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WO1999041351A1 - Corps moules nettoyants et detergents contenant des agents de blanchiment - Google Patents

Corps moules nettoyants et detergents contenant des agents de blanchiment Download PDF

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Publication number
WO1999041351A1
WO1999041351A1 PCT/EP1998/006474 EP9806474W WO9941351A1 WO 1999041351 A1 WO1999041351 A1 WO 1999041351A1 EP 9806474 W EP9806474 W EP 9806474W WO 9941351 A1 WO9941351 A1 WO 9941351A1
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WO
WIPO (PCT)
Prior art keywords
weight
detergent
washing
cleaning agent
article according
Prior art date
Application number
PCT/EP1998/006474
Other languages
German (de)
English (en)
Inventor
Gerhard Blasey
Christian Block
Monika Böcker
Heinke Jebens
Hans-Friedrich Kruse
Andreas Lietzmann
Antoni Machin
Fred Schambil
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.)
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Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=25681999&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1999041351(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP98955440A priority Critical patent/EP1056833B1/fr
Priority to SK1202-2000A priority patent/SK12022000A3/sk
Priority to DE59803243T priority patent/DE59803243D1/de
Priority to ES98955440T priority patent/ES2173640T3/es
Priority to JP2000531532A priority patent/JP2002503761A/ja
Priority to AT98955440T priority patent/ATE213768T1/de
Priority to HU0100727A priority patent/HUP0100727A2/hu
Publication of WO1999041351A1 publication Critical patent/WO1999041351A1/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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts

Definitions

  • the present invention relates to detergent tablets. which contain bleach.
  • the invention relates to moldings such as detergent tablets, detergent tablets, bleach tablets or water softener tablets with bleach.
  • the dichotomy between a sufficiently hard molded body and a sufficiently fast disintegration time is a central problem. Since sufficiently stable, that is to say shape and break-resistant molded articles can only be produced by relatively high compression pressures, there is a strong compression of the molded article components and consequent delayed disintegration of the molded article in the aqueous liquor and thus to a slow release of the active substances in the Washing or cleaning process.
  • the delayed disintegration of the moldings has the further disadvantage that conventional detergent tablets cannot be washed in via the induction chamber of household washing machines, since the tablets cannot be taken in quickly enough 2
  • EP-A-0 522 766 discloses moldings made from a compact, particulate detergent composition containing surfactants, builders and disintegration aids (for example based on cellulose), at least some of the particles being coated with the disintegration agent, which is both binder and also shows disintegration effects when the moldings are dissolved in water.
  • This document also indicates the general difficulty of producing moldings with adequate stability and good solubility at the same time.
  • the particle size in the mixture to be pressed should be above 200 ⁇ m, the upper and lower limits of the individual particle sizes should not differ from one another by more than 700 ⁇ m.
  • EP-A-0 716 144 (Unilever), which describes tablets with an external shell made of water-soluble material
  • EP-A-0 711 827 (Unilever), which contain a citrate with a defined solubility as an ingredient.
  • binders which may have an explosive effect (in particular polyethylene glycol), is disclosed in EP-A-0 711 828 (Unilever), which describes detergent tablets which are formed by pressing a particulate 3
  • Detergent compositions are produced at temperatures between 28 ° C and the melting point of the binding material, always pressing below the melting temperature. From the examples in this document it can be seen that the moldings produced in accordance with their teaching have higher breaking strengths when compression is carried out at elevated temperature.
  • the present invention is therefore based on the object of providing detergent tablets which contain bleaching agents and have a high hardness and have excellent disintegration properties.
  • These laundry detergent and cleaning product tablets should also be able to be metered through the induction chamber without the consumer suffering disadvantages as a result of residues in the induction chamber and too little detergent in the detergent solution.
  • the washing and cleaning performance of the moldings according to the invention should also be exemplary.
  • the invention relates to detergent tablets made of compressed particulate detergent and detergent, comprising bleach, builder (s) and optionally further detergent and detergent components in which the bleach has an average particle size above 0.4 mm. 4
  • the average particle size is a computational size which results from the multiplication of the percentage of a sieve fraction by the mesh size of the sieve.
  • the individual values of such mean values can vary widely if, for example, extremely small and extremely large particles are present side by side. In the context of the present invention, however, it is preferred that the particle size distribution of the bleaching agent does not vary widely, but rather is relatively narrow around the mean. In particular, fine fractions should be largely excluded, so that detergent tablets are preferred in the context of the present invention in which the bleaching agent is substantially free of particles with sizes below 0.2 mm.
  • substantially free means contents below 2% by weight, preferably below 1% by weight and in particular below 0.5% by weight.
  • the content of particles with a size below 0.4 mm should also be kept as small as possible. Preference is given to detergent tablets in which the bleach contains less than 30% by weight, preferably less than 20% by weight and in particular less than 10% by weight, of particles having a size below 0.4 mm.
  • the proportion of larger bleach particles should be as high as possible.
  • the particles of the bleaching agent are not only larger than 0.4 mm, but significantly larger, for example larger than 0.8 mm.
  • detergent tablets are preferred in which the bleaching agent has more than 10% by weight, preferably more than 20% by weight and in particular more than 30% by weight of particles of a size above 0.8 mm.
  • the bleach should of course not be incorporated in the form of coarse lumps in the detergent tablets of the present invention. From a practical point of view, particle sizes of the bleaching agent below 2.0 mm have proven successful, it being preferred if this is in the washing and 5
  • Bleach contained in detergent tablets is substantially free of particles larger than 1.6 mm.
  • the detergent tablets of the present invention contain one or more bleaches.
  • bleaches include sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • the bleaching agents are used in varying amounts in the detergent tablets according to the invention. Usual contents are between 5 and 50% by weight, preferably between 10 and 40% by weight and in particular between 15 and 35% by weight, in each case based on the entire molded body.
  • bleaching agents the content of these substances in the shaped bodies also depends on the intended use of the shaped bodies. While conventional universal detergents in tablet form contain between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular between 12.5 and 22.5% by weight of bleaching agent, the contents of bleaching agent or bleach booster tablets are between 15 and 50% by weight, preferably between 22.5 and 45% by weight and in particular between 30 and 40% by weight.
  • bleaching agents are sodium perborate or sodium percarbonate.
  • Sodium perborate monohydrate is used with particular preference.
  • the detergent tablets according to the invention can contain bleach activator (s), which is preferred in the context of the present invention.
  • Bleach activators are incorporated into detergents and cleaning agents to help with washing at temperatures of 60 ° C and 6 including an improved bleaching effect. Can be used as bleach activators
  • aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • 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.
  • the moldings according to the invention each contain, based on the entire mold, between 0.5 and 30% by weight, preferably between 1 and 20% by weight and in particular between 2 and 15% by weight, of one or more bleach activators or bleach catalysts. These amounts can vary depending on the intended use of the moldings produced. For example, bleach activator contents of between 0.5 and 10% by weight, preferably between 2 and 8% by weight and in particular between 4 and 6% by weight are common in typical universal detergent tablets, while bleach tablets have definitely higher contents, for example between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular between 10 and 20% by weight. The person skilled in the art is not restricted in his freedom of formulation and can in this way bleach more or less 7
  • a particularly preferred bleach activator is N, N, N ', N'-tetraacetylethylenediamine, which is widely used in detergents and cleaning agents. Accordingly, preferred detergent tablets are characterized in that tetraacetylethylenediamine is used as the bleach activator in the amounts mentioned above.
  • the detergent tablets according to the invention can contain further ingredients, the amounts of which depend on the intended use of the tablets.
  • substances from the groups of surfactants, builders and polymers are particularly suitable for use in the detergent tablets according to the invention.
  • the person skilled in the art will have no difficulty selecting the individual components and their amounts.
  • a universal detergent tablet will contain higher amounts of surfactant (s), while bleach tablets may even be dispensed with.
  • the amount of builders) used also varies depending on the intended use.
  • All of the builders usually used in detergents and cleaning agents can be present in the detergent tablets according to the invention, in particular thus zeolites, silicates, carbonates, organic cobuilders and — where there are no ecological prejudices against their use — also the phosphates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2 ⁇ +1 'H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x is 2, 3 or 4.
  • M sodium or hydrogen
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20 and preferred values for x is 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 ⁇ 5 'yH 2 O are preferred, 8 where ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X. ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® 9 and by the formula
  • the zeolite can be used both as a builder in a granular compound and can also be used for a type of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates as builder substances, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
  • the amount of builder is usually between 10 and 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight.
  • the amount of builders used depends on the intended use, so that bleach tablets can have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight) ), for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 to 45% by weight and in particular between 17.5 and 37.5% by weight).
  • Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as 10
  • Citric acid Citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Preferred detergent tablets further contain one or more surfactant (s).
  • Anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these can be used in the detergent tablets according to the invention. Mixtures of anionic and nonionic surfactants are preferred from an application point of view.
  • the total surfactant content of the moldings is 5 to 60% by weight, based on the weight of the moldings, with surfactant contents above 15% by weight being preferred.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • surfactants of the sulfonate type preference is given to C 1 -C 8 -alkyl benzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C 12 -C 8 monoolefins with an end or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which consist of C ⁇ 2 .
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as 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 sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid. 11
  • Caprylic acid capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C 2 -C 8 fatty alcohols, for example from coconut fatty 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.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials.
  • the C 12 - Ci 6 alkyl sulfates and C 2 -C 5 alkyl sulfates and C 4 -C 4 alkyl sulfates are preferred for washing technology reasons.
  • 2,3-Alkyl sulfates which are produced, for example, in accordance with US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN, are also suitable anionic surfactants.
  • 2 -Alcohols such as 2-methyl-branched C 9 -n alcohols with an average of 3.5 moles of ethylene oxide (EO) or -C 2 - ⁇ 8 fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8- ⁇ 8 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • 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 can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 2 -C 4 alcohols with 3 EO or 4 EO, C 9 . u alcohol with 7 EO, C ⁇ 3 . 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 - ⁇ s alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ⁇ 2 - ⁇ 4 - alcohol with 3 EO and C ⁇ 2- i 8 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, too 13
  • Fatty alcohols with more than 12 EO can be used. Examples of this 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 denotes a primary 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 for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. stands.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 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 with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as them 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-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.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • 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 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred
  • [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated, derivatives thereof Rest.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted, for example according to the teaching of international application WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired polyhydroxy fatty acid amides. 15
  • detergent tablets which contain anionic (s) and non-ionic (s) surfactant (s), with application technology advantages being able to result from certain quantitative ratios in which the individual classes of surfactants are used.
  • detergent tablets are particularly preferred in which the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2.
  • disintegration aids so-called tablet disintegrants
  • disintegration aids can be incorporated into them in order to shorten the disintegration times.
  • Römpp (9th edition, vol. 6, p. 4440) and Voigt "textbook 16 of pharmaceutical technology "(6th edition, 1987, pp. 182-184) understood auxiliaries which ensure the rapid disintegration of tablets in water or gastric juice and the release of the pharmaceuticals in an absorbable form.
  • Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the weight of the tablet.
  • Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 H ! O ⁇ 5 ) n and, formally speaking, represents a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted.
  • celluloses, in which the hydroxyl groups against functional groups that do not have an oxygen atom 1? are bound, replaced, can be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • Cellulose derivatives are preferably not used alone as disintegrants
  • the content of cellulose derivatives in these mixtures is preferably below 50% by weight. particularly preferably below 20% by weight, based on the disintegrant
  • Cellulose base Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
  • the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be compressed.
  • Detergent tablets which contain disintegrants in granular or, if appropriate, cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application PCT / EP 98/1203 (Henkel) . These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • the above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ® TF-30-HG from Rettenmaier available in the present invention.
  • 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 the crystalline areas (approx. 70%) Leave 18 undamaged.
  • a subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
  • Detergent tablets which additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular of 4 to 6% by weight, based in each case on the weight of the shaped body, are particularly preferred in the context of the present invention.
  • a disintegration aid preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular of 4 to 6% by weight, based in each case on the weight of the shaped body, are particularly preferred in the context of the present invention.
  • the detergent tablets according to the invention can contain further ingredients from the group of dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors, which are common in detergents and cleaning agents. Color transfer inhibitors and corrosion inhibitors included.
  • the detergent tablets can be colored with suitable dyes.
  • Preferred dyes the selection of which does not pose any difficulty to the person skilled in the art, have a high storage stability and are insensitive to the other ingredients of the compositions and to light, and have no pronounced substantivity to textile fibers, in order not to dye them.
  • Preferred for use in the laundry detergent tablets according to the invention are all colorants which can be oxidatively destroyed in the washing process, and also mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances.
  • a possible colorant is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part
  • Pigmosol Blau 6900 (CI 74160) is another colorant.
  • Pigmosol ® Green 8730 (CI 74260), Basonyl ® Red 545 FL (CI 45170), Sandolan ®
  • Rhodamine EB400 (CI 45100), Basacid ® Yellow 094 (CI 47005), Sicovit ® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), Pigment Blue 15 (CI 74160) , Supranol ® Blue GLW (CAS 12219-32-8, CI Acidblue 221)), Nylosan ® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and or Sandolan ® Blue (CI Acid Blue 182, CAS 12219-26-0).
  • the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers.
  • suitable colorants it must also be taken into account that colorants have different stabilities against oxidation.
  • water-insoluble colorants are more stable to oxidation than water-soluble colorants.
  • concentration of the colorant in the washing or cleaning agents varies.
  • colorants which are readily water-soluble e.g. the above
  • colorant concentrations are typically chosen in the range from a few 10 2 to 10 3 % by weight.
  • suitable concentration of the colorant in washing or cleaning agents is typically a few 10 "3 to 10 " 4 % by weight.
  • the moldings can contain optical brighteners of the type of derivatives of diaminostilbenedisulfonic acid or their alkali metal salts.
  • Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or, for example, are suitable 20 similarly structured compounds which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino 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.
  • the optical brighteners are used in the detergent tablets according to the invention in concentrations between 0.01 and 1% by weight, preferably between 0.05 and 0.5% by weight and in particular between 0.1 and 0.25% by weight. %, each based on the entire molded body, used.
  • Fragrances are added to the agents according to the invention in order to improve the aesthetic impression of the products and, in addition to the softness, to provide the consumer with a visually and sensorially "typical and unmistakable" product.
  • 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, allylcyclohexyl benzylatepylpionate, allylcyclohexyl propyl pionate.
  • the ethers include, for example, benzyl ethyl ether
  • the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
  • the ketones include, for example, the jonones, oc-isomethyl ionone and methyl cedryl ketone
  • the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol
  • the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, 21
  • the fragrance content of the laundry detergent tablets according to the invention is usually up to 2% by weight of the total formulation.
  • the fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • 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.
  • laundry detergent and cleaning product tablets may also contain components which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • washable and cleaning-active molded articles is carried out by applying pressure to a mixture to be pressed, which is located in the cavity of a press.
  • the mixture to be tabletted is directly, i.e. pressed without prior granulation.
  • the advantages of this so-called direct tableting are its simple and inexpensive application, since no further process steps and consequently no further plants are required.
  • these advantages are offset by disadvantages.
  • a powder mixture that is to be tabletted directly must have sufficient plastic deformability and have good flow properties; furthermore, it must not show any tendency to segregate during storage, transport and filling of the die.
  • 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.
  • Detergent tablets preferred in the context of the present invention are formed by pressing particulate premixes 23 obtained at least one surfactant-containing granulate and at least one subsequently admixed powdery component.
  • the surfactant-containing granules can be produced using conventional granulation processes such as mixer and plate granulation, fluidized bed granulation, extrusion, pelletizing or compacting. It is advantageous for the later detergent tablets if the premixes to be pressed have a bulk density that comes close to that of conventional compact detergents. In particular, it is preferred that the premix to be pressed has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular above 700 g / 1.
  • detergent tablets are preferred in which the granules have particle sizes between 10 and 4000 ⁇ m, preferably between 100 and 2000 ⁇ m and in particular between 600 and 1400 ⁇ m.
  • the subsequently admixed component (s) comprise the bleaching agent in the particle size distribution according to the invention mentioned.
  • the premix Before the particulate premix is pressed into detergent tablets, the premix can be "powdered” with finely divided surface treatment agents. This can be advantageous for the nature and physical properties of both the premix (storage, pressing) and the finished detergent tablets. Finely divided powdering agents are well known in the art, mostly zeolites, silicates or other inorganic salts being used. However, the premix is preferably “powdered” with finely divided zeolite, zeolites of the faujasite type being preferred. In the context of the present invention, the term “faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 (compare Donald W.
  • Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which do not necessarily have to belong to the zeolite structural group 4, can be used as powdering agents, it being advantageous if at least 50% by weight of the powdering agent from a zeolite of faujasite -Type exist.
  • detergent tablets consist of a particulate premix containing granular components and subsequently admixed pulverulent substances, the or one of the subsequently admixed pulverulent components being a zeolite of the faujasite type with particle sizes below 100 ⁇ m, is preferably below 10 ⁇ m and in particular below 5 ⁇ m and makes up at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be pressed.
  • the finely divided processing components with the particle sizes mentioned above can be dry mixed into the premix to be pressed. However, it is also possible and preferred to "stick" them to the surface of the coarser particles by adding small amounts of liquid substances.
  • Non-ionic surfactants or aqueous solutions of surfactants or other detergent ingredients can be used, for example, as liquid components which are suitable for promoting the adhesion of the powdering agents.
  • perfume it is preferred to use perfume as the liquid adhesion promoter between the finely divided powdering agent and the coarse-grained particles.
  • the premixes are 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. 25th
  • the tableting takes place in commercially available tablet presses, which in principle include
  • Single or double stamps can be equipped. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down.
  • eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine.
  • the pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disk, the number of die holes being correspondingly increased.
  • the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available.
  • Each die on the die table is assigned an upper and lower stamp, with the pressing pressure being active only by the upper or lower die. Lower stamp, but can also be built up by both stamps.
  • the die table and the stamps move around a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation.
  • these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks.
  • the die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premixes.
  • the pressing pressure on the respective premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure building up by the rolling of the punch shaft heads past adjustable pressure rollers.
  • Rotary presses can also be equipped with two or more filling shoes to increase the throughput.
  • two filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling.
  • jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible.
  • Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing.
  • the throughputs of modern rotary tablet presses are over one million molded articles per hour.
  • Tableting machines suitable within the scope of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy NV, Halle (BE / LU).
  • the hydraulic double pressure press HPF 630 from LAEIS, D. is particularly suitable.
  • the shaped bodies can be manufactured in a predetermined spatial shape and size, whereby they always consist of several phases, i.e. Layers, inclusions or cores and rings exist. Practically all practical configurations can be considered as the spatial shape, for example, the design as a board, the bar or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can each be designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. However, it is also possible to form compacts, 27 which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points.
  • the portioned compacts as tablets, in cylinder or cuboid form can be expedient, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred.
  • Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such pressed articles.
  • the spatial shape of another embodiment of the molded body is adapted in its dimensions to the detergent dispenser of commercially available household washing machines, so that the molded body can be metered directly into the dispenser without metering aid, where it dissolves during the dispensing process.
  • the detergent tablets can also be used without problems using a dosing aid.
  • Another preferred multi-phase molded body that can be produced has a plate-like or panel-like structure with alternately thick long and thin short segments, so that individual segments of this "multi-phase lock" are broken off at the predetermined breaking points, which represent the short thin segments and can be entered into the machine.
  • 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. For optical reasons, it makes sense to design the triangular base that connects the individual segments as one phase, while the triangle tip forms the second phase. Different coloring of both phases is particularly attractive in this embodiment.
  • the breaking strength of cylindrical shaped bodies can be measured 28 of the diametrical fracture stress can be detected. This can be determined according to
  • ⁇ stands for diametral fracture stress (DFS) in Pa
  • P is the force in N that leads to the pressure exerted on the molded body that causes the molded body to break
  • D is the molded body diameter in meters and t the height of the molded body.
  • a surfactant granulate was mixed with other processing components and pressed into tablets on an eccentric tablet press.
  • the bleaching agent sodium perborate monohydrate
  • the composition of the surfactant granules is given in Table 1 below, the composition of the premix to be ves ⁇ ress (and thus the composition of the molded article) can be found in Table 2.
  • Table 3 shows the particle size distributions of the perborate monohydrate used in the different molded articles.
  • Zeolite A (anhydrous active substance) 31.3
  • the hardness of the tablets was measured by deformation of the tablet to break, the force acting on the side surfaces of the tablet and the maximum ICraft that the tablet withstood.
  • the tablet was placed in a beaker with water (600 ml of water, temperature 30 ° C.) and the time until the tablet disintegrated completely.
  • the wash-in chamber was pulled out and visually assessed.
  • the individual premixes were pressed into series of tablets using an eccentric tablet press. By varying the pressure, two different hard series of tablets were produced.
  • the molded bodies El and El 'according to the invention additionally have an improved cleaning performance on enzymatically removable soils (egg, blood, cocoa).

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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)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des corps moulés nettoyants et détergents contenant des agents de blanchiment. Ces corps moulés se distinguent par une dureté et une vitesse de décomposition élevées, lorsque l'agent de blanchiment qu'ils renferment présente une dimension moyenne de particules supérieure à 0,4 mm. De préférence, l'agent de blanchiment est constitué, pour moins de 30 % de son poids, de particules présentant des dimensions inférieures à 0,4 mm.
PCT/EP1998/006474 1998-02-16 1998-10-13 Corps moules nettoyants et detergents contenant des agents de blanchiment WO1999041351A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP98955440A EP1056833B1 (fr) 1998-02-16 1998-10-13 Corps moules nettoyants et detergents contenant des agents de blanchiment
SK1202-2000A SK12022000A3 (sk) 1998-02-16 1998-10-13 Tvarovaný výrobok pracích a čistiacich prostriedkov s bieliacim prostriedkom
DE59803243T DE59803243D1 (de) 1998-02-16 1998-10-13 Wasch- und reinigungsmittelformkörper mit bleichmittel
ES98955440T ES2173640T3 (es) 1998-02-16 1998-10-13 Cuerpos moldeados de agentes de lavado y de limpieza con agente de blanqueo.
JP2000531532A JP2002503761A (ja) 1998-02-16 1998-10-13 漂白剤を含むタブレット
AT98955440T ATE213768T1 (de) 1998-02-16 1998-10-13 Wasch- und reinigungsmittelformkörper mit bleichmittel
HU0100727A HUP0100727A2 (hu) 1998-02-16 1998-10-13 Fehérítőt tartalmazó, formázott mosó- és tisztítószer készítmény

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19806200A DE19806200A1 (de) 1998-02-16 1998-02-16 Wasch- und Reinigungsmittelformkörper mit Bleichmittel
DE19806200.1 1998-02-16
CA002315298A CA2315298A1 (fr) 1998-02-16 2000-08-17 Article solide de lavage et de nettoyage renfermant un agent de blanchiment

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WO1999041351A1 true WO1999041351A1 (fr) 1999-08-19

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JP (1) JP2002503761A (fr)
CN (1) CN1284991A (fr)
AT (1) ATE213768T1 (fr)
CA (1) CA2315298A1 (fr)
DE (2) DE19806200A1 (fr)
ES (1) ES2173640T3 (fr)
HU (1) HUP0100727A2 (fr)
PL (1) PL342343A1 (fr)
SK (1) SK12022000A3 (fr)
WO (1) WO1999041351A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000022086A1 (fr) * 1998-10-14 2000-04-20 Henkel Kommanditgesellschaft Auf Aktien Corps moules detergents et nettoyants contenant des activateurs de blanchiment
JP2002180098A (ja) * 2000-12-15 2002-06-26 Kao Corp 錠剤型洗剤及びその製造方法
US9670434B2 (en) 2012-09-13 2017-06-06 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US9752105B2 (en) 2012-09-13 2017-09-05 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
US9994799B2 (en) 2012-09-13 2018-06-12 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US11865219B2 (en) 2013-04-15 2024-01-09 Ecolab Usa Inc. Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19918722A1 (de) * 1999-04-24 2000-10-26 Henkel Kgaa Bleichmittel-haltige Waschmitteltabletten
CN105331459A (zh) * 2015-12-15 2016-02-17 濮阳宏业环保新材料股份有限公司 一种染色过碳酸钠及其制备方法
CN107312645B (zh) * 2017-06-19 2021-04-13 深圳市科玺化工有限公司 一种活氧洗衣片及其制备方法
CN107488531A (zh) * 2017-08-29 2017-12-19 广州立白企业集团有限公司 一种中性速溶型块状洗涤剂组合物及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4405486A (en) * 1981-08-31 1983-09-20 Warner-Lambert Company Method for preparing granulated perborate salts containing a polymeric fluorocarbon
EP0481793A1 (fr) * 1990-10-19 1992-04-22 Unilever Plc Compositions détergentes sous forme de tablettes
EP0522766A2 (fr) * 1991-07-01 1993-01-13 Unilever Plc Compositions détergentes sous forme de tablettes
EP0711828A2 (fr) * 1994-11-14 1996-05-15 Unilever Plc Compositions détergentes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4405486A (en) * 1981-08-31 1983-09-20 Warner-Lambert Company Method for preparing granulated perborate salts containing a polymeric fluorocarbon
EP0481793A1 (fr) * 1990-10-19 1992-04-22 Unilever Plc Compositions détergentes sous forme de tablettes
EP0522766A2 (fr) * 1991-07-01 1993-01-13 Unilever Plc Compositions détergentes sous forme de tablettes
EP0711828A2 (fr) * 1994-11-14 1996-05-15 Unilever Plc Compositions détergentes

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000022086A1 (fr) * 1998-10-14 2000-04-20 Henkel Kommanditgesellschaft Auf Aktien Corps moules detergents et nettoyants contenant des activateurs de blanchiment
JP2002180098A (ja) * 2000-12-15 2002-06-26 Kao Corp 錠剤型洗剤及びその製造方法
JP4619526B2 (ja) * 2000-12-15 2011-01-26 花王株式会社 錠剤型洗剤
US10358622B2 (en) 2012-09-13 2019-07-23 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
US9752105B2 (en) 2012-09-13 2017-09-05 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
US9994799B2 (en) 2012-09-13 2018-06-12 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US9670434B2 (en) 2012-09-13 2017-06-06 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US10377971B2 (en) 2012-09-13 2019-08-13 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US11001784B2 (en) 2012-09-13 2021-05-11 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US11053458B2 (en) 2012-09-13 2021-07-06 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US11859155B2 (en) 2012-09-13 2024-01-02 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US11952556B2 (en) 2012-09-13 2024-04-09 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US11865219B2 (en) 2013-04-15 2024-01-09 Ecolab Usa Inc. Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing

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DE19806200A1 (de) 1999-08-19
PL342343A1 (en) 2001-06-04
CN1284991A (zh) 2001-02-21
JP2002503761A (ja) 2002-02-05
EP1056833A1 (fr) 2000-12-06
SK12022000A3 (sk) 2001-05-10
ATE213768T1 (de) 2002-03-15
HUP0100727A2 (hu) 2001-06-28
ES2173640T3 (es) 2002-10-16
EP1056833B1 (fr) 2002-02-27
CA2315298A1 (fr) 2000-10-29
DE59803243D1 (de) 2002-04-04

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