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WO1999063045A1 - Corps moules detergents stables a la rupture et se dissolvant rapidement - Google Patents

Corps moules detergents stables a la rupture et se dissolvant rapidement Download PDF

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Publication number
WO1999063045A1
WO1999063045A1 PCT/EP1999/003566 EP9903566W WO9963045A1 WO 1999063045 A1 WO1999063045 A1 WO 1999063045A1 EP 9903566 W EP9903566 W EP 9903566W WO 9963045 A1 WO9963045 A1 WO 9963045A1
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WO
WIPO (PCT)
Prior art keywords
weight
detergent
washing
acid
premix
Prior art date
Application number
PCT/EP1999/003566
Other languages
German (de)
English (en)
Inventor
Christian Block
Sandra WITT-NÜSSLEIN
Monika Böcker
Michael Feist
Fred Schambil
Bernhard Müller
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to KR1020007013625A priority Critical patent/KR20010052496A/ko
Priority to EP99926386A priority patent/EP1086203A1/fr
Priority to JP2000552242A priority patent/JP2002517559A/ja
Publication of WO1999063045A1 publication Critical patent/WO1999063045A1/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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D3/395—Bleaching agents

Definitions

  • the present invention is in the field of compact moldings which have washing and cleaning properties.
  • Such detergent tablets comprise, for example, detergent tablets for washing textiles, detergent tablets for machine dishwashing or cleaning hard surfaces, bleach tablets for use in washing machines or dishwashers, water softening tablets or stain remover tablets.
  • 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.
  • Fluctuations in the volumetric dosage result in a tablet that is pressed to predetermined external dimensions becoming softer with less premix and harder with more premix than the average of the tablets.
  • the resulting fluctuations in the hardness of the resulting tablets can lead to mechanically unstable or, in other extreme cases, to completely insoluble molded articles.
  • the extent of this variation is also affected by the individual premix. If one applies the pressing force exerted on the mixture via the tablet press in a diagram over the dissolving speed of the molded bodies obtained, the straight line described above results in a straight line which, depending on the individual premix, runs more or less steeply.
  • European patent application EP 799 886 (Cleantabs A / S) also describes hard, unbreakable and yet rapidly soluble detergent tablets, each containing 0.1 to 15% by weight of nonionic and amphoteric surfactant, 20 to 50% by weight of a polyfunctional carboxylic acid or their Salt, 1 to 30 wt .-% builder and 5 to 70 wt .-% potassium carbonate.
  • the physical properties of the premixes to be ve ⁇ ressen should be positively influenced to the extent that the course of the straight line "pressing force over disintegration time" is as flat as possible, ie that small fluctuations in the pressing force do not lead to serious changes in the solubility of the shaped bodies
  • the invention relates to detergent tablets made of compressed particulate detergent and detergent, comprising surfactant (s) and / or builder (s) and / or bleach and, if appropriate, further detergent and detergent components, the potassium carbonate 1,5-water and / or contain sodium sesquicarbonate.
  • Potassium carbonate-1,5-water (“potash hydrate”) is the stable phase of the potassium carbonate in contact with the saturated solution in the range from 0 ° C to approx. 110 ° C and can be obtained by crystallization from supersaturated potassium carbonate solutions become. It crystallizes in shiny, practically dust-free crystals and has a density of 2.155 likes "3 and completely loses its crystal water at temperatures of 130 to 160 ° C. Most large-scale manufacturing processes for potassium carbonate initially lead to potassium carbonate 1,5-water, which in rotary kilns at 200 to 350 ° C leads to 98 to 100% potassium carbonate If this calcination is not carried out, the crystallized potassium carbonate 1,5 hydrate is dried at 110 to 120 ° C.
  • Ion exchange is of minor importance or only of historical interest he process (starting materials: KC1 and (NH 4 ) 2 CO 3 ), the magnesia process (Engel-Precht process, Neustatterfurt process; Starting materials: KC1, MgC0 3 '3 H 2 O and C0 2 ), the formate potash process (starting materials: potassium sulfate, calcium hydroxide and carbon monoxide), the Piesteritz process (starting materials: potassium sulfate and calcium cyanamide) and the Le Blanc process (starting materials : Potassium sulfate, calcium carbonate and carbon).
  • Sodium carbonate sesquihydrate is found in nature as a mineral (Trona) and is described by the formula Na ⁇ CO j 'NaHC0 3 ' 2 H 2 O.
  • Large Trona deposits are found, for example, in the USA (Green River / Wyoming), Kenya (Lake Magadi) and the Republic of Sudan (Dongola). While the deposits in Africa can be exploited in the open pit, the Trona in the USA is mined. Trona has a density of 2.17 like 3 and a Mohs hardness of 2.5. Trona is usually used for the production of pure soda, but pure Na ⁇ O j 'NaHCO,' 2 H 2 O can also be produced by the sodium sesquicarbonate process, which is sold.
  • Preferred detergent tablets in the context of the present invention contain potassium carbonate-1,5-water and / or sodium sesquicarbonate in amounts of 0.5 to 15% by weight, preferably in amounts of 1.0 to 12.5% by weight. , particularly preferably in amounts of 1.5 to 10% by weight and in particular in amounts of 2.0 to 7.5% by weight, in each case based on the weight of the molded body.
  • the detergent tablets contain customary ingredients of detergents and cleaning agents, in particular from the groups of surfactants and / or builders and / or Bleach.
  • Other ingredients that can be used in the detergent tablets according to the invention are, for example, bleach activators, enzymes, dyes and fragrances, optical brighteners, polymers, foam inhibitors, etc.
  • the detergent tablets according to the invention can 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.I3 - alkyl benzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and the disulfonates obtained, for example, from C l2 _ 18 monoolefins with terminal or internal double bond by sulfonation with Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which consist of C 12 .
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are 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.
  • the alk (en) yl sulfates are the alkali and, in particular, the sodium salts of the sulfuric acid semiesters of the C 1 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -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, 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.
  • alkyl sulfates and C i2 -C 15 are - as well as alkyl sulfates, preferably C 14 -C 15 alkyl sulfates.
  • alkyl sulfates preferably C 14 -C 15 alkyl sulfates.
  • 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.
  • the Schwefelklasted Acidmonoester of linear or branched C ethoxylated with 1 to 6 mol ethylene oxide 7 _ 21 alcohols such as 2-methyl-branched C 9. ⁇ alcohols containing on average 3.5 mol ethylene oxide (EO) or C 12 _ I g -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 . I 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 triefhanolamine.
  • 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
  • anionic surfactants that are used in the detergent tablets according to the invention, there are no general conditions to be observed that prevent freedom of formulation.
  • preferred detergent tablets have a soap content which exceeds 0.2% by weight, based on the total weight of the tablet.
  • Anionic surfactants to be used with preference 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 fatty alcohol sulfate (s), based in each case on the molded body - important, included
  • 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.
  • the preferred ethoxylated alcohols include, for example, C 12 .
  • 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 JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • 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 is a linear or branched, in particular methyl-branched, saturated or unsaturated ahphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the 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),
  • R-CO-N- [Z] (II) in which RCO stands for an ahphatic acyl radical with 6 to 22 carbon atoms, R for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [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)
  • 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 represents an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C, .4- 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 residue.
  • [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.
  • the builders mentioned can also be used in surfactant-free moldings, so that it is possible according to the invention to produce moldings which can be used for water softening.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x 0 2x + ] ⁇ 2 0, 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 are.
  • 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 Ni-S ⁇ O j 'yH, 0 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 “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.
  • 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.
  • 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 kind of "powdering" of the entire mixture to be ve ⁇ ressed, usually both ways of inco ⁇ oration of the zeolite in 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 which 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), provided that such use is not objectionable for ecological reasons, and mixtures of these this.
  • 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.
  • tablet disintegrants In order to facilitate the disintegration of highly compressed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, in order to shorten the disintegration times.
  • tablet disintegrants or disintegration accelerators 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 1 to 5% by weight and in particular 2 to 4% by weight of a disintegration aid, in each case based on the molded article weight.
  • 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 bratto composition (C 6 H 10 O 5 ) n and, formally speaking, represents a ⁇ -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.
  • 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 cellulose produced by the hydrolysis sen supplies the microcrystalline celluloses, which have primary particle sizes of approx. 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
  • detergent tablets 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 in the context 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, pelleting 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 a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular above 700 g / 1.
  • the potassium carbonate, 1,5-water and / or sodium sesquicarbonate used to improve the solubility of the moldings can simply be added to the premix before being compressed, but it can also be part of one or more granules or compounds without being impaired in its action .
  • the potassium carbonate, 1,5-water and / or sodium sesquicarbonate is the or one of the components of the premix to be admixed which is subsequently added.
  • the premix Before the particulate premix is pressed into detergent and cleaning product shaped bodies, 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. 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.
  • zeolite-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, Toronto, 1974, page 92).
  • 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 structure group 4, can also be used as powdering agents, it being advantageous if at least 50% by weight of the powdering agent consist of a zeolite of the faujasite type.
  • detergent tablets consist of a particulate premix which contains 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 is 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 and silicone oils , Anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.
  • 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. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkyl peroxy acids, but also peroxy- ⁇ -naphthoic acid and magnesium monope ⁇ hthalat, (b) the ahphatician or substituted ahphatician peroxy acids such as peroxylauric acid, peroxy stearic acid, ⁇ -phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanklare (PAP)], o- Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic acid and N - nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassyl acid, the diperoxyphthalic acids, 2-decyl
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in molded articles for automatic dishwashing.
  • Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid,
  • Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium are considered.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • bleach activators can be incorporated as the sole component 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. Suitable are substances which carry O- and / or N-acyl groups of the stated number of carbon atoms and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylene diamine (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, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • 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 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 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.
  • nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl grapple 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
  • polymers of phthalic acid and / or terephthalic acid or of 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.
  • the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • the moldings can contain derivatives of diammostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are e.g. 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 Grappe 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 washing and cleaning agent shaped articles according to the invention in order to improve the aesthetic impression of the products and to provide the consumer with a visual and sensory "typical and unmistakable" product in addition to the softness performance.
  • Individual fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexylpropylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylateylalylatepylate.
  • the ethems include, for example, benzyl ethyl ether, for the aldehydes, for example the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, for the ketones, for example the jonones, oc-isomethylionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and te ⁇ ineol, the hydrocarbons mainly include tephenols 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, citras, 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 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.
  • 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 feeding them into tablets, whereby conventional methods can be used.
  • the premix is compacted in a so-called die between two punches to form a solid compact. This process, which is briefly referred to below as tabletting, 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 metering, even at high mold throughputs, is preferably calibrated via a 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.
  • the premix particles are also crushed and sintering of the premix occurs at even higher pressures.
  • 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.
  • the weight of the molded body is finally determined, since the compacts can still change their shape and size due to physical processes (stretching, crystallographic effects, cooling, etc.). Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches.
  • 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 disc, the number of die bores 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 punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps.
  • the die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compaction, plastic deformation and ejection by means of rail-like cam 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 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.
  • 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 washing and / or cleaning medium corresponds. However, it is also possible to form compacts which combine a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by 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 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 Ausftihrangsform the molded body is adapted in its dimensions of the induction chamber of commercial household washing machines, so that the shaped body can be metered directly into the induction chamber without metering aid, where it dissolves during the induction process.
  • metering aid a metering aid
  • Another preferred molded body that can be produced has a plate-like or plate-like structure with alternating 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 realized 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 application properties of the molded body. If, for example, components are contained in the molded body that are mutually negative tiv influence, it is possible to integrate one component in the more rapidly soluble layer and to incorporate the other component in a slower 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 outer 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 multilayer molded bodies have the advantage that they can be used not only via a dispensing chamber or via a metering device which is added to the washing liquor; rather, in such cases it is also possible to put the molded body into direct contact with the textiles in the machine, without fear of bleaching by bleaching agents 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 melt coating method. After pressing, the detergent tablets have a high stability.
  • the breaking strength of cylindrical shaped bodies can be determined via the measured quantity of the diametrical break load. This can be determined according to
  • ⁇ stands for diametrical fracture stress (DFS) in Pa
  • P is the force in N, which 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.
  • Another object of the present invention is the use of potassium carbonate-1,5-water and / or sodium sesquicarbonate to increase the hardness while reducing the rate of dissolution of detergent and detergent tablets.
  • Potassium carbonate-1,5-water and / or sodium sesquicarbonate used according to the invention leads to the fact that despite varying press pressure on the premix to be ve ⁇ resse wash and cleaning agent foils are obtained, the dissolution rate of which does not deviate significantly from the mean. In this way, increased process reliability in the production of molded bodies is guaranteed.
  • premixes were produced which were pressed into detergent tablets in a Korsch tablet press.
  • the press was set so that three series of molded bodies were obtained each, which differ in their hardness.
  • the premix which leads to the shaped bodies El and E2 according to the invention, contained 4% by weight of potassium carbonate 1,5-water or sodium sesquicarbonate, while a comparative premix, which provided the shaped bodies VI and V2 when subjected to pressure, contained anhydrous potassium carbonate or did not contain any of the substances mentioned.
  • 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).
  • anhydrous potassium carbonate (VI) initially also leads to shaped bodies with fluctuating pressing forces, which are characterized by a small variation in the dissolving speed, the shaped bodies show no desirable properties: when stored, the tablets V2 soften to some extent - the advantage according to the invention Compensation of the process uncertainty by varying pressing forces does not occur here, since the process uncertainty is only shifted to the storage.
  • 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 which 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)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des corps moulés détergents constitués d'un détergent particulaire comprimé, comportant un ou des tensioactifs et/ou un ou des adjuvants de lavage et/ou des agents de blanchiment, ainsi que du carbonate de potassium 1,5-eau et/ou du sesquicarbonate de sodium.
PCT/EP1999/003566 1998-06-03 1999-05-25 Corps moules detergents stables a la rupture et se dissolvant rapidement WO1999063045A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020007013625A KR20010052496A (ko) 1998-06-03 1999-05-25 파쇄-안정성, 빠른-용해성의 세정제 성형체
EP99926386A EP1086203A1 (fr) 1998-06-03 1999-05-25 Corps moules detergents stables a la rupture et se dissolvant rapidement
JP2000552242A JP2002517559A (ja) 1998-06-03 1999-05-25 洗剤タブレット

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19824743A DE19824743A1 (de) 1998-06-03 1998-06-03 Bruchstabile und schnellösliche Wasch- und Reinigungsmittelformkörper
DE19824743.5 1998-06-03

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WO1999063045A1 true WO1999063045A1 (fr) 1999-12-09

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WO (1) WO1999063045A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109691959A (zh) * 2017-10-20 2019-04-30 青岛海尔洗碗机有限公司 一种水软及洗涤剂添加一体式装置及洗碗机

Families Citing this family (1)

* 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

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1191721A (en) * 1966-04-21 1970-05-13 Colgate Palmolive Co Production of Detergent Laundry Bars of Low Specific Gravity
EP0242138A2 (fr) * 1986-04-14 1987-10-21 Unilever Plc Procédé de fabrication de détergents en poudre
JPH03172398A (ja) * 1989-11-30 1991-07-25 Shin Etsu Chem Co Ltd 医療用手術刀の洗浄剤
WO1993000419A1 (fr) * 1991-06-27 1993-01-07 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de produits de lavage en comprimes pour le lavage de la vaisselle en machine
EP0799886A2 (fr) * 1996-04-03 1997-10-08 Cleantabs A/S Tablettes de détergent pour du linge
EP0903405A2 (fr) * 1997-09-23 1999-03-24 Unilever Plc Composition pour lave-vaisselle

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1191721A (en) * 1966-04-21 1970-05-13 Colgate Palmolive Co Production of Detergent Laundry Bars of Low Specific Gravity
EP0242138A2 (fr) * 1986-04-14 1987-10-21 Unilever Plc Procédé de fabrication de détergents en poudre
JPH03172398A (ja) * 1989-11-30 1991-07-25 Shin Etsu Chem Co Ltd 医療用手術刀の洗浄剤
WO1993000419A1 (fr) * 1991-06-27 1993-01-07 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de produits de lavage en comprimes pour le lavage de la vaisselle en machine
EP0799886A2 (fr) * 1996-04-03 1997-10-08 Cleantabs A/S Tablettes de détergent pour du linge
EP0903405A2 (fr) * 1997-09-23 1999-03-24 Unilever Plc Composition pour lave-vaisselle

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 9136, Derwent World Patents Index; Class A96, AN 91-263184, XP002114810 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109691959A (zh) * 2017-10-20 2019-04-30 青岛海尔洗碗机有限公司 一种水软及洗涤剂添加一体式装置及洗碗机

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DE19824743A1 (de) 1999-12-09
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JP2002517559A (ja) 2002-06-18

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