions, such that their reaction with water hardness-forming anions, in particular carbonate, to suppress insoluble compounds is suppressed.
  • the builders in particular in textile detergents, are intended to prevent the redeposition of the dirt detached from the fiber or in general from the surface to be cleaned, and also from the reaction of water-hardness-forming cations with water-hardness-forming anions to form insoluble compounds on the cleaned textile or the surface.
  • co-builders usually polymeric polycarboxylates, are used which, in addition to their contribution to the secondary washing ability, also have a complexing action against the water-hardness-forming cations.
  • detergents generally contain further constituents which can be summarized under the term washing auxiliaries and which comprise such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents, bleach activators and color transfer inhibitors.
  • auxiliary substances also include substances which give the laundry fiber dirt-repellent egg properties and which, if present during the washing process, support the dirt-removing ability of the other detergent components. The same applies analogously to cleaning agents for hard surfaces.
  • dirt-removing substances are often referred to as "soil-release" substances.
  • the dicarboxylic acid units , Alkylene glycol units and polyalkylene glycol units contain dirt-containing copolyesters of the type mentioned, and their use in detergents has been known for a long time
  • German Offenlegungssch ⁇ ft DT 16 17 141 describes a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers.
  • German laid-open specification DT 22 00 911 relates to detergents which contain nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate.
  • German published specification DT 22 53 063 are acidic textile finishing agents called a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally an alkylene or cycloalkylene glycol Dicarboxylic acid contained in certain molar ratios.
  • European or European patent EP 185 427 describes methyl or ethyl group-terminated polyesters with ethylene and / or propylene terephthalate and polyethylene Oxide terephthalate units and detergents containing such a soil release polymer are known.
  • 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 glycene units
  • German published patent application DE 33 24 258 therefore proposes spraying a solution or dispersion of a dirt-releasing active ingredient in non-ionic surfactant onto a detergent particle containing builder. With this procedure, there is a risk of the sprayed particles sticking together due to the low-melting point nonionic surfactant on their surface.
  • One object of the invention is a process for the production of granular detergent components which can be poured and poured and which contain a dirt-releasing polymer and a finely divided carrier material, with a Room temperature-solid dirt-releasing polymer, which in particular contains ethylene terephthalate and polyoxyethylene terephthalate groups, is heated to a temperature at which it has a viscosity below 5000 mPas and the surfactant-free polymer melt thus obtained is applied to the finely divided carrier material in a compacting mixer at a mixing temperature which is at least as high as the solidification temperature of the polymer, or on a fluidized bed of the support material at a temperature which is at most as high as the solidification temperature of the polymer is applied, which is characterized in that the carrier material contains dextrin
  • the invention therefore furthermore relates to detergents and cleaning agents which contain a combination of dirt-releasing polymer and dextrin.
  • this combination is preferably achieved by using an abovementioned granular detergent component which contains a dirt-releasing polymer and dextins as the carrier material included introduced.
  • Another object of the invention is thus the use of such granular detergent components for the production of solid, in particular particulate detergents and cleaning agents
  • a polymer to be used in the process according to the invention it is possible to heat a polymer to be used in the process according to the invention to a temperature, for example 150 ° C., at which it becomes very thin, for example having a viscosity of only 5 mPas to 10 mPas If the polymer is heated to a temperature at which it has a viscosity in the range from 10 mPas to 4500 mPas, in particular from 50 mPas to 2000 mPas, these viscosity regions are normally at temperatures of at most about 100 ° C., in particular about 50 ° C above the solidification or softening temperature of the polymer, which is then in the form of a melt.
  • the viscosity can be determined by conventional methods, for example with the aid of a shear stress-controlled plate viscometer or a rotary viscometer (shear rate 10 s 1 to 100 s 1 )
  • the solidification or softening temperature of the polymer which can be determined by known methods, for example by means of DSC, is preferably in the range from 40 ° C. to 80 ° C.
  • the polymers preferably have molar masses in the range from 600 to 100,000.
  • the process according to the invention makes it easy to produce ⁇ esel and free-flowing, non-sticky granules with a high content of dirt-releasing polymer. Based on the resulting granules, preferably 15% by weight to 75% by weight, in particular 20% by weight to 60% by weight % and particularly preferably 30% by weight to 60% by weight of polymer onto the carrier material.
  • dirt-releasing polymers which contain ethylene terephthalate and polyoxyethylene terephthalate groups in molar ratios of from 9 1 to 1.9.
  • Other monomer units for example propylene glycol, polypropylene glycol, alkylene or alkenylene dicarboxylic acids, isophthalic acid, carboxy- or sulfonic acid-substituted phos- phosubstituted phthalate-substituted phthalate ⁇ possible polymer may be included.
  • Derivatives which are capped by end groups that is to say polymers which have neither free hydroxyl groups nor free carboxyl groups but instead carry, for example, C 1-4 alkyl groups or are terminally esterified with monobasic carboxylic acids, for example benzoic acid or sulfobenzoic acid, can also be used according to the invention.
  • polyesters which, in addition to oxyethylene groups and terephthalic acid units, contain 1, 2-propylene, 1, 2-butylene and / or 3-methoxy-1, 2-propylene groups and glycerol units and are end-capped with C r to C 4 alkyl groups, the soil release polymers used in EP 253 567 with a molecular weight of 900 to 9000 made of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 0 , 6 to 0.95, known from EP 272 033, at least in part by C 1-4 -Al alkyl or acyl residues end-capped polyesters with poly-propylene terephthalate and polyoxyethylene terephthalate units, the sulfoethyl-end group-capped terephthalate-containing soil-
  • a is a number from 2 to 8
  • b is a number from 1 to 300
  • o is a number from 2 to 8
  • p is a number from 1 to 300
  • y is a number from 1 to 500
  • Ph an o-, m- or p-phenylene radical, which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R is selected from hydrogen, an alkyl radical having 1 to 22 carbon atoms and their mixtures
  • X and Y independently of one another from hydrogen, alkyl and aryl monocarboxylic acid residues with 5 to 32 carbon atoms, hydroxymonocarboxylic acid residues with 2 to 22 carbon atoms and a degree of oligomerization from 1 to 100 and dicarboxylic acid half-ester residues
  • the second carboxylic acid group is esterified with an alcohol A- (OCHZCH 2 )
  • the dirt-free polymer can be applied in admixture with small amounts of other substances, for example fabric softeners, silicones, oxidation inhibitors and / or discoloration inhibitors, in the process according to the invention, it being essential that the admixtures at the desired process temperature increase the viscosity of the then do not increase the mixture present above the limit value specified above.
  • the admixtures are therefore at the temperature to which the polymer is applied before spraying, either liquid or homogeneous, dissolved in the dirt-releasing polymer. Your proportion, based on the mixture to be applied, is preferably not more than 10% by weight.
  • dextrin can be used as the sole carrier material or additional finely divided substances in the form of a carrier material mixture can be used.
  • additional finely divided substances include very fine powdery materials with diameters in the micrometer range, for example zeolites in detergent quaternate, in particular Zeohth-A and / or Zeolite-P, but also coarser materials with diameters down to the millimeter range.
  • the additional carrier materials are preferably with an average grain diameter in the range from 2 ⁇ m to 1.5 mm, in particular from 3 ⁇ m to 10 ⁇ m or from 0.1 mm to 1 mm , used The nature of the additional carrier material is not critical, provided that it is stable at the processing temperature.
  • Substances which are common ingredients of detergents and cleaning agents are preferably also used as additional carrier materials.
  • Alkali sulfates, alkali are particularly suitable carbonates, alkali hydrogen carbonates, silica, alkali silicates, which can be amorphous or crystalline, and alkali alumosilicates, which can also be amorphous or crystalline, but also organic substances, such as alkali citrates, and mixtures thereof.
  • Preferred additional carrier materials include synthetic, especially X-ray amorphous, since when they are used particularly large amounts, that is to say more than 60% by weight, based on the resulting granulate, of dirt-releasing polymer can be applied, and a particularly uniform, fine grain spectrum of the resulting granulate is obtained.
  • Such additional carrier materials can, if desired, be used in amounts of up to 99% by weight. %, usually up to 50% by weight and in particular from 0.5% by weight to 10% by weight, in each case based on the entire carrier material, can be used.
  • the proportion of the powdering agent, based on the resulting powdered granules being of the order of about 1% by weight to about 10% by weight, for example about 4% by weight
  • at least a proportion of the carrier material for the dirt-releasing polymer in the process according to the invention, or a further component of the combination essential to the invention is dextrin.
  • dextrins are understood to be ohgo- or polymers of carbohydrates which are partially hydrolysed by starches
  • the hydrolysis can be carried out by customary, for example acid- or enzyme-catalyzed, processes. It is preferably hydrolysis products with average molecular weights in the range from 440 to 500,000.
  • the dextrin used in the process according to the invention or in the compositions according to the invention is preferably a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which is a DE of 100, usable are both maltodextins (DE 3 to 20) and dry glucose syrups (DE 20 to 37) as well as so-called yellow dextrins and white dextrins with higher average molecular weights in the range from about 2,000 to 30,000.
  • a preferred dextrin is in Europe Patent application EP 0 793 292 described
  • the washing or cleaning agents according to the invention preferably contain 0.5% by weight to 10% by weight, in particular 2% by weight to 7% by weight of dextrin and 0.1% by weight to 5% by weight, in particular 0.2% by weight. contain up to 2.5% by weight of dirt-releasing polymer
  • the weight ratio of dextrin to dirt-releasing polymer is preferably in the range from 25 1 to 1 2, in particular from 10 1 to 1 1% by weight
  • the detergents and cleaning agents according to the invention which can be present in particular as particulate solids, pastes, homogeneous solutions or suspensions, can, in addition to the active ingredient combination of dirt-releasing polymer and dextrin, in principle contain all known ingredients customary in such agents - and cleaning agents can in particular surface-active surfactants, bleaching agents, bleach activators, water-miscible organic solvents, enzymes, additional builder substances, sequestering agents, electrolytes, pH regulators and other auxiliary substances such as optical brighteners, graying agents. inhibitors, color transfer inhibitors, foam regulators, abrasives, dyes and fragrances
  • the agents according to the invention can contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof.
  • Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched Alcohols each having 12 to 18 carbon atoms in the alkyl part and 3 to 20, preferably 4 to 10 alkyl ether groups.
  • corresponding ethoxylation and / or propoxylation products of N-alkyl amines, vicinal diols, fatty acid esters and fatty acid amides are the same as those mentioned with regard to the alkyl part correspond to long-chain alcohol derivatives, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical
  • Suitable anionic surfactants are, in particular, soaps and those which contain sulfate or sulfonate groups with preferably alkali non-ions as cations.
  • Usable soaps are preferably the alkali metal salts of saturated or unsaturated fatty acids with 12 to 18 carbon atoms. Such fatty acids can also be used in a form which is not completely neutralized
  • the surfactants of the sulfate type which can be used include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 C atoms and the sulfation products of the nonionic surfactants mentioned with a low degree of ethoxylation.
  • the sulfonate-type surfactants which can be used include linear alkylbenzenesulfonates with 9 to 14 carbon atoms in the alkyl part, alkane sulfonates with 12 to 18 carbon atoms, and olefin sulfonates with 12 to 18 carbon atoms, which are formed in the reaction of corresponding mono-olefins with sulfur trioxide, and alpha-sulfofatty acid esters, which are used in the sul - Formation of fatty acid methyl or ethyl esters arise
  • Such surfactants are present in the cleaning or washing agents according to the invention in proportions of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30% by weight.
  • the agents mentioned for cleaning dishes can have the lower limits mentioned are below, the surfactant content in such agents is preferably 0.1% by weight to 20% by weight, in particular 0.2% by weight to 5% by weight
  • Suitable peroxygen-based bleaching agents in the agents according to the invention are, in particular, organic peracids, hydrogen peroxide and inorganic salts which give off hydrogen peroxide under the cleaning conditions, such as percarbonate, perborate and / or persihkat.
  • solid peroxygen compounds are to be used, they can be used in the form of powders or granules which can also be encased in a manner known in principle.
  • Alkali perborate monohydrate and / or alkali percarbonate is preferably used.
  • Peroxygen compounds are in amounts of preferably 10% by weight to 30% by weight, in particular 15% by weight to 25% by weight. available
  • the bleach activators optionally contained in the agents according to the invention include, in particular, compounds which, under perhydrolysis conditions, yield aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances which are O- and / or carry N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • Carboxylic acid anhydrides especially phthalic anhydride, acylated polyhydric alcohols, especially t ⁇ acetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dydhydrofura ⁇ and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767 as well as acetylated sorbitol and mannitol or their in the mixtures described in European patent application EP 0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or t-acylated lac,
  • N-benzoylcaprolactam which are known from international
  • the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0 446 982 and EP 0 453 003 may also be present as so-called bleaching catalysts.
  • the transition metal compounds in question include, in particular, the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 195 29 905 and their N-analog compounds known from German patent application DE 196 20 267, the manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes known from German patent application DE 195 36 082, the manganese, iron, cobalt described in German patent application DE 196 05 688 , Ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripods, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 196 20 411, which are described in the German patent application Manganese, copper and cobalt complexes described in DE 44 16 438, the cobalt complexes described in the European patent application EP 0 272 030, the M known from the European patent application EP 0 693 550 an
  • bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO 95/27775.
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in conventional amounts, preferably in an amount of up to 1% by weight, in particular of 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total average
  • An agent according to the invention preferably contains, in addition to dextrin, at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • polyphosphates preferably sodium phosphate
  • crystalline or amorphous materials are considered as water-insoluble, water-dispersible inorganic builder materials
  • Alkalumuminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid formulations in particular from 1% by weight to 5% by weight, are used.
  • crystalline sodium aluminosilicates in detergent quaternate in particular zeolite A , Zeolite P and optionally zeolite X, preferably amounts close to the upper limit mentioned are preferably used in solid, particulate compositions.
  • Suitable aluminosilicates in particular have no particles with a grain size greater than 30 ⁇ m and preferably do not exist enough at least 80% by weight of particles with a size of less than 10 ⁇ m.
  • Your calcium binding capacity which can be determined according to the information in German patent DE 24 12 837, is generally in the range from 100 to 200 mg CaO per gram
  • Suitable substitutes or partial substitutes for the alumosilicate mentioned are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to Si0 2 below 0.95, in particular of 1 1, 1 to 1 12 and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na 2 0 SiO 2 of 1 2 to 1 2.8 those with a molar ratio Na 2 O S ⁇ O 2 of 1 1, 9 to 1 2.8 can be prepared by the process of European patent application EP 0 425427. In the preparation of agents according to the invention they are preferably added as a solid and not in the form of a solution.
  • crystalline silicates the alone or in a mixture with amorphous silicates, are preferably crystals talline layered silicates of the general formula Na 2 S ⁇ x 0 2x + 1 y H2O, in which x, the so-called modulus, is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514.
  • Preferred crystalline layered silicates are those in which x in the general formula mentioned assumes the values 2 or 3 in particular Both ⁇ - and ⁇ -sodium disilicate (Na 2 Si 2 O 5 y H 2 O) are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the method described in international patent application WO 91/08171 ⁇ -sodium silicate with a modulus between 1, 9 and 3.2 can be prepared in accordance with Japanese patent applications JP 04/238 809 or JP 04/260 610. Practically anhydrous crystalline alkali silicates of the above general formula, in which x is a number of.
  • agents according to the invention prepared from amorphous alkali silicates 1, 9 to 2.1 means producible as described in European patent applications EP 0 548 599, EP 0 502 325 and EP 0 452 428, k Can be used in agents according to the invention
  • a crystalline sodium layer layer with a modulus of 2 to 3 is used, as can be produced from sand and soda by the process of European patent application EP 0 436 835 with crystalline layer layers
  • alkali aluminum silicate If additional builder substance is also used, alkali aluminum silicate, If zeolite is present in particular, the weight ratio of aluminosilicate to silicate, based in each case on water-free active substances, is preferably 4 1 to 10 1. In compositions which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably two se 1 2 to 2 1 and in particular 1 1 to 2 1
  • the water-soluble organic builder substances include aminopolycarboxylic acids, in particular nit ⁇ lot ⁇ acetic acid and ethylenediaminetetraacetic acid, polyphosphonic acids, in particular aminotronic acid (methylenephosphonic acid), ethylenediamine tetrak ⁇ s (methylenephosphonic acid) and 1-hydroxyethane, polyacid-1-acid, 1-cyanonic acid , and polymeric (poly) carboxylic acids, in particular polycarboxylates accessible by oxidation of polysaccharides, such as those obtained from European patent applications EP 427 349, EP 472 042 and EP 542 496 and the international patent applications WO 93/08251, WO 93/16110, WO 95/07303 and WO 95/12619 are known.
  • aminopolycarboxylic acids in particular nit ⁇ lot ⁇ acetic acid and ethylenediaminetetraacetic acid
  • polyphosphonic acids in particular aminotronic acid (methylenephosphonic acid), ethylenediamine tet
  • This oxidative modification can be carried out, for example, using Fe, Cu, Ag, Co or Ni catalysts, as described in international patent application WO 92/18542, with the aid of Pd, Pt, Rh or Os catalysts, as in the European EN Patent EP 0 232 202 described, or by means of a quinone / hydroquinone system in alkaline with the addition of oxygen and optionally aftertreatment with hydrogen peroxide.
  • cobuilders are polymeric acrylic acids, methacrylic acids, cornic acids and copolymers of these, which also contain small amounts of polymerizable substances can be incorporated in a polymerized form without carboxylic acid functionality.
  • the relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, in each case 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 ether, such as vinyl methyl ether, vinyl esters, ethylene, propylene and styrene of 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 a vinyl alcohol derivative 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 a C 4 -C 8 -dicarbonic acid, preferably a C 4 -C 8 -dicarboxylic acid, maleic acid being particularly
  • the third monomeric unit is in this case formed from vinyl alcohol and / or an esterified vinyl alcohol.
  • vinyl alcohol derivatives are preferred, in which short-chain carboxylic acids, for example C 1 -C 4 -carboxylic acids, are esterified with vinyl alcohol.
  • Preferred terpolymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and 5% by weight to 40% by weight %, preferably 10% by weight to 30% by weight, vinyl alcohol and / or vinyl acetate.
  • the second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is substituted in the 2-position with an alkyl radical, preferably with a C r C 4 alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives.
  • Preferred terpolymers contain 40% by weight % to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight, preferably 15% by weight to 25% by weight % Methallylsulfonic acid or methallylsulfonate and as third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight of a carbohydrate.
  • This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono- , Di- or Oligosaccha ⁇ de are preferred. Among these, sucrose is particularly preferred.
  • terpolymers 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 between 1,000 and 200,000, preferably between 200 and 50,000 and in particular between 3,000 and 10,000 on further 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.
  • the organic builders ⁇ substances especially for the production of liquid agents, in the form of aqueous lo solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions.
  • All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • dextrin makes it possible to dispense entirely with such conventional organic co-builders, in particular with polymerization products of unsaturated carboxylic acids, without suffering any loss in the performance of the detergent or cleaning agent.
  • conventional organic builder substances can be present in amounts of up to 5% by weight, in particular from 1% by weight to 4% by weight. Quantities close to the upper limit mentioned are preferably used in pasty or liquid compositions.
  • Builder substances in total are preferably contained in the washing or cleaning agents according to the invention in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight
  • Enzymes which can be used in the compositions are those from the class of proteases, lipases, cutinases, amylases, pullulanases, cellulases, oxidases and peroxidases and mixtures thereof. Enzymes obtained from fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas alcaligenes, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia are particularly suitable.
  • the enzymes which may be used, as described for example in international patent applications WO 92/1 1347 or WO 94/23005, can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature inactivation. They are present in the washing and cleaning agents according to the invention in amounts of preferably not more than 2% by weight, in particular from 0.2% by weight to 1.5% by weight.
  • the organic solvents which can be used in the agents according to the invention include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms , in particular ethylene glycol and propylene glycol, as well as their mixtures and the ethers derivable from the compound classes mentioned.
  • Such water-miscible solvents are preferably present in the washing, cleaning and disinfecting agents according to the invention not more than 30% by weight, in particular from 6% by weight to 20% by weight
  • the agents according to the invention can include systemic and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid. but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkahydroxides, contain.
  • systemic and environmentally compatible acids in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid.
  • mineral acids in particular sulfuric acid, or bases, in particular ammonium or alkahydroxides, contain.
  • pH regulators are preferably not contained in the agents according to the invention above 20% by weight, in particular from 1 2% to 17% by weight
  • compositions according to the invention does not offer any difficulties and can be carried out in a known manner, for example by spray drying or granulation, dextrin and dirt-releasing polymer being incorporated individually or in the form of granules according to the invention.
  • Thermally sensitive ingredients can optionally be added separately later
  • Production of agents according to the invention with increased debris weight, in particular in the range from 650 g / l to 950 g / l, is a process known from European patent EP 486 592 and having an extrusion step, preferably detergents or cleaning agents according to the invention in the form of conventional solvents, which contain liquid or pasty Solutions are usually made by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer
  • a dirt-releasing ethylene terephthalate-polyoxyethylene terephthalate polymer (Velvetol® 251 C, manufacturer Rhone-Poulenc) was heated to approx. 105 ° C. and applied to a maltodextine (DE approx. 12) placed in a Lod ⁇ ge® mixer with the chopper switched on Powdered (FK 320)
  • a free-flowing, fine-grain granulate (debris density 660 g / l) was obtained, which had 71% by weight maltodextine and 4% by weight silica and had a polymer content of 25% by weight

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un procédé pour la préparation de constituants détergents granulés coulants qui contiennent un polymère antisouillure et un support finement divisé. Ledit procédé est destiné à améliorer la capacité d'incorporation du polymère antisouillure, essentiellement grâce à l'emploi d'un support contenant de la dextrine. L'association d'un polymère antisouillure et d'une dextrine dans les détergents et les produits de lavage permet de se dispenser des co-adjuvants classiques du type des polycarboxylates polymères.
EP96941046A 1995-12-07 1996-11-28 Procede pour la preparation de granules antisouillure a support de dextrine, et agents les contenant Withdrawn EP0876456A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19545723 1995-12-07
DE1995145723 DE19545723A1 (de) 1995-12-07 1995-12-07 Verfahren zur Herstellung schmutzlösender Granulate mit Dextrin-Träger und Mitte welche diese enthalten
PCT/EP1996/005253 WO1997020904A1 (fr) 1995-12-07 1996-11-28 Procede pour la preparation de granules antisouillure a support de dextrine, et agents les contenant

Publications (1)

Publication Number Publication Date
EP0876456A1 true EP0876456A1 (fr) 1998-11-11

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EP96941046A Withdrawn EP0876456A1 (fr) 1995-12-07 1996-11-28 Procede pour la preparation de granules antisouillure a support de dextrine, et agents les contenant

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EP (1) EP0876456A1 (fr)
DE (1) DE19545723A1 (fr)
WO (1) WO1997020904A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19718664A1 (de) * 1997-05-02 1998-11-05 Clariant Gmbh Verfahren zur Herstellung von lagerstabilen schmutzablösevermögende Polymere (Soil Release Polymere, SRP) enthaltende Granulate und ihre Verwendung zur Herstellung fester Wasch- und Reinigungsmittel

Family Cites Families (4)

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Publication number Priority date Publication date Assignee Title
US3803285A (en) * 1971-01-20 1974-04-09 Cpc International Inc Extrusion of detergent compositions
US4020015A (en) * 1971-10-12 1977-04-26 Lever Brothers Company Detergent compositions
US4737308A (en) * 1974-03-19 1988-04-12 Pearson Elmer O Cleaning agent
GB9419091D0 (en) * 1994-09-22 1994-11-09 Cerestar Holding Bv Process for decreasing the build up of inorganic incrustations on textiles and detergent composition used in such process

Non-Patent Citations (1)

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Title
See references of WO9720904A1 *

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DE19545723A1 (de) 1997-06-12
WO1997020904A1 (fr) 1997-06-12

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