WO1999042556A1 - Wasch- und reinigungsmittelformkörper mit verbessertem eigenschaftsprofil - Google Patents

Wasch- und reinigungsmittelformkörper mit verbessertem eigenschaftsprofil Download PDF

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Publication number
WO1999042556A1
WO1999042556A1 PCT/EP1998/006475 EP9806475W WO9942556A1 WO 1999042556 A1 WO1999042556 A1 WO 1999042556A1 EP 9806475 W EP9806475 W EP 9806475W WO 9942556 A1 WO9942556 A1 WO 9942556A1
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WIPO (PCT)
Prior art keywords
detergent
weight
alcohols
nonionic
surfactant
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PCT/EP1998/006475
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German (de)
English (en)
French (fr)
Inventor
Monika Böcker
Markus Semrau
Gerhard Blasey
Fred Schambil
Heinke Jebens
Andreas Lietzmann
Christian Block
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Henkel Kommanditgesellschaft Auf Aktien
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Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP98952703A priority Critical patent/EP1056831A1/de
Priority to SK1231-2000A priority patent/SK12312000A3/sk
Priority to HU0100719A priority patent/HUP0100719A2/hu
Priority to JP2000532497A priority patent/JP2002504593A/ja
Publication of WO1999042556A1 publication Critical patent/WO1999042556A1/de

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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • C11D17/0065Solid detergents containing builders
    • C11D17/0073Tablets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/825Mixtures of compounds all of which are non-ionic
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/835Mixtures of non-ionic with cationic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38Cationic compounds
    • C11D1/52Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/662Carbohydrates or derivatives
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to highly compressed detergents and cleaning agents which are produced in predetermined spatial shapes.
  • the invention relates to detergent tablets which are used for washing textiles in a household washing machine and are briefly referred to as detergent tablets.
  • the dichotomy between a sufficiently hard molded body and a sufficiently fast disintegration time is a central problem. Since sufficiently stable, ie dimensionally and fracture-resistant molded articles can only be produced by relatively high compression pressures, there is a strong compression of the Molded body constituents and the consequent delayed disintegration of the shaped body in the aqueous liquor and thus the release of the active substances too slowly in the washing or cleaning process.
  • the delayed disintegration of the moldings has the further disadvantage that conventional detergent tablets cannot be washed in via the washing-in chamber of household washing machines, since the tablets do not disintegrate into secondary particles that are small enough to be washed into the washing drum from the washing-in chamber to become.
  • EP-A-0 522 766 discloses moldings made from a compact, particulate detergent composition containing surfactants, builders and disintegration aids (for example based on cellulose), at least some of the particles being coated with the disintegration agent, which is both binder and also shows disintegration effects when the moldings are dissolved in water.
  • This document also indicates the general difficulty of producing moldings with adequate stability and good solubility at the same time.
  • the particle size in the mixture to be pressed should be above 200 ⁇ m, the upper and lower limits of the individual particle sizes should not differ from one another by more than 700 ⁇ m.
  • EP-A-0 716 144 which tablets with an external shell describes water-soluble material
  • EP-A-0 711 827 which contain a citrate with a defined solubility as an ingredient.
  • binders which may have an explosive action (in particular polyethylene glycol) is disclosed in EP-A-0 711 828 (Unilever), which describes detergent tablets which are formed by pressing a particulate detergent composition at temperatures between 28 ° C. and the melting point of the binder material be produced, always being pressed below the melting temperature. From the examples in this document it can be seen that the moldings produced in accordance with their teaching have higher breaking strengths when compression is carried out at elevated temperature.
  • the invention relates to detergent tablets made of compressed particulate detergent and detergent, comprising surfactant (s), builders (e) and, if appropriate, further detergent and detergent components, the tablets
  • detergent tablets are preferred in which the total content of nonionic surfactants, that is to say surfactants from groups a) and b), is between 1 and 15% by weight.
  • the ratio of sugar surfactants a) and alkoxylates b) can be varied as desired within the framework described. While in principle any ratio a) to b) between 10 to 1 to 1 to 10 is possible and works according to the invention, detergent tablets are preferred for reasons of cost, in which the ratio of nonionic surfactants from the group of the alkyl polyglycosides and / or glucaminde to the nonionic surfactants from the group of alkoxylated alcohols is 2: 1 to 1: 8, preferably 1: 1 to 1: 7 and in particular 1: 2 to 1: 4.
  • the nonionic surfactants of category a) come from the group of alkyl polyglycosides and / or glucamides.
  • detergent tablets which are 0.2 to 8% by weight, preferably 0.5 to 5, being preferred % By weight and in particular 1 to 3% by weight of one or more nonionic surfactants from the group of the alkypolyglycosides and / or glucamides.
  • Alkypolyglycosides which can be used according to the invention satisfy the general formula RO (G) z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • detergent tablets are preferred which, as nonionic surfactant (s) a) alkyl polyglycoside (s), have a degree of glycosidation of 1.0 to 4.0, preferably 1.0 to 2.0 and contained in particular from 1.1 to 1.4.
  • Linear alkyl polyglucosides ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used. These can be described using the following formula
  • x is the degree of glycosidation z reduced by 1 described above
  • preferred values of x are therefore between 0 and 3, preferably between 0 and 1 and in particular between 0.1 and 0.4.
  • the number n of methylene groups is preferably between 7 and 21, preferably between 11 and 17, carbon atoms.
  • Preferred detergent tablets contain as nonionic surfactant (s) a) alkyl polyglucoside (s), that is APG, in which the polyglycosyl residue is a glucose residue.
  • the alkylpolyglycosides used according to the invention can be prepared by known processes based on known raw materials. For example, dextrose is reacted in the presence of an acidic catalyst with n-butanol to give butylpolyglycoside mixtures, which are transglycosidated with long-chain alcohols, likewise in the presence of an acidic catalyst, to give the desired alkylpolyglycoside mixtures. It is also possible to glycosidate dextrose directly with the desired long-chain alcohol to the desired alkyl polyglycoside mixtures.
  • the structure of the products can be varied within certain limits.
  • the alkyl radical is determined by the selection of the long-chain alcohol.
  • the industrially accessible alcohols having 8 to 22 carbon atoms, in particular native alcohols from the hydrogenation of carboxylic acids or carboxylic acid derivatives are preferred.
  • the alcohols obtainable from technical alcohol syntheses, such as oxo alcohols and Ziegleral alcohols, can also be used.
  • the polyglycosyl radicals G y are determined on the one hand by the selection of the carbohydrate and on the other hand by setting the average degree of polymerization (degree of glycosidation y), as described, for example, in DE 19 43 689.
  • polysaccharides for example starches, maltodextrins, dextrose, galactose, mannose, xylose, etc.
  • the commercially available carbohydrates starch, maltodextrins and in particular dextrose are preferred.
  • the alkyl polyglycosides are always mixtures of oligomers, which in turn represent mixtures of different isomeric forms. They exist side by side with - and ß-glycosidic bonds in pyranose and furanose form. The junctions between two saccharide residues are also different.
  • Alkyl polyglycosides which can be used according to the invention can also be prepared by mixing alkyl polyglycosides with alkyl monoglycosides.
  • alkyl monoglycosides can be obtained or enriched from alkyl polyglycosides using polar solvents such as acetone using the process disclosed in EP 092 355.
  • the degree of glycosidation of alkyl polyglycosides is usually determined by 1H nuclear magnetic resonance measurements.
  • glucamides can also be used as nonionic surfactants of category a).
  • glucamides is to be understood as a generic term for all polyhydroxy fatty acid amides that can be described by the formula (I):
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R * for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • Preferred detergent tablets contain as nonionic surfactant (s) a) polyhydroxy fatty acid amide (s) of the formula (I)
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups
  • Polyhydroxy fatty acid amides of the formula I are preferably used, in which the acyl radical RCO has a narrower chain distribution and the radical [Z] is selected from conventional sugar radicals.
  • detergent tablets are therefore preferred which use a polyhydroxy fatty acid amide of the formula (I) in which RCO is an aliphatic acyl radical having 12 to 18 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 Carbon atoms and [Z] stands for a glucose, fructose, maltose, lactose, galactose, mannose or xylose residue.
  • glucamides does not generally refer to polyhydroxy fatty acid amides, but to the substance class of the glucamides, ie compounds of the formula I in which the radical [Z] is derived from glucose.
  • Compounds of the formula also belong to the group of polyhydroxy fatty acid amides, which are simply referred to as glucamides in the context of the present invention
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R represents a linear, branched or cyclic alkyl radical or an aryl radical or is an oxyalkyl radical having 1 to 8 carbon atoms, preference being given to methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl or phenyl radicals
  • [Z] for a linear polyhydroxyalkyl radical stands, whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • the detergent tablets according to the invention contain nonionic surfactant (s) from the group of the alkoxylated alcohols in amounts of 1 to 15% by weight, based on the tablet.
  • nonionic surfactant (s) from category b) are used are preferably within narrow limits, so that detergent tablets are formed are preferred which contain 1 to 12 wt .-%, preferably 2.5 to 10 wt .-% and in particular 4 to 8 wt .-% of one or more nonionic surfactants from the group of alkoxylated alcohols.
  • alcohols can be used as alcohols, the alkoxylation of which provides the nonionic surfactants of group b).
  • the industrially accessible alcohols having 8 to 22 carbon atoms in particular native alcohols from the hydrogenation of carboxylic acids or carboxylic acid derivatives (so-called fatty alcohols), are preferred.
  • the alcohols obtainable from technical alcohol syntheses, such as oxo alcohols and Ziegleral alcohols, can also be used.
  • the alcohols are in particular primary alcohols with preferably 8 to 18 carbon atoms, in which the alcohol radical may be methyl-branched linearly or preferably in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • the alcohol residue is still narrower in its chain distribution so that preferred detergent and cleaning agent shaped body as nonionic surfactant (s) (e) b) alkoxylated (s) alcohol (s), which are derived from C 8-22 alcohols , preferably from C 8 . 20 alcohols and in particular from C ⁇ 2 . 18 - Derive alcohols.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 2. 4 alcohols with 3 EO or 4 EO, C 4 alcohol with 7 EO, C 3 . 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 - ⁇ 8 - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 .j 4 - alcohol with 3 EO and C ⁇ 2 . 18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • NRE narrow range ethoxylates
  • Surfactants can also use fatty alcohols with more than 12 EO. Examples Who are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Preferred detergent tablets contain as nonionic surfactant (s) b) ethoxylated alcohols with degrees of ethoxylation between 2.0 and 10, preferably between 5.0 and 8.0 and in particular between 5.5 and 7.0.
  • alkoxylated alcohols that have not only been reacted with ethylene or propylene oxide or other alkoxylating agents, but can also be obtained by synchronous or sequential reaction with several alkoxylating agents (e.g. ethoxylation / propoxylation).
  • alkoxylated nonionic surfactants can have a statistical sequence of the individual EO-PO units or be in the form of a block or graft polymer.
  • detergent tablets which contain mixed alkoxylated, preferably ethoxylated and propoxylated alcohols as the nonionic surfactant (s) b).
  • the detergent tablets according to the invention can contain further surface-active substances from the group of anionic, zwitterionic or cationic surfactants, anionic surfactants being clearly preferred for economic reasons and on the basis of their performance spectrum.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Preferred surfactants of the sulfonate type are C. 3 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12 . 18 -monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates from C 12 - ⁇ 8 alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization,
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half-esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 1 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials.
  • the C 12 - C 16 alkyl sulfates and C 12 -Ci 5 alkyl sulfates and C 4 -Ci 5 alkyl sulfates are preferred for washing technology reasons.
  • 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • 21 -alcohols such as 2 -methyl-branched C - ⁇ -alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ⁇ 2 - ⁇ 8 fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 - ⁇ 8 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • anionic surfactants that are used in the laundry detergent and cleaning product tablets according to the invention, there are no basic conditions to be observed which prevent them from being formulated.
  • preferred detergent tablets have a soap content which exceeds 0.2% by weight, based on the total weight of the tablet.
  • the preferred anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates.
  • builders are the most important ingredients in detergents and cleaning agents.
  • the detergent tablets according to the invention can contain all builders normally used in detergents, especially zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - the phosphates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 'HO, where M is sodium or hydrogen, x 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.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 'yH 2 O are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • the zeolite can be used both as a builder in a granular compound and can also be used for a type of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates as builder substances, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
  • Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid,
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • disintegration aids so-called tablet disintegrants
  • tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.
  • Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the weight of the tablet.
  • Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 until 6
  • Pure cellulose has the formal gross composition (C 6 Hjo ⁇ 5 ) n and, formally speaking, is a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • CMC carboxymethyl cellulose
  • the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
  • the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.
  • the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be pressed.
  • Detergent tablets which contain disintegrants in granular or, if appropriate, cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application PCT / EP 98/1203 (Henkel) . These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged.
  • a subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
  • Detergent tablets which additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular of 4 to 6% by weight, based in each case on the weight of the shaped body, are particularly preferred in the context of the present invention.
  • a disintegration aid preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular of 4 to 6% by weight, based in each case on the weight of the shaped body, are particularly preferred in the context of the present invention.
  • washable and cleaning-active molded articles is carried out by applying pressure to a mixture to be pressed, which is located in the cavity of a press.
  • a mixture to be tabletted In the simplest case of molded article production, which is simply called tableting below, the mixture to be tabletted is directly, i.e. pressed without prior granulation.
  • the advantages of this so-called direct tableting are its simple and inexpensive application, since no further process steps and consequently no further plants are required. However, these advantages are offset by disadvantages.
  • a powder mixture that is to be tabletted directly must have sufficient plastic deformability and good
  • Preferred detergent tablets within the scope of the present invention are obtained by pressing a particulate premix comprising at least one surfactant-containing granulate and at least one subsequently admixed powdery component. It is advantageous for the later detergent tablets if the premix to be pressed has a bulk density that comes close to that of conventional compact detergents. In particular, it is preferred that the premix to be pressed has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular above 700 g / 1.
  • the premix Before the particulate premix is pressed into detergent tablets, the premix can be "powdered” with finely divided surface treatment agents. This can be advantageous for the nature and physical properties of both the premix (storage, pressing) and the finished detergent tablets. Finely divided powdering agents are well known in the art, mostly zeolites, silicates or other inorganic salts being used. However, the premix is preferably “powdered” with finely divided zeolite, zeolites of the faujasite type being preferred.
  • detergent tablets consist of a particulate premix which contains granular components and subsequently admixed powdery substances, the or one of the subsequently admixed pulverulent components being a faujasite-type zeolite with particle sizes below 100 ⁇ m, is preferably below 10 ⁇ m and in particular below 5 ⁇ m and makes up at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be pressed.
  • the detergent tablets according to the invention can contain further ingredients customary in detergents and cleaning agents from the group of bleaching agents, bleach activators, enzymes, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical agents Brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors included.
  • bleaching agents that serve as bleaching agents and supply H 2 O 2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • bleach activators can be incorporated as the sole constituent or as an ingredient of component b).
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Substances are suitable which contain O- and / or N-acyl groups of the specified number of carbon atoms and / or
  • acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetyloxy and 2,5-diacetyloxy and 2,5-glycolacet
  • bleach catalysts can also be incorporated into the moldings.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the shaped bodies according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the laundry detergent and cleaning product tablets may also contain components which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear if a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • the moldings can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which, instead of the morpholino group, have a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type may be present, e.g.
  • Dyes and fragrances are added to the agents according to the invention in order to improve the aesthetic impression of the products and to provide the consumer with a visually and sensorially "typical and unmistakable" product in addition to the softness performance.
  • perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Fragrance compounds of the ester type are e.g. Benzyl acetate,
  • the ethers include, for example, benzyl ethyl ether
  • the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
  • the ketones include, for example, the jonones, oc-isomethyl ionone and methyl cedryl ketone
  • the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol
  • the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the dye content of the plasticizers according to the invention is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the entire formulation.
  • the fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • dyes In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and are insensitive to the other ingredients of the compositions and to light
  • the moldings according to the invention are first produced by dry mixing the constituents, which can be wholly or partially pregranulated, and then providing them, in particular pressing them into tablets, using conventional methods.
  • the premix is compressed in a so-called die between two punches to form a solid compressed product.
  • This process which is briefly referred to as tableting in the following, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.
  • the premix is introduced into the die, the filling quantity and thus the weight and the shape of the molding being formed being determined by the position of the lower punch and the shape of the pressing tool.
  • the constant metering, even at high molding throughputs, is preferably achieved by volumetric metering of the premix.
  • the upper punch touches the premix and lowers further in the direction of the lower punch.
  • the particles of the premix are pressed closer together, the void volume within the filling between the punches continuously decreasing. From a certain position of the upper punch (and thus from a certain pressure on the premix) the plastic deformation begins, in which the particles flow together and the molded body is formed.
  • part of the premix particle is also crushed and sintering of the premix occurs at even higher pressures.
  • increasing pressing speed that is to say high throughput quantities, the phase of elastic deformation is shortened further and further, so that the resulting shaped bodies can have more or less large cavities.
  • the finished molded body is pressed out of the die by the lower punch and transported away by subsequent transport devices. At this point, only the weight of the molded body is final
  • Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down.
  • eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine.
  • the pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disk, the number of die holes being correspondingly increased.
  • the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available.
  • Each die on the die table is assigned an upper and lower stamp, with the pressing pressure being active only by the upper or lower die. Lower stamp, but can also be built up by both stamps.
  • the die table and the stamps move around a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation.
  • these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks.
  • the die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix.
  • the pressure on the premix is over the press paths for
  • Rotary presses can also be provided with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet.
  • several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before the further filling.
  • jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible.
  • Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing.
  • the throughputs of modern rotary tablet presses are over one million tablets per hour.
  • Tableting machines suitable within the scope of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy NV, Halle (BE / LU).
  • the hydraulic double pressure press HPF 630 from LAEIS, D. is particularly suitable.
  • the moldings can be manufactured in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. It is also possible, however, to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points.
  • the portioned compacts can be designed as tablets, in cylindrical or cuboid form, with a diameter / height ratio in the range from approximately 0.5: 2 to 2: 0.5 is preferred.
  • Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such compacts.
  • the spatial shape of another embodiment of the shaped body is adapted in its dimensions to the induction chamber of commercially available household washing machines, so that the shaped bodies can be dosed directly into the induction chamber without metering aid, where they dissolve during the induction process.
  • the detergent tablets can also be used without problems using a metering aid.
  • Another preferred molded body that can be produced has a plate-like or plate-like structure with alternately thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, broken off and into the Machine can be entered.
  • This principle of the "bar-shaped" shaped body detergent can also be implemented in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side.
  • the various components are not pressed into a uniform tablet, but that shaped bodies are obtained which have several layers, that is to say at least two layers. It is also possible that these different layers have different dissolving speeds. This can result in advantageous performance properties of the molded articles. If, for example, components are contained in the moldings
  • the layer structure of the shaped bodies can be stacked, with the inner layer (s) already loosening at the edges of the shaped body when the outer layers have not yet been completely detached, but it is also possible for the inner layer (s) to be completely encased ) can be achieved by the layer (s) lying further outwards, which leads to the premature dissolution of components of the inner layer (s).
  • a shaped body consists of at least three layers, i.e. two outer and at least one inner layer, at least one peroxy bleaching agent being contained in at least one of the inner layers, while the two cover layers are used in the case of the stacked shaped body and the is in the case of the shell-shaped shaped body outermost layers, however, are free of peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes that may be present in one molded body.
  • Such multilayered moldings have the advantage that they can not only be used via a dispensing chamber or via a metering device which is added to the wash liquor; rather, it is also possible in such cases to put the molded body in direct contact with the textiles in the machine without fear of bleaching and the like.
  • the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else they can be coated using the method of melt coating.
  • the breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to
  • stands for diametral fracture stress (DFS) in Pa
  • P is the force in N that leads to the pressure exerted on the molded body that causes the molded body to break
  • D is the molded body diameter in meters and t the height of the molded body.
  • APG ethoxylate ratio of 1: 5.82
  • the surfactant granules B which were pressed into the molded bodies VI, only 0.5% by weight of APG and 7.0% by weight of ethoxylated alcohol (APG: ethoxylate ratio of 1:14) were used; the surfactant granules C, which delivered the molded article V2, contained exactly the opposite amounts of APG or ethoxylated nonionic surfactant (APG: ethoxylate ratio of 14: 1)
  • Tables 1 and 2 show the composition of the surfactant granules and the composition of the premixes to be treated (and thus the molded article).
  • Zeolite A anhydrous active substance
  • the hardness of the tablets was measured by deforming the tablet to fracture, the force acting on the side surfaces of the tablet and the maximum force that the tablet was able to withstand.
  • the tablet was placed in a beaker with water (600 ml water, temperature 30 ° C.) and the time to complete

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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)
  • Detergent Compositions (AREA)
PCT/EP1998/006475 1998-02-20 1998-10-13 Wasch- und reinigungsmittelformkörper mit verbessertem eigenschaftsprofil WO1999042556A1 (de)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP98952703A EP1056831A1 (de) 1998-02-20 1998-10-13 Wasch- und reinigungsmittelformkörper mit verbessertem eigenschaftsprofil
SK1231-2000A SK12312000A3 (sk) 1998-02-20 1998-10-13 Tvarované výrobky pracích a čistiacich prostriedkov
HU0100719A HUP0100719A2 (hu) 1998-02-20 1998-10-13 Mosó- és tisztítószer formatestek
JP2000532497A JP2002504593A (ja) 1998-02-20 1998-10-13 改善された特性を有する洗剤成形体

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DE19807321A DE19807321A1 (de) 1998-02-20 1998-02-20 Wasch- und Reinigungsmittelformkörper mit verbessertem Eigenschaftsprofil
DE19807321.6 1998-02-20
CA002315303A CA2315303A1 (en) 1998-02-20 2000-08-22 Shaped bodies of detergent with improved properties

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DE (1) DE19807321A1 (cs)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001081518A1 (en) * 2000-04-25 2001-11-01 Cognis Corporation Process for inhibiting gel formation of hydrated detergent tablets containing nonionic surfactant ethoxylates
EP1249489A1 (de) * 2001-04-12 2002-10-16 Cognis Deutschland GmbH & Co. KG Wasch- und Reinigungsmittelformkörper mit verbesserten Zerfallseigenschaften

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9918087D0 (en) * 1999-08-02 1999-10-06 Mcbride Robert Ltd Detergent tablets
DE10006306A1 (de) * 2000-02-12 2001-08-23 Buck Chemie Gmbh Wirkstoff-Tablette, insbesondere als Reiniger- und/oder Entkalkertablette
CN106753866B (zh) * 2016-12-08 2019-07-09 江苏金太阳纺织科技股份有限公司 一种溶解性能好的洗衣片及其制备方法
CN106811329B (zh) * 2016-12-08 2019-07-09 江苏金太阳纺织科技股份有限公司 一种抗菌防螨的洗衣片及其制备方法
CN106811330B (zh) * 2016-12-08 2019-07-09 江苏金太阳纺织科技股份有限公司 一种洗衣泡腾片剂及其制备方法
CN112898632A (zh) * 2019-12-07 2021-06-04 嘉兴若天新材料科技有限公司 一种透明软管用无色无味环保液体稳定剂

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04164999A (ja) * 1990-10-29 1992-06-10 Kao Corp 錠剤型洗剤
JPH06108099A (ja) * 1992-09-30 1994-04-19 Lion Corp タブレット洗剤組成物
DE19509752A1 (de) * 1995-03-17 1996-09-19 Henkel Kgaa Verfahren zur Herstellung eines pulverförmigen Waschmittels
EP0799886A2 (en) * 1996-04-03 1997-10-08 Cleantabs A/S Laundry detergent tablets

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04164999A (ja) * 1990-10-29 1992-06-10 Kao Corp 錠剤型洗剤
JPH06108099A (ja) * 1992-09-30 1994-04-19 Lion Corp タブレット洗剤組成物
DE19509752A1 (de) * 1995-03-17 1996-09-19 Henkel Kgaa Verfahren zur Herstellung eines pulverförmigen Waschmittels
EP0799886A2 (en) * 1996-04-03 1997-10-08 Cleantabs A/S Laundry detergent tablets

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 9230, Derwent World Patents Index; Class A97, AN 92-245794, XP002085066 *
DATABASE WPI Section Ch Week 9420, Derwent World Patents Index; Class A97, AN 94-164283, XP002078352 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001081518A1 (en) * 2000-04-25 2001-11-01 Cognis Corporation Process for inhibiting gel formation of hydrated detergent tablets containing nonionic surfactant ethoxylates
US6566317B2 (en) 2000-04-25 2003-05-20 Cognis Corporation Process for inhibiting gel formation of hydrated detergent tablets containing nonionic surfactant ethoxylates
EP1249489A1 (de) * 2001-04-12 2002-10-16 Cognis Deutschland GmbH & Co. KG Wasch- und Reinigungsmittelformkörper mit verbesserten Zerfallseigenschaften

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DE19807321A1 (de) 1999-08-26
JP2002504593A (ja) 2002-02-12
CZ20003029A3 (cs) 2001-09-12
CN1284992A (zh) 2001-02-21
PL342316A1 (en) 2001-06-04
HUP0100719A2 (hu) 2001-06-28

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