WO1997026317A1 - Procede de production de corps moules constitues d'un produit de lavage ou de nettoyage - Google Patents
Procede de production de corps moules constitues d'un produit de lavage ou de nettoyage Download PDFInfo
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- WO1997026317A1 WO1997026317A1 PCT/EP1997/000087 EP9700087W WO9726317A1 WO 1997026317 A1 WO1997026317 A1 WO 1997026317A1 EP 9700087 W EP9700087 W EP 9700087W WO 9726317 A1 WO9726317 A1 WO 9726317A1
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- surfactants
- sodium silicate
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- 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
- C11D3/08—Silicates
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- 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
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0086—Laundry tablets
Definitions
- the invention relates to a method for producing detergent tablets containing surfactants.
- Microwave technology offers another possibility for the production of detergent tablets.
- international application WO 94/25563 describes the production of washing and cleaning-active molded articles using microwave technology, which have an extremely high dissolving rate or disintegration rate.
- This technique can be used to produce so-called macrosoiids, which can usually contain up to 40% by weight of surfactants.
- one of the raw materials used in substantial quantities is a crystalline layered silicate, in particular of the type SKS-6 ® (crystalline sodium disilicate; commercial product from Hoechst AG, Germany), the surfactant content can even be up to 60% by weight.
- microwave molded articles which contain anionic surfactants in substantial amounts, for example in amounts above 10% by weight, and inorganic salts in amounts below 60% by weight are to be produced, these can be prepared according to the teaching of the earlier German application P 4429550.2 by introducing the anionic surfactants into the process in the form of one or more compounds.
- the invention therefore relates to a process for the production of detergent tablets containing surfactants, the starting materials being admixed in solid form with amorphous sodium silicate, which has a water content of less than 15% by weight, and this mixture is then molded in a manner known per se is transferred.
- the process according to the invention is characterized in that amorphous sodium silicate in solid form, which has a water content of less than 15% by weight, is added to the starting materials. It is advantageous to introduce the amorphous sodium silicate into the process as finely divided as possible, that is to say as a powder.
- the amorphous sodium silicates used in the process according to the invention are preferably silicates in the module range (molar ratio SiO 2 / Na 2 O) 1, 3 to 3.0, in particular 1.8 to 3.
- the term "amorphous" is used in the context of Invention also understood “X-ray amorphous".
- the water content of the amorphous sodium silicates used according to the invention is below 15% by weight, preferably between 0.5 and 13% by weight and in particular between 2 and 8% by weight.
- the amorphous silicates used according to the invention with a water content of less than 15% by weight can be produced, for example, according to the process of EP 542 131 by drying water glass solutions with hot air or flue gas.
- the use of dried amorphous sodium silicate is also preferred, as is described in German patent application DE 44 00 024.
- the detergent tablets produced according to the invention preferably have a proportion of dried amorphous sodium silicate, based on the total weight of the tablets, between 1 and 25% by weight, preferably between 3 and 15% by weight.
- the moldings can be obtained in a manner known per se, for example by pressing or by casting the constituents or with the aid of microwave technology.
- the moldings are produced using microwave technology.
- the premixed components are placed in a mold and pressed under pressure.
- the amount of pressure is selected depending on the desired strength of the molded body.
- the moldings can be produced by casting if all or some of the components can be converted into a liquid form, for example by melting or pressurization, and all components are stable under these conditions.
- the liquid mixture is poured into a mold and then allowed to solidify.
- the radiation leads to elevated temperatures and to the local sintering of the ingredients at the contact points, the cavities in the molded body being retained, ie complete fusion of the ingredients with one another is avoided.
- the cavities that exist between the individual ingredients before the irradiation with microwaves bring about a high porosity of the resulting shaped bodies and thus contribute to improving the dissolving properties of the shaped bodies.
- starting materials In order for local sintering of the starting materials to be possible, at least some of them must have sintering properties on the surface. For this purpose, it is necessary that the starting materials themselves or their surface contain enough water so that the contact points of the ingredients are fused by the heating of this water. Therefore, in a preferred embodiment of the present invention, starting materials are used, some of which are in hydrated form. In the context of this application, “hydrated” means “hydrated under certain conditions with regard to temperature, pressure or relative humidity of the atmosphere to which the raw material is exposed or with which the raw material is in equilibrium”.
- shaped body is not restricted to a specific spatial shape. In principle, any spatial shape is possible that can be forced onto the starting materials due to an outer container. Preference is given to tablets in a conventional sense, ie cylindrical bodies, the height of the cylinder being smaller is than its diameter
- the spatial shape of a particularly preferred embodiment of the tablet is adapted in its dimensions to the induction chamber of commercially available household washing machines, so that the tablet can be dosed directly into the induction chamber without metering aid, where it dissolves during the induction process
- Another preferred shaped body which can be produced has a plate-like or plate-like structure with alternately thick long and thin short segments, so that individual segments of this "bolt" at the predetermined breaking points, which represent the short thin segments, are broken off and into the Machine can be entered
- This principle of the "cone-shaped” tablet detergent can also be implemented in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides
- the individual starting materials are used in the form of compounds, that is to say pre-prepared mixtures of individual starting materials, surfactant compounds are particularly preferably used, in particular compounds containing anionic surfactants, which may also contain nonionic, amphoteric or kattonic surfactants.
- the surfactant compounds usually have a surfactant content of at least 10% by weight, preferably at least 40% by weight, particularly preferably 60 to 95% by weight, based on the compound.
- the tablets which have a mutually negative effect
- the layer structure of the tablets can take place in a stack-like manner, with the inner layer (s) already loosening at the edges of the tablet when the outer layers have not yet been completely dissolved, but it is also possible to completely encase the inner layer (s) ) can be achieved by the outer layer (s), which leads to the premature dissolution of components of the inner layer (s).
- a tablet consists of at least three layers, that is to say 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 tablet in the form of a tablet, the two outer layers and in the case of the envelope Tablet the outermost layers, however, are free from peroxy bleach. Furthermore, it is also possible to spatially separate peroxy bleaching agents and any bleach activators and / or enzymes present in a tablet. Such multilayer tablets have the advantage that they can be used not only via a dispenser or via a metering device which is added to the washing liquor; rather, it is also possible in such cases to put the tablet in direct contact with the textiles in the machine without fear of bleaching and the like.
- compounds containing anionic surfactants which contain various anionic surfactants - for example alkyl sulfates and alkylbenzenesulfonates and / or soap or alkyl sulfates and sulfated fatty acid glycerol esters - and / or anionic surfactants in combination with nonionic surfactants - for example alkyl sulfates and ethoxylated fatty alcohols or alkyl sulfonates, alkylbenzene sulfates, ethoxylated fatty alcohols and / or alkyl glycosides or alkyl sulfates, soap, ethoxylated fatty alcohols and glucamides - contain. These are preferably compounds which contain anionic surfactants and nonionic surfactants in a weight ratio of 10: 1 to 1:10.
- Another preferred embodiment of the invention provides that at least two different types of compounds are used in the process.
- At least 15% by weight, preferably 35% by weight and in particular at least 50% by weight of the total formulation of the laundry detergent or cleaning product tablets produced consist of one or more different types of compounds. It can be particularly advantageous to use at least 75% by weight and up to 100% by weight of the total formulation as a compound, which has optionally been post-treated.
- conventional and commercially available washing or cleaning agents which contain at least one compound containing anionic surfactants can be converted into moldings in the manner according to the invention. Examples of this are spray-dried detergents with bulk densities of about 300 to 600 g / l, which preferably contain 5 to 40% by weight of anionic surfactants in the spray-dried proportions.
- Non-ionic surfactants are to be mentioned here as preferred liquid constituents, for example finely divided zeolites, silicas, sulfates and / or calcium stearates as powdering agents.
- spray-dried granules containing anionic surfactants are present in addition to spray-dried or granulated compounds which consist of carrier materials such as zeolite, crystalline sheet silicates, polymeric polycarboxylates, carbonates and optionally also silicates and with liquid to paste-like or wax-like ingredients such as nonionic surfactants and / or foam inhibitors or conventional textile softeners are impregnated.
- carrier materials such as zeolite, crystalline sheet silicates, polymeric polycarboxylates, carbonates and optionally also silicates and with liquid to paste-like or wax-like ingredients such as nonionic surfactants and / or foam inhibitors or conventional textile softeners are impregnated.
- the shaped articles produced according to the invention are aftertreated with further substances, in particular ingredients of washing or cleaning agents.
- further substances in particular ingredients of washing or cleaning agents.
- substances that are not stable under the conditions of manufacture such as high temperatures or pressures.
- these include, for example, enzymes and perfumes.
- enzymes and perfumes When using microwave technology it may be advantageous for enzymes to be irradiated because of the better possible temperature control or the lower temperature load of the overall mixture.
- the moldings produced according to the invention are provided with a coating of hydrated salts, such as sodium acetate trihydrate or the di-, hepta- or dodecahydrate of disodium hydrogen phosphate, according to the teaching of European patent application EP-A-0 002 293.
- hydrated salts such as sodium acetate trihydrate or the di-, hepta- or dodecahydrate of disodium hydrogen phosphate
- Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
- Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained from C 12 -C B monoolefins with a terminal or internal double bond by sulfonating Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
- alkanesulfonates obtained from C 2 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
- Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
- Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
- Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
- Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
- alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid semiesters of C 1 -C 8 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 0 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
- alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
- C 6 -C 8 alk (en) yl sulfates are particularly preferred for washing technology reasons. It can also be particularly advantageous, and particularly advantageous for machine detergents, C 16 -C 8 -alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and at relatively low Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize.
- the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably C 2 -C 18 fatty alkyl sulfates or mixtures of Ci 2 -Ci 4 fatty alkyl sulfates or C 2 -C 8 fatty alkyl sulfates with C 1 -C 8 8 - Fatty alkyl sulfates and in particular C 12 -C 5 fatty alkyl sulfates with C ⁇ rC ⁇ fatty alkyl sulfates.
- saturated alkyl sulfates not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
- Mixtures of saturated sulfated fatty alcohols consisting predominantly of C 1 and unsaturated sulfated fatty alcohols consisting predominantly of C 8 are preferred, for example those derived from solid or liquid fatty alcohol mixtures of the HD-Ocenol ® type (commercial product of the applicant).
- Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred. 2,3-alkyl sulfates are also suitable.
- the sulfuric acid monoesters of the straight-chain or branched C 7 -C 2 -alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 -C ⁇ 8 fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in detergents 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 in particular ethoxylated fatty alcohols.
- alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8 -C 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).
- 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 soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
- those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 2 -C 24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
- the anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and 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.
- nonionic, cationic, zwitterionic or amphoteric surfactants can also be used in the moldings.
- Nonionic surfactants are particularly preferred.
- Preferred nonionic surfactants are alkoxylated, advantageously ethoxylated, in particular primary alcohols with 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 residue may be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched residues in the mixture, as is usually present in oxo alcohol residues.
- EO ethylene oxide
- the preferred ethoxylated alcohols include, for example, C 2 -C 4 - Alcohols with 3 EO or 4 EO, Crd alcohol with 7 EO, -C 3 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C ⁇ 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 2 -Cn alcohol with 3 EO and C 2 -C 8 alcohol with 5 EO.
- the degrees of ethoxylation given represent statistical mean values which are 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 these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO
- alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R is a p ⁇ maren straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10, preferably x is 1, 2 to 1, 4
- 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 having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as those are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533
- nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and
- Fatty acid alkanolamides can 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.
- Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
- R-CO for an aliphatic acyl radical having 6 to 22 carbon atoms
- R 1 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 (II), R 3 -OR 4
- R 2 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 3 is a linear, branched or cyclic alkyl radical or an aryl radical is 2 to 8 carbon atoms
- R 4 is a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, CrC 4 alkyl or phenyl radicals being preferred
- [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- the N-alkoxy or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst
- the moldings can contain all of the usual ingredients of detergents or cleaning agents in their overall formulation.
- these include, in particular, inorganic and organic builder substances, components which prevent the textile fabric from being soiled again (soil repellents), and graying inhibitors, alkaline salts, Bleaching agents and bleach activators, foam inhibitors, fabric softening substances, neutral salts as well as colorings and fragrances
- suitable inorganic builders are, in particular, aluminosilicates of the Zeohth type.
- the low-calorie, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P in detergent quaternate.
- zeolite X and mixtures of A, X and / or are also suitable P
- Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMS ⁇ x 0 2x + ⁇ y H2 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 are 2, 3 or 4.
- Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
- Preferred crystalline layered silicates are those in which M represents sodium and x assumes the values 2 or 3 both ß- and ⁇ -Nat ⁇ umdisihkate Na 2 S ⁇ 2 0 5 yH 2 0 preferred
- Usable organic scent substances are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acid, ammocarboxylic acids, nitric acid acetic acid (NTA), provided that such use is not objectionable for ecological reasons, and these salts are not objectionable; are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acid and mixtures of these Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
- Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
- Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid, have proven to be particularly suitable.
- Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
- biodegradable polymers with more than two different monomer units, for example those which are salts of acrylic acid and as monomers maleic acid and vinyl alcohol or vinyl alcohol derivatives (DE 43 00 772.) or the monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives (DE 42 21 381).
- copolymers are those which are described in German patent applications DE 43 03 320 and P 44 17 734.8 and which preferably contain acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers.
- oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts are described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110.
- polyaspartic acids or their salts and derivatives are also to be mentioned as further preferred builder substances.
- polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223.
- Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
- the inorganic and / or organic builder substances are preferably used in the tablets in amounts of approximately 10 to 60% by weight, in particular 15 to 50% by weight.
- the agents can also contain components which have a positive influence on the oil and fat washability from textiles. This effect is particularly evident 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 in particular methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ethers, 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. They can take effect in small quantities. Their content is therefore preferably 0.2 to 10% by weight and in particular up to 5% by weight.
- Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying.
- Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
- Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc.
- Polyvinylpyrrolidone can also be used.
- cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the detergent, are preferred used.
- Other suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates and carbonates.
- the sodium carbonate and / or bicarbonate content of the agents is preferably up to 50% by weight, advantageously between 10 and 25% by weight.
- bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 0 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
- the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate and / or percarbonate.
- bleach activators can be incorporated into the preparations.
- these are N-acyl or O-acyl compounds which form organic peracids with H 2 0 2 , preferably N, N'-tetraacylated diamines, p-
- bleach activators are acetylated mixtures of sorbitol and mannitol, as are described, for example, in European patent application EP-A-0 525 239.
- the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
- bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
- TAED N, N, N ', N'-tetraacetylethylenediamine
- DADHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine
- SORMAN acetylated sorbitol-mannitol mixtures
- Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 2 -C 8 fatty acids.
- Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicone, paraffins or To grow.
- the foam inhibitors, in particular silicone- or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or water-dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
- the salts of polyphosphonic acids which are preferably used are the neutral sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate,
- Diethylenetriaminepentamethyienphosphonat or ethylenediaminetetramethylenephosphonate used in amounts of 0.1 to 1, 5 wt .-%.
- 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 the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
- the tablets can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-mo ⁇ holino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, 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) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. Examples Example 1
- a tablet was produced from the compounds, powders and liquids listed below in accordance with the teaching of international patent application WO 94/25563.
- Granulated compounds were used as starting materials (Table 1), which were mixed in a mixer to form a homogeneous overall mixture, which was then converted into a shaped body filled and pre-pressed for 10 seconds with a pressure of 13 N / cm 2 (the force exerted on the circular area was 35 N on an area of 2.7 cm 2 ).
- the microwave irradiation was then carried out at 2450 MHz and 250 watts. 5 seconds
- the tablets had a diameter of 4 cm, a height of 2.5 cm and a weight of 20 g.
- the amorphous sodium silicate (module 2.0) used had a water content of 13% by weight (measured as glow loss, produced according to the Method of DE 44 00 024)
- the compressive strength of the tablets was measured with a SCHLEUNIGER tablet hardness test device model 6D
- a shaped body (20 g) was added to dry laundry (3.5 kg) in a conventional metering device in a washing machine (type Miele Novotronic W 918). After water had run in, the metering device was weighed with the shaped body. A colored washing program was then carried out (111 water, 16 ° C.). After 5 and 10 minutes the washing program was interrupted and the metering device with the remnants of the shaped body was weighed. The differences from the first measurement of the dosing device with molded body can be found in Table 1.
- Tablets were produced by the same procedure as in Example 1.
- the amorphous sodium silicate (module 2.0) had a water content of 8% by weight (measured as loss on ignition, produced by the process of DE 44 00 024).
- the tablets produced in this way had a compressive strength of at least 20 N / cm 2 and disintegrated in cold water after no more than 60 seconds. (To measure the rate of disintegration, the tablets were placed in a beaker with 750 ml of water and the time at which the tablets had disintegrated was determined).
- the recipes can be found in Table 2.
Landscapes
- 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)
- Detergent Compositions (AREA)
Abstract
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP97900991A EP0877791B1 (fr) | 1996-01-19 | 1997-01-10 | Procede de production de corps moules constitues d'un produit de lavage ou de nettoyage |
AT97900991T ATE193548T1 (de) | 1996-01-19 | 1997-01-10 | Verfahren zur herstellung von wasch- oder reinigungsmittelformkörpern |
DE59701807T DE59701807D1 (de) | 1996-01-19 | 1997-01-10 | Verfahren zur herstellung von wasch- oder reinigungsmittelformkörpern |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19601840A DE19601840A1 (de) | 1996-01-19 | 1996-01-19 | Verfahren zur Herstellung von Wasch- oder Reinigungsmittelformkörpern |
DE19601840.4 | 1996-01-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997026317A1 true WO1997026317A1 (fr) | 1997-07-24 |
Family
ID=7783177
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1997/000087 WO1997026317A1 (fr) | 1996-01-19 | 1997-01-10 | Procede de production de corps moules constitues d'un produit de lavage ou de nettoyage |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0877791B1 (fr) |
AT (1) | ATE193548T1 (fr) |
DE (2) | DE19601840A1 (fr) |
ES (1) | ES2148923T3 (fr) |
WO (1) | WO1997026317A1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5866531A (en) * | 1994-08-19 | 1999-02-02 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of detergent or cleaning tablets |
US5914309A (en) * | 1994-11-07 | 1999-06-22 | Henkel-Ecolab Gmbh & Co. Ohg | Process for the production of detergent tablets by microwave and hot air treatment |
WO2000015752A2 (fr) * | 1998-09-10 | 2000-03-23 | Henkel Kommanditgesellschaft Auf Aktien | Procede de production de corps moules de lavage et de nettoyage |
GB2362161A (en) * | 2000-03-11 | 2001-11-14 | Mcbride Robert Ltd | Detergent tablets |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19636036A1 (de) * | 1996-09-05 | 1998-03-12 | Henkel Kgaa | Verfahren zur Herstellung tensidhaltiger Formkörper mit Mikrowellenstrahlung |
DE19709411A1 (de) * | 1997-03-07 | 1998-09-10 | Henkel Kgaa | Waschmittelformkörper |
US5961663A (en) * | 1997-05-29 | 1999-10-05 | Colgate-Palmolive Co. | Microwave-dried amorphous alkali metal silicate powders and their use as builders in detergent compositions |
DE19910819A1 (de) * | 1999-03-11 | 2000-09-14 | Henkel Kgaa | Wasch- und Reinigungsmittelformkörper mit Tensid-Bleichmittel-Builderkombination |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1077067A (en) * | 1963-10-18 | 1967-07-26 | Unilever Ltd | Detergent tablet |
US3366570A (en) * | 1961-05-15 | 1968-01-30 | Lever Brothers Ltd | Process of preparing detergent tablets |
US3674700A (en) * | 1967-07-18 | 1972-07-04 | Conrad J Gaiser | Detergent tablet of amorphous sodium silicate having inherent binding properties,containing a surfactant,and method of making such tablet |
EP0126963A1 (fr) * | 1983-05-02 | 1984-12-05 | Henkel Kommanditgesellschaft auf Aktien | Procédé pour la production de comprimés d'agent de nettoyage |
WO1994025563A1 (fr) * | 1993-05-05 | 1994-11-10 | Henkel-Ecolab Gmbh & Co. Ohg | Procede de consolidation de solides particulaires et produits de nettoyage a base de ceux-ci |
DE4400024A1 (de) * | 1994-01-03 | 1995-07-06 | Henkel Kgaa | Silikatische Builder und ihre Verwendung in Wasch- und Reinigungsmitteln sowie Mehrstoffgemische für den Einsatz auf diesem Sachgebiet |
DE4404279A1 (de) * | 1994-02-10 | 1995-08-17 | Henkel Kgaa | Tablette mit Buildersubstanzen |
DE4429550A1 (de) * | 1994-08-19 | 1996-02-22 | Henkel Kgaa | Verfahren zur Herstellung von Wasch- oder Reinigungsmitteltabletten |
-
1996
- 1996-01-19 DE DE19601840A patent/DE19601840A1/de not_active Withdrawn
-
1997
- 1997-01-10 ES ES97900991T patent/ES2148923T3/es not_active Expired - Lifetime
- 1997-01-10 EP EP97900991A patent/EP0877791B1/fr not_active Revoked
- 1997-01-10 WO PCT/EP1997/000087 patent/WO1997026317A1/fr not_active Application Discontinuation
- 1997-01-10 AT AT97900991T patent/ATE193548T1/de not_active IP Right Cessation
- 1997-01-10 DE DE59701807T patent/DE59701807D1/de not_active Revoked
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3366570A (en) * | 1961-05-15 | 1968-01-30 | Lever Brothers Ltd | Process of preparing detergent tablets |
GB1077067A (en) * | 1963-10-18 | 1967-07-26 | Unilever Ltd | Detergent tablet |
US3674700A (en) * | 1967-07-18 | 1972-07-04 | Conrad J Gaiser | Detergent tablet of amorphous sodium silicate having inherent binding properties,containing a surfactant,and method of making such tablet |
EP0126963A1 (fr) * | 1983-05-02 | 1984-12-05 | Henkel Kommanditgesellschaft auf Aktien | Procédé pour la production de comprimés d'agent de nettoyage |
WO1994025563A1 (fr) * | 1993-05-05 | 1994-11-10 | Henkel-Ecolab Gmbh & Co. Ohg | Procede de consolidation de solides particulaires et produits de nettoyage a base de ceux-ci |
DE4400024A1 (de) * | 1994-01-03 | 1995-07-06 | Henkel Kgaa | Silikatische Builder und ihre Verwendung in Wasch- und Reinigungsmitteln sowie Mehrstoffgemische für den Einsatz auf diesem Sachgebiet |
DE4404279A1 (de) * | 1994-02-10 | 1995-08-17 | Henkel Kgaa | Tablette mit Buildersubstanzen |
DE4429550A1 (de) * | 1994-08-19 | 1996-02-22 | Henkel Kgaa | Verfahren zur Herstellung von Wasch- oder Reinigungsmitteltabletten |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5866531A (en) * | 1994-08-19 | 1999-02-02 | Henkel Kommanditgesellschaft Auf Aktien | Process for the production of detergent or cleaning tablets |
US5914309A (en) * | 1994-11-07 | 1999-06-22 | Henkel-Ecolab Gmbh & Co. Ohg | Process for the production of detergent tablets by microwave and hot air treatment |
WO2000015752A2 (fr) * | 1998-09-10 | 2000-03-23 | Henkel Kommanditgesellschaft Auf Aktien | Procede de production de corps moules de lavage et de nettoyage |
WO2000015752A3 (fr) * | 1998-09-10 | 2007-07-26 | Henkel Kgaa | Procede de production de corps moules de lavage et de nettoyage |
GB2362161A (en) * | 2000-03-11 | 2001-11-14 | Mcbride Robert Ltd | Detergent tablets |
Also Published As
Publication number | Publication date |
---|---|
EP0877791B1 (fr) | 2000-05-31 |
ATE193548T1 (de) | 2000-06-15 |
ES2148923T3 (es) | 2000-10-16 |
DE59701807D1 (de) | 2000-07-06 |
DE19601840A1 (de) | 1997-07-24 |
EP0877791A1 (fr) | 1998-11-18 |
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