EP0746601B1 - Granulares wasch- oder reinigungsmittel - Google Patents
Granulares wasch- oder reinigungsmittel Download PDFInfo
- Publication number
- EP0746601B1 EP0746601B1 EP95910492A EP95910492A EP0746601B1 EP 0746601 B1 EP0746601 B1 EP 0746601B1 EP 95910492 A EP95910492 A EP 95910492A EP 95910492 A EP95910492 A EP 95910492A EP 0746601 B1 EP0746601 B1 EP 0746601B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- extrudate
- detergent
- surfactants
- extrudates
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
Links
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
- C11D3/395—Bleaching agents
-
- 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
-
- 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
Definitions
- the invention relates to a granular detergent or cleaning agent which a high proportion of extruded components and an improved Has dissolving behavior.
- the object of the invention was both to dissolve the extrudate Detergents or cleaning agents in the washing or cleaning liquor as well as the induction behavior of extrudate-containing detergents to improve.
- the agents according to the invention can also contain further granular ones, in particular contain extruded components that are added to the mixture of these two partial extrudates are added.
- extruded components that are added to the mixture of these two partial extrudates are added.
- a partial extrudate I which contains surfactants from 25 to 40 wt .-% and a content of builder substances from the Group of zeolites (based on anhydrous active substance) and others Silicates, such as the amorphous silicates and the crystalline layered silicates, from 20 to 60% by weight.
- Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and their mixtures, such as those used in the production by esterification of a monoglycerol with 1 to 3 mols of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mols of glycerol be preserved.
- anionic surfactants of the sulfate type are like the salts the sulfuric acid monoester from primary alcohols natural and synthetic Origin preferred.
- alk (en) yl sulfates the alkali metal salts and in particular the sodium salts of the sulfuric acid half esters of the C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and preferred those secondary alcohols of this chain length.
- alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
- C 16 -C 18 alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C 16 -C 18 -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 relatively low ones 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 mixtures of C 12 -C 14 fatty alkyl sulfates or C 12 -C 18 fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates and in particular C 12 -C 16 -Fatty alkyl sulfates with C 16 -C 18 fatty 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.
- the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in relatively small amounts in detergents.
- Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, also known as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols represent. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or use their salts.
- Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid or behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
- soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 24 fatty acid soaps.
- the anionic surfactants and the soaps can be in the form of their alkali salts such as the sodium, potassium or ammonium salts and as soluble organic salts Bases, such as mono-, di- or triethanolamine, are present.
- Bases such as mono-, di- or triethanolamine, are present.
- the anionic surfactants and soaps in the form of their sodium or potassium salts, especially in the form of the sodium salts.
- the content of the partial extrudates I in anionic surfactants is preferably 10 to 35 wt .-%, in particular 15 to 30 wt .-% fatty alk (en) yl sulfates and / or alkylbenzenesulfonate.
- 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 can 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 fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
- the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohol with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 E0.
- 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).
- the partial extrudates I preferably contain 2 to 15% by weight of alkoxylated C 8 -C 18 alcohols and in particular 5 to 10% by weight of ethoxylated C 12 -C 18 alcohols.
- non-ionic surfactants that either as the sole nonionic surfactant or in combination with others nonionic surfactants, especially together with alkoxylated Fatty alcohols used 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 ester, as for example in the Japanese patent application JP-A-58/217598 are described or which are preferably according to the in the international patent application W0-A-90/13533 become.
- surfactants described in JP 06/116599, which prevent gelation can also improve the Dissolving speed can be used.
- More structure breakers that instead of these surfactants or can also be used are the Description can be found in the international patent application WO-A-93/02176.
- 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 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; x is preferably 1.2 to 1.4.
- the content of partial extrudates I in alkyl glycosides is generally about 0 to 5% by weight and preferably 0.5 to 3% by weight.
- nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may be suitable.
- the amount of this nonionic Surfactants are preferably no more than that of the ethoxylated ones Fatty alcohols and the alkoxylated fatty acid alkyl esters, in particular not more than half of it.
- Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in the R 2 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
- 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 finely crystalline, synthetic and bound water-containing zeolite used as builder substance is preferably zeolite NaA in detergent quality.
- zeolite X or zeolite P and mixtures of NaA and NaX are also suitable.
- the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
- the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups or ethoxylated isotridecanols.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water.
- Layer substitutes are suitable substitutes or partial substitutes for the zeolite natural and synthetic origin.
- Such layered silicates are, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405.
- Their usability is not one special composition or structural formula limited. Are preferred here, however, smectites, especially bentonites.
- M sodium or hydrogen
- x is a number from 1.9 to 4
- y is a number Number is 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 of the formula (II) are those in which M is sodium and x is 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
- Amorphous silicates in particular sodium silicates with an Na 2 O: SiO 2 ratio of 1: 2.0 to 1: 3.0, preferably up to 1: 2.5, and / or carbonate-silicate compounds such as are also suitable they are commercially available as substitutes for the zeolite.
- amorphous also means “X-ray amorphous” Roger that.
- X-ray amorphous This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections as they do for crystalline ones Substances are typical, but at most one or more maxima scattered x-rays that are several units wide of the diffraction angle. However, it may very well be too special good builder properties lead when the silicate particles in electron diffraction experiments provide washed-out or even sharp diffraction maxima. This is to be interpreted as meaning that the products are microcrystalline Have ranges of size 10 to a few hundred nm.
- the zeolite content of the partial extrudates I is preferably 25 to 50 wt .-% and in particular 25 to 45 wt .-%, with the Use of zeolite and crystalline layered silicates (II) a weight ratio 4: 1 to 1: 2, advantageously from 3: 1 to 1: 1, in particular is preferred.
- weight ratios of 3: 1 to 1 : 3 and in particular from 2: 1 to 1: 2 are preferred.
- organic builder substances can also be used.
- Useful organic builder substances are preferred, for example polycarboxylic acids used in the form of their salts, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided such use ecological reasons are not objectionable, as well as mixtures of these.
- Preferred salts are the sodium salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
- Their content in the partial extrudates I can generally 0 to 15 wt .-%.
- Suitable polymeric polycarboxylates are, for example, the sodium salts 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 acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain.
- Their relative molecular mass, 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.
- polymeric polycarboxylates also preferred terpolymers described in the older German patent DE-C-42 21 381 and the older German patent application DE-A-43 00 722 to be discribed.
- the content of polymeric polycarboxylates and inclusive the terpolymers is preferably 2 to 7% by weight.
- Suitable ingredients of the partial extrudates I are - as already mentioned in part - water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these;
- alkali carbonate and amorphous alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
- the sodium carbonate content of the partial extrudates I is preferably up to 20% by weight, advantageously between 2 and 15% by weight.
- the content of amorphous sodium silicate in the agents is generally up to 10% by weight and preferably between 1 and 5% by weight if the silicate is not used as a builder, because then the content can also significantly exceed 10% by weight .
- the partial extrudates I can contain other known additives commonly used in detergents, for example Graying inhibitors, salts of polyphosphonic acids, enzymes, enzyme stabilizers, small amounts of neutral filling salts and, if necessary Dyes and fragrances, opacifiers or pearlescent and optical Brightener included.
- the enzymes are advantageous not as components of partial extrudates I or II, but as a component another preferred granular component that also extrudes can be used.
- the agents can also contain components that the oil and Influencing fat washability from textiles positively. This effect becomes particularly clear when a textile that is already soiled is soiled previously several times with a detergent according to the invention that this oil and contains fat-dissolving component, is washed.
- nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion on methoxyl groups from 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, as well as the polymers of phthalic acid known from the prior art and / or terephthalic acid or its derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates.
- Graying inhibitors have the task of detaching from the fiber Keep dirt suspended in the fleet and prevent 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 Starch or the cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose.
- soluble ones Use starch preparations and other starch products than those mentioned above, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
- cellulose ethers such as carboxymethyl cellulose are preferred.
- Carboxymethyl cellulose (sodium salt), Methyl cellulose, methyl hydroxyethyl cellulose and their mixtures and polyvinyl pyrrolidone are preferred, for example in amounts of 0.1 to 5 % By weight, based on the partial extrudates I, used.
- the salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and Diethylenetriaminepentakis (methylenephosphonate) in amounts of 0.1 to 1.5 % By weight used.
- the agents can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed connections that instead the morpholino group is a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present be, e.g.
- the partial extrudate II preferably contains 0.1 to 15% by weight and in particular 2 to 12 wt .-%, each based on the partial extrudate II, surfactants such as given above, anionic surfactants and in particular alk (en) yl sulfates and / or alkylbenzenesulfates are preferred.
- surfactants such as given above, anionic surfactants and in particular alk (en) yl sulfates and / or alkylbenzenesulfates are preferred.
- the content of Soaps as above can range from 0 to about 2% by weight.
- the partial extrudates II contain 30 to 55% by weight, advantageously 40 to 50% by weight, of peroxy bleaching agent, with perborate monohydrate, perborate tetrahydrate or percarbonate being particularly preferred.
- peroxy bleaching agent for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
- the partial extrudates II can contain inorganic and organic builder substances as indicated above. It is preferred that these builder substances are present in amounts not exceeding 35% by weight, in particular in amounts of 10 to 30% by weight, based in each case on partial extrudate II.
- the partial extrudate II is a foam inhibitor based on silicone and / or paraffin. It was surprisingly found that the effectiveness of the foam inhibitor can be raised after storage of the agent if it is not incorporated into partial extrudate I or subsequently mixed in, but is incorporated into the partial extrudate II.
- the washing or cleaning agents according to the invention can be the partial extrudates I and II included in a wide weight ratio. It is however, it is particularly preferred that the agents partial extrudate I and partial extrudate II in a weight ratio greater than 1: 1, preferably from 1.2: 1 to 3: 1 and in particular from 1.5: 1 to 2.5: 1.
- the partial extrudates can be made by any of the known extrusion or pelleting processes getting produced. In particular, however, it is preferred the partial extrudates according to the teaching of international patent application WO-A-91/02047 or WO-A-93/02176.
- the partial extrudates can also contain components that increase the solubility of the densified Improve granules. Such components and the introduction of such Components are, for example, in the international patent application W0-A-93/02176 and in the older German patent application P 42 03 031.5 described.
- the components preferably used include in particular Fatty alcohols with 10 to 80 moles of ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol with 30 EO and tallow fatty alcohol with 40 EO, as well as polyethylene glycols with a molecular weight between 200 and 2000. It has now been shown in production engineering trials that the lower pressure of at least 25 bar is not an absolutely fixed limit, but dependent on the type of extruder and throughput, for example can also fall below 7000 kg / h. At such high Throughputs obviously play a major role in apparatus technology parameters Role at smaller throughputs, for example between 600 and 2000 kg / h were unpredictable.
- the anionic surfactants that may be present during manufacture of the solid premix intended for extrusion in the form of a spray-dried, granulated or extruded compounds. Furthermore, a method is preferred in which the surface of the partial extrudates to reduce the stickiness of the granules rich in nonionic surfactants is treated afterwards. Suitable surface modifiers are known from the prior art.
- finely divided zeolites amorphous aluminosilicates, silicas, amorphous Silicates, fatty acids or fatty acid salts, for example calcium stearate, in particular, however, mixtures of zeolite and silica or zeolite and calcium stearate are particularly preferred.
- the agents contain in addition to the partial extrudates I and II at least one further solid, which is preferably present as a granular component.
- at least one further solid which is preferably present as a granular component.
- bleach activators, enzymes and / or perfume to mix.
- bleach activators are the N-acyl or O-acyl compounds forming with H 2 O 2 organic peracids, preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonate, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate .
- Particularly preferred bleach activators are N, N, N'N'-tetraacetylethylene diamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
- Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. They are particularly well suited from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably become proteases of the subtilisin type and in particular proteases, which are obtained from Bacillus lentus.
- enzyme mixtures for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, Amylase and lipase or protease, lipase and cellulase, in particular Cellulase-containing and protease-containing mixtures of particular interest.
- (Per) oxidases are also suitable.
- the enzymes can on carriers adsorbed and / or embedded in enveloping substances around them protect against premature decomposition. It is also possible to use Proteases with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme, are stabilized.
- the bulk density of the preferred granular agents is generally 300 to 1100 g / l, in particular 500 to 1000 g / l.
- agents according to the invention which total about 10 to 35% by weight, advantageously 12 to 30% by weight of anionic and nonionic surfactants, 20 up to 60% by weight of builder substances, 10 to 25% by weight of peroxy bleach, 2 up to 15 wt .-%, in particular 5 to 10 wt .-% inorganic and alkaline acting salts such as carbonate and amorphous silicates, insofar as they do not belong to the Builder substances are to be expected, as well as foam inhibitors, bleach activators and contain enzymes.
- the Agents according to the invention at 80 to 95% by weight from the partial extrudates, advantageously consists of the partial extrudates I and II.
- Such agents preferably have a bulk density above 650 g / l and in particular at least 700 g / l.
- Partial extrudate I contained 14.5% by weight of C 16 -C 18 alkyl sulfate, 8.5% by weight of C 12 -C 14 alkyl sulfate, 9.5% by weight of C 12 -C 18 fatty alcohol with 3 EO , 5.5% by weight sodium carbonate, 5% by weight Sokalan CP 5 (R) (copolymer of acrylic acid; commercial product from BASF, Federal Republic of Germany), 2.5% by weight sodium silicate with a Na 2 O: SiO 2 Ratio of 1: 2.0, 38.5 wt .-% zeolite (anhydrous active substance), 4 wt .-% sodium sulfate, 1.65 wt .-% salts from raw materials and the rest water.
- the bulk density of extrudate I was 773 g / l.
- Partial extrudate II contained 6.6% by weight of C 16 -C 18 alkyl sulfate, 4% by weight of C 12 -C 14 alkyl sulfate, 5.5% by weight of sodium carbonate, 5% by weight of Sokalan CP 5 ( R) , 1.7 wt .-% silicone oil, 2.2 wt .-% sodium silicate with a modulus of 2.0, 1.2 wt .-% sodium silicate with a modulus of 3.0, 7 wt .-% zeolite (based on anhydrous active substance), 49.5% by weight sodium perborate monohydrate, 9.5% by weight sodium sulfate, 0.8% by weight other salts from raw materials and the rest water.
- the bulk density of extrudate II was 787 g / l.
- agent M1 was produced, which consists of 65% by weight of extrudate I and consisted of 35 wt .-% of extrudate II. Another agent contained M2 59.8% by weight of extrudate 1, 32.2% by weight of extrudate II and 8% by weight of others Ingredients such as tetraacetylethylene diamine, protease, lipase and / or cellulase and perfume.
- an agent V1 was produced from a uniform extrudate, that the ingredients of extrudates I and II in the quantitative ratio 65: 35 contained.
- the solving time at 90% resolution was 2 for M1 Minutes and 29 seconds, for V1 3 minutes and 20 seconds.
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)
Description
Claims (12)
- Granulares Wasch- oder Reinigungsmittel, enthaltend Granulate, welche durch Extrusion hergestellt werden, dadurch gekennzeichnet, daß es mindestens zwei Teilextrudate enthält, wobei das Teilextrudat I 20 bis 50 Gew.-%, bezogen auf das Teilextrudat I, Tenside enthält und frei von Bleichmitteln ist und das Teilextrudat II 0 bis 15 Gew.-%, bezogen auf das Teilextrudat II, Tenside und 20 bis 60 Gew.-% Bleichmittel enthält.
- Mittel nach Anspruch 1, dadurch gekennzeichnet, daß das Teilextrudat 1 25 bis 40 Gew.-% Tenside und 20 bis 60 Gew.-%, vorzugsweise 25 bis 50 Gew.-% Buildersubstanzen aus der Gruppe der Zeolithe (bezogen auf wasserfreie Aktivsubstanz) und der amorphen Silikate und der kristallinen Schichtsilikate enthält.
- Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Teilextrudat Zeolith und kristalline Schichtsilikate (II) NaMSixO2x+1 ·yH2O, wobei M Natnum oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte von x 2, 3 oder 4 sind, in Mengen von 25 bis 45 Gew.-% enthält, wobei ein Gewichtsverhältnis von 4:1 bis 1:2 bevorzugt ist.
- Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Teilextrudat I Zeolith und röntgenamorphe Silikate oder Carbonat-Silikat-Compounds im Gewichtsverhältnis von 3 : 1 bis 1 : 3, insbesondere von 2 : 1 bis 1 : 2 enthält.
- Mittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das Teilextrudat II 0,1 bis 15 Gew.-%, vorzugsweise 2 bis 12 Gew.-%, jeweils bezogen auf das Teilextrudat II, Tenside und 30 bis 55 Gew.-%, vorzugsweise 40 bis 50 Gew.-% Peroxy-Bleichmittel, insbesondere Perboratmonohydrat, Perborattetrahydrat oder Percarbonat, enthält.
- Mittel nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Teilextrudat II anorganische und organische Buildersubstanzen in Mengen nicht oberhalb 35 Gew,-%, vorzugsweise von 10 bis 30 Gew.-%, jeweils bezogen auf das Teilextrudat II, enthält.
- Mittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Teilextrudat II einen Schauminhibitor auf Silikon- und/oder Paraffin-Basis enthält.
- Mittel nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß das Mittel Teilextrudat I und Teilextrudat II in einem Gewichtsverhältnis von größer als 1 : 1, vorzugsweise von 1,2 : 1 bis 3 : 1 und insbesondere von 1,5 : 1 bis 2,5 : 1 enthält.
- Mittel nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß mindestens ein Teilextrudat mit einem Oberflächenmodifizierer nachträglich behandelt wurde, wobei feinteilige Zeolithe, amorphe Alumosilikate, Kieselsäuren, amorphe Silikate, Fettsäuren oder Fettsäuresalze und insbesondere Mischungen aus Zeolith und Kieselsäuren oder Zeolith und Calciumstearat bevorzugt sind.
- Mittel nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß es mindestens einen weiteren Feststoff, vorzugsweise eine granulare Komponente, enthält.
- Mittel nach Anspruch 10, dadurch gekennzeichnet, daß eine weitere granulare Komponente Enzyme enthält.
- Mittel nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß es zu 80 bis 95 Gew.-% aus Teilextrudaten, vorteilhafterweise aus den Teilextrudaten I und II, besteht.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4406210A DE4406210A1 (de) | 1994-02-25 | 1994-02-25 | Granulares Wasch- oder Reinigungsmittel |
DE4406210 | 1994-02-25 | ||
PCT/EP1995/000567 WO1995023207A1 (de) | 1994-02-25 | 1995-02-16 | Granulares wasch- oder reinigungsmittel |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0746601A1 EP0746601A1 (de) | 1996-12-11 |
EP0746601B1 true EP0746601B1 (de) | 2000-01-12 |
Family
ID=6511245
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95910492A Expired - Lifetime EP0746601B1 (de) | 1994-02-25 | 1995-02-16 | Granulares wasch- oder reinigungsmittel |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0746601B1 (de) |
AT (1) | ATE188730T1 (de) |
AU (1) | AU1757895A (de) |
DE (2) | DE4406210A1 (de) |
DK (1) | DK0746601T3 (de) |
ES (1) | ES2143044T3 (de) |
HU (1) | HUT75202A (de) |
PL (1) | PL315976A1 (de) |
WO (1) | WO1995023207A1 (de) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4429550A1 (de) * | 1994-08-19 | 1996-02-22 | Henkel Kgaa | Verfahren zur Herstellung von Wasch- oder Reinigungsmitteltabletten |
DE19501117A1 (de) * | 1995-01-17 | 1996-07-18 | Henkel Kgaa | Bleichendes Waschmittel in Granulatform |
DE19519139A1 (de) * | 1995-05-30 | 1996-12-05 | Henkel Kgaa | Granulares Wasch- oder Reinigungsmittel mit hoher Schüttdichte |
DE19524722A1 (de) * | 1995-07-12 | 1997-01-16 | Henkel Kgaa | Granulares Wasch- oder Reinigungsmittel mit hoher Schüttdichte |
GB9711356D0 (en) † | 1997-05-30 | 1997-07-30 | Unilever Plc | Particulate detergent composition |
US20200332230A1 (en) * | 2017-12-29 | 2020-10-22 | Zobele Holding S.P.A. | Laundry Additive for Removing Stains |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0672237B2 (ja) * | 1984-09-14 | 1994-09-14 | 花王株式会社 | 流動性の改良された高密度の粒状洗剤の製法 |
US4678594A (en) * | 1985-07-19 | 1987-07-07 | Colgate-Palmolive Company | Method of encapsulating a bleach and activator therefor in a binder |
GB8625474D0 (en) * | 1986-10-24 | 1986-11-26 | Unilever Plc | Soap noodles |
JPH05500076A (ja) * | 1989-08-09 | 1993-01-14 | ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチェン | 洗剤中で使用する高密度顆粒の製造方法 |
-
1994
- 1994-02-25 DE DE4406210A patent/DE4406210A1/de not_active Withdrawn
-
1995
- 1995-02-16 ES ES95910492T patent/ES2143044T3/es not_active Expired - Lifetime
- 1995-02-16 AU AU17578/95A patent/AU1757895A/en not_active Abandoned
- 1995-02-16 DK DK95910492T patent/DK0746601T3/da active
- 1995-02-16 AT AT95910492T patent/ATE188730T1/de not_active IP Right Cessation
- 1995-02-16 DE DE59507614T patent/DE59507614D1/de not_active Expired - Fee Related
- 1995-02-16 EP EP95910492A patent/EP0746601B1/de not_active Expired - Lifetime
- 1995-02-16 WO PCT/EP1995/000567 patent/WO1995023207A1/de active IP Right Grant
- 1995-02-16 PL PL95315976A patent/PL315976A1/xx unknown
- 1995-02-16 HU HU9602333A patent/HUT75202A/hu unknown
Also Published As
Publication number | Publication date |
---|---|
PL315976A1 (en) | 1996-12-23 |
HUT75202A (en) | 1997-04-28 |
DE59507614D1 (de) | 2000-02-17 |
DK0746601T3 (da) | 2000-05-29 |
ATE188730T1 (de) | 2000-01-15 |
WO1995023207A1 (de) | 1995-08-31 |
DE4406210A1 (de) | 1995-08-31 |
ES2143044T3 (es) | 2000-05-01 |
AU1757895A (en) | 1995-09-11 |
EP0746601A1 (de) | 1996-12-11 |
HU9602333D0 (en) | 1996-10-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0746599B1 (de) | Waschmittel mit amorphen silikatischen buildersubstanzen | |
EP0859827B1 (de) | Verfahren zur herstellung eines amorphen alkalisilikats mit imprägnierung | |
DE19956802A1 (de) | Waschmitteltabletten | |
DE19953793A1 (de) | Tensidgranulate mit verbesserter Auflösegeschwindigkeit | |
EP0804529B1 (de) | Amorphes alkalisilikat-compound | |
EP0682692A1 (de) | Gerüststoff für wasch- oder reinigungsmittel. | |
EP0674700B1 (de) | Granulare wasch- und reinigungsmittel mit hohem tensidgehalt | |
EP0746601B1 (de) | Granulares wasch- oder reinigungsmittel | |
EP0828818B1 (de) | Granulares wasch- oder reinigungsmittel mit hoher schüttdichte | |
EP0814152A2 (de) | Verfahren zur Herstellung von festen Wasch- oder Reinigungsmitteln | |
EP0793708B1 (de) | Verfahren zur herstellung extrudierter wasch- oder reinigungsmittel mit wasserlöslichen buildersubstanzen | |
EP0840780B1 (de) | Granulares wasch- oder reinigungsmittel mit hoher schüttdichte | |
EP0845028B1 (de) | Verfahren zur herstellung eines amorphen alkalisilikats mit imprägnierung | |
DE19622443A1 (de) | Granulare Waschmittel, enthaltend optischen Aufheller | |
EP0705328A1 (de) | Waschmittel mit verfärbungsinhibierenden eigenschaften | |
EP0705330A1 (de) | Verfahren zur herstellung wasch- oder reinigungsaktiver extrudate | |
EP0713524A1 (de) | Waschmittel, enthaltend nichtionische celluloseether | |
EP0799302A1 (de) | Amorphes alkalisilikat mit imprägnierung | |
EP0814149A2 (de) | Verfahren zur Herstellung von festen Wasch- oder Reinigungsmitteln | |
DE19953792A1 (de) | Waschmitteltabletten | |
WO1995004129A1 (de) | Verfahren zur herstellung wasch- oder reinigungsaktiver extrudate | |
EP0769045B1 (de) | Waschmittel mit cellulase | |
DE19939804A1 (de) | Schaumkontrollierte feste Waschmittel | |
WO1996029390A1 (de) | Pulverförmige bis granulare wasch- oder reinigungsmittel | |
WO1996011254A1 (de) | Verfahren zur herstellung wasch- oder reinigungsaktiver extrudate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19960817 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB IT LI NL |
|
17Q | First examination report despatched |
Effective date: 19980216 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE DK ES FR GB IT LI NL |
|
REF | Corresponds to: |
Ref document number: 188730 Country of ref document: AT Date of ref document: 20000115 Kind code of ref document: T |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 59507614 Country of ref document: DE Date of ref document: 20000217 |
|
ITF | It: translation for a ep patent filed |
Owner name: STUDIO JAUMANN P. & C. S.N.C. |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2143044 Country of ref document: ES Kind code of ref document: T3 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20000512 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20010131 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20010212 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20010213 Year of fee payment: 7 Ref country code: DK Payment date: 20010213 Year of fee payment: 7 Ref country code: CH Payment date: 20010213 Year of fee payment: 7 Ref country code: AT Payment date: 20010213 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20010214 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20010228 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20010427 Year of fee payment: 7 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020216 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020216 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020218 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020228 Ref country code: DK Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020228 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020228 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020228 |
|
BERE | Be: lapsed |
Owner name: HENKEL K.G.A.A. Effective date: 20020228 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020901 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20020903 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20020216 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: EBP |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20021031 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20020901 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20031122 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20050216 |