WO1999055812A1 - Corps moules detergents a proprietes de decomposition ameliorees - Google Patents

Corps moules detergents a proprietes de decomposition ameliorees Download PDF

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Publication number
WO1999055812A1
WO1999055812A1 PCT/EP1999/002596 EP9902596W WO9955812A1 WO 1999055812 A1 WO1999055812 A1 WO 1999055812A1 EP 9902596 W EP9902596 W EP 9902596W WO 9955812 A1 WO9955812 A1 WO 9955812A1
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WIPO (PCT)
Prior art keywords
weight
detergent
washing
molded article
acid
Prior art date
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PCT/EP1999/002596
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German (de)
English (en)
Inventor
Christian Block
Monika Böcker
Andreas Lietzmann
Christian Nitsch
Markus Semrau
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Henkel Kommanditgesellschaft Auf Aktien
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Publication of WO1999055812A1 publication Critical patent/WO1999055812A1/fr

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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • 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
    • C11D11/02—Preparation in the form of powder by spray drying
    • 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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
    • 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
    • C11D3/50—Perfumes

Definitions

  • the present invention is in the field of compact molded articles which have washing and cleaning properties.
  • 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.
  • Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have a number of advantages over powdered ones: They are easier to dose and handle and, thanks to their compact structure, have advantages in terms of storage and transport. Detergent tablets are therefore also comprehensively described in the patent literature. A problem that occurs again and again when using shaped articles which are active in washing and cleaning is the insufficient rate of disintegration and dissolution of the shaped articles under conditions of use.
  • 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 - As well as disintegration effect when dissolving the moldings 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 (Unilever), which describes tablets with an external shell made of water-soluble material, and EP-A-0 711 827 (TJnilever), which contain a citrate with a defined solubility as an ingredient.
  • binders which may have an explosive action in particular polyethylene glycol
  • EP-A-0 711 828 TJnilever
  • Detergent tablets in which individual ingredients are present separately from others are also described in EP-A-0 481 793 (TJnilever).
  • the detergent tablets disclosed in this document contain sodium percarbonate, which is spatially separated from all other components that could influence its stability.
  • the present invention is therefore based on the object of providing detergent tablets which combine the desired properties of high hardness and mechanical stability and nevertheless favorable disintegration rates.
  • the invention accordingly relates to detergent tablets made from compressed particulate detergent and detergent, comprising surfactant (s), builder (s) and, if appropriate, further detergent and cleaning agent constituents, the aromatic sulfonates of the formula I SO 3 " X
  • each of the radicals R ,, R 2 , R 3 , R 4 , R 5 is independently selected from H or a C ,. 5 alkyl or alkenyl radical and X represents a cation.
  • the use of the aromatic sulfonates mentioned drastically improves the solubility and the rate of disintegration of detergent tablets.
  • the molded bodies have good solubilities and disintegration times even with high hardness.
  • the detergent tablets according to the invention can be produced with significantly greater hardness, which has a positive effect on their handling during packaging and transport.
  • Aromatic sulfonates according to the invention are those of the formula I.
  • each of the radicals R 1 , R 3 , R 4 , R 5 is independently selected from H or a C,. 5 alkyl or alkenyl radical and X represents a cation.
  • Preferred substituents R l5 R 2, R 3, R 4, R 5 are independently selected from H or a methyl, ethyl, H-propyl, z 'so-propyl, "-butyl, iso-butyl , tert-butyl, "-pentyl, z ' so-pentyl or” eo-pentyl.
  • At least three of the radicals R 1 to R 5 mentioned are hydrogen atoms, preference being given to aromatic sulfonates in which three or four sub- are substituents on the aromatic ring hydrogen atoms. The remaining or the remaining two residues can take any position on the sulfonate group and each other.
  • R 3 is an alkyl radical, while R "R 2, R 4, and R 5 is H ( ⁇ ra substitution).
  • particularly preferred aromatic sulfonates are toluene, cumene or xylene sulfonate.
  • the /? ⁇ ra isomer is preferred for the purposes of the present invention.
  • The? ⁇ r -isopropylbenzenesulfonate is also the preferred compound in the case of the cumene sulfonates.
  • xylene is usually used industrially as a mixture of isomers
  • the commercially available xylene sulfonate is also a mixture of several compounds which are derived from the sulfonation of ortho-, meta - and para-xylene result.
  • X in the general formula I represents a cation, for example an alkali metal cation such as sodium or potassium.
  • X can also represent the charge-equivalent proportion of a polyvalent cation, for example Mg 2 72 or Al 3 73, sodium being preferred among the cations mentioned.
  • the sulfonates are preferably used in amounts of 0.2 to 10% by weight, preferably 0.3 to 5% by weight and in particular 0.5 to 3% by weight, based in each case on the weight of the molded article.
  • the detergent tablets contain customary ingredients of detergents and cleaning agents, in particular from the groups of surfactants and builders.
  • Other ingredients that are used in the washing and shaped detergent bodies can be used, for example, bleaches, bleach activators, enzymes, dyes and fragrances, optical brighteners, polymers, foam inhibitors, etc.
  • the detergent tablets according to the invention contain surface-active substances from the group of anionic, nonionic, 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.
  • Suitable surfactants of the sulfonate type are preferably C 9 _ 13 - alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C 12 _ 18 -Monoolefmen with terminal or internal double bond by sulfonation with Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • Alkanesulfonates which are derived from C 12 are also suitable.
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • sulfonated fatty acid glycerol esters 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 become.
  • Preferred sulfated fatty acid glycerol esters are the sulfate 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 especially the sodium salts of the Schwefelhoffregurester C I2 -C 18 fatty alcohols, for example coconut fatty alcohol, Talgfettalko- 7
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical which is produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C, 4 -C 15 alkyl sulfates are preferred for reasons of washing technology.
  • 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 9. ⁇ alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12 .
  • 18 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 . 18 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).
  • 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, 8th
  • 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.
  • 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.
  • detergent tablets which contain 5 to 50% by weight, preferably 7.5 to 40% by weight and in particular 10 to 20% by weight of anionic surfactant (s), based in each case on the Molded body weight, included.
  • anionic surfactant s
  • 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, with preferred detergent tablets 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s) in each case based on the molded body weight
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • Preferred ethoxylated alcohols include, for example, C 12 _ 14 alcohols with 3 EO or 4 EO, C 9 " n alcohol with 7 EO, C 13 _ 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C, 2 . 18 - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 . 14 alcohol with 3 EO and C 12 . 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).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters as described, for example, in Japanese patent application J "58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
  • Alkypolyglycosides that can be used 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 Is a 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.
  • 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.
  • the detergent tablets according to the invention can preferably contain alkyl polyglycosides, with APG contents in the tablet of more than 0.2% by weight, based on the total tablet, being preferred.
  • Particularly preferred detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • surfactants are polyhydroxy fatty acid amides of the formula (II),
  • 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.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (III) 11
  • 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 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms
  • C - alkyl or phenyl radicals being preferred
  • [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated, derivatives of this rest.
  • [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 be converted, for example according to the teaching of international application WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired polyhydroxy fatty acid amides.
  • builders are the most important ingredients in detergents and cleaning agents.
  • all builders commonly used in detergents and cleaning agents can be present, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 ' H 2 O, 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.
  • M sodium or hydrogen
  • x is a number from 1.9 to 4
  • 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- 12
  • crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • M represents sodium
  • x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na ⁇ O j 'yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • Amorphous sodium silicates with a modulus Na ⁇ O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used, which are delayed release and have secondary washing properties.
  • 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 “amo ⁇ h” is also understood to mean “roentgenamo ⁇ h”.
  • 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 integrated in such a way 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 are preferred.
  • 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. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray silicates.
  • 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.
  • zeolite A (approx. 80% by weight 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 kind of "powdering" of the entire mixture to be used, usually both ways of incohering 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, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • 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
  • disintegration accelerators are understood to be auxiliaries which are quick to use 14
  • Preferred detergent tablets contain 0.5 to 10% by weight, preferably 1 to 5% by weight and in particular 2 to 4% by weight of a disintegration aid, in each case based on the weight of the molded article.
  • Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred washing and cleaning agent shaped bodies such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 1 to 5% by weight and in particular 2 contain up to 4 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 H, 0 O 5 ) n and, viewed formally, 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. But also celluloses in which the hydroxyl groups against functional groups that are not bound via an oxygen atom 15
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • 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 cellulose-based disintegrant.
  • 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 resulting from the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, to granules with an average particle size of 200 ⁇ m.
  • detergent tablets show mixing tendencies. These three requirements are extremely difficult to master with many substance mixtures, so that direct tableting is not often used, particularly in the production of detergent tablets.
  • the usual way of producing detergent tablets is therefore based on powdery components (“primary particles”) which are agglomerated or granulated by suitable processes to form secondary particles with a larger particle diameter. These granules or mixtures of different granules are then mixed with individual powdery additives and fed to the tableting.
  • 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.
  • the granules containing surfactant can be produced by conventional industrial granulation processes such as compacting, extrusion, mixer granulation, pelletization or fluidized bed granulation. It is advantageous for the later detergent tablets if the premix to be ve ⁇ resses has a bulk density that comes close to the usual compact detergent. In particular, it is preferred that the premix to be ve ⁇ ress 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 of advantage for the quality and physical properties of both the premix (storage, molding) as well as the finished detergent tablets. Fine particle size reducing 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. In the context of the present invention, the term “faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 (compare Donald W. Breck: “Zeolite Molecular Sieves”, John Wiley & Sons, New York , London, Sydney, To- 17
  • zeolite X zeolite Y and faujasite and mixtures of these compounds can also be used, the pure zeolite X being preferred.
  • Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which do not necessarily have to belong to the zeolite structural group 4, can also be used as powdering agents, it being advantageous if at least 50% by weight of the powder means consist of a zeolite of the faujasite type.
  • detergent tablets consist of a particulate premix containing granular components and subsequently admixed powdery substances, the or one of the subsequently admixed powdery components being a zeolite of the faujasite type 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 treated.
  • 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 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. 18th
  • 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 with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • TAED tetraacetylethylene
  • 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 from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and li 19
  • 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 detergent tablets can also contain components that positively influence the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when 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, in each case based 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 shaped bodies can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-mo ⁇ holino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the Mo ⁇ holino- Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) - 20th
  • Dyes and fragrances are added to the detergent tablets according to the invention, in order to improve the aesthetic impression of the products and, in addition to the softness, to provide the consumer with a visually and sensorially "typical and unmistakable" product.
  • 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.
  • the ethers include, for example, benzyl ethyl ether, the aldehydes, for example.
  • the linear alkanals with 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, oc-isomethylionon and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and Te ⁇ ineol, the hydrocarbons mainly include the Te ⁇ ene such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance.
  • perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. 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, lentil flower 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 total 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.
  • the agents according to the invention 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 insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity to textile fibers, in order not to dye them.
  • the molded articles according to the invention are first produced by dry mixing the constituents, which can be wholly or partially pregranulated, and then providing information, in particular compresses to tablets, using conventional methods.
  • the premix is compacted 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 molded body being formed being determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosing, even at high mold throughputs, is preferably achieved by volumetric dosing of the premix.
  • the upper punch touches the premix and lowers further in the direction of the lower punch. During this compression, 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 stamp (and thus from a certain 22
  • 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 increased accordingly.
  • 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 punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps.
  • Stamps move around a common vertical axis, whereby the stems are brought into the positions for filling, compression, plastic deformation and ejection with the help of rail-like cam tracks during circulation. Wherever a particularly serious lifting or lowering of the punches is required (filling, compacting, ejecting), 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 pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.
  • 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 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 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 molded articles 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 molded body 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 as tablets, in cylinder or cuboid form can be expedient, with a diameter / height ratio in the range from about 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 pressed articles.
  • the spatial shape of another embodiment of the molded body is adapted in its dimensions to the detergent dispenser of commercially available household washing machines, so that the molded body can be metered directly into the dispenser without metering aid, where it dissolves during the dispensing process.
  • the detergent tablets without problems using a metering aid and is preferred in the context of the present invention.
  • 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 25th
  • 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 application properties of the molded body. If, for example, components are contained in the moldings that mutually influence one another negatively, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a more slowly soluble layer, so that the first component has already reacted. when the second goes into solution.
  • the layer structure of the molded body can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the molded body when the outer layers have not yet been completely removed, 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 molded body consists of at least three layers, i.e. two outer and at least one inner layer, at least one of the inner layers containing a peroxy bleaching agent, while in the case of the stacked molded body the two cover layers and in the case of the shell-shaped molded body the 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 a molded body. Such multi-layer molded bodies have the advantage that they are not only used via a dispensing chamber or via a metering device which is added to the wash liquor. 26
  • the bodies to be coated can, for example, be sprayed with aqueous solutions or emulsions, or else they can be coated using the melt coating method.
  • the breaking strength of cylindrical shaped bodies can be determined via the measurand of the diametrical fallow response. This can be determined according to
  • D diametral fracture stress (DFS) in Pa
  • P is the force in N which leads to the pressure exerted on the molded body, which causes the molded body to break
  • D is the molded body diameter in meters and t the height of the molded body.
  • the molded body El, E2 and E3 or VI, V2 and V3 differ only in their hardness, not in their composition. 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 28.5 29.9
  • Foam inhibitor 3.5
  • the hardness of the tablets was measured by deforming the tablet until it broke, the force acting on the side surfaces of the tablet and the maximum force that the tablet withstood being determined.
  • the tablet was placed in a beaker with water (600 ml of water, temperature 30 ° C.) and the time until the tablet disintegrated completely.

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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)

Abstract

L'invention concerne des corps moulés détergents qui se caractérisent par une dureté élevée et ainsi une bonne résistance au transport et à la manipulation, et possèdent également d'excellentes caractéristiques de décomposition. Ces caractéristiques avantageuses sont obtenues grâce au fait que les corps moulés contiennent des sulfonates aromatiques de la formule générale (I) dans laquelle chacun des radicaux R1, R2, R3, R4, R5 est sélectionné indépendamment des autres parmi H ou bien un radical alkyle C1-5 ou un radical alcényle, et X représente un cation.
PCT/EP1999/002596 1998-04-28 1999-04-17 Corps moules detergents a proprietes de decomposition ameliorees WO1999055812A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1998118965 DE19818965A1 (de) 1998-04-28 1998-04-28 Wasch- und Reinigungsmittelformkörper mit verbesserten Zerfallseigenschaften
DE19818965.6 1998-04-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001029162A1 (fr) * 1999-10-21 2001-04-26 Henkel Kommanditgesellschaft Auf Aktien Corps moules detergents et nettoyants presentant une resistance amelioree a l'abrasion

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19944218A1 (de) * 1999-09-15 2001-03-29 Cognis Deutschland Gmbh Waschmitteltabletten
EP1398368B1 (fr) * 2002-09-16 2005-11-23 Unilever N.V. Compositions de nettoyage

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JPS6230197A (ja) * 1985-07-31 1987-02-09 ライオン株式会社 タブレツト洗剤組成物
JPH04239100A (ja) * 1991-01-11 1992-08-26 Lion Corp タブレット洗剤組成物
JPH0617099A (ja) * 1992-06-29 1994-01-25 Lion Corp タブレット洗剤組成物
JPH07286199A (ja) * 1994-04-15 1995-10-31 Lion Corp タブレット洗剤組成物の製造方法
WO1998042817A1 (fr) * 1997-03-24 1998-10-01 Unilever Plc Compositions detergentes

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Publication number Priority date Publication date Assignee Title
JPS6230197A (ja) * 1985-07-31 1987-02-09 ライオン株式会社 タブレツト洗剤組成物
JPH04239100A (ja) * 1991-01-11 1992-08-26 Lion Corp タブレット洗剤組成物
JPH0617099A (ja) * 1992-06-29 1994-01-25 Lion Corp タブレット洗剤組成物
JPH07286199A (ja) * 1994-04-15 1995-10-31 Lion Corp タブレット洗剤組成物の製造方法
WO1998042817A1 (fr) * 1997-03-24 1998-10-01 Unilever Plc Compositions detergentes

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DATABASE WPI Section Ch Week 9241, Derwent World Patents Index; Class D25, AN 92-335478, XP002900589 *
DATABASE WPI Section Ch Week 9408, Derwent World Patents Index; Class A97, AN 94-062268, XP002900592 *
DATABASE WPI Section Ch Week 9601, Derwent World Patents Index; Class D25, AN 96-007117, XP002900591 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001029162A1 (fr) * 1999-10-21 2001-04-26 Henkel Kommanditgesellschaft Auf Aktien Corps moules detergents et nettoyants presentant une resistance amelioree a l'abrasion

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