EP1416040B2 - Agents builders hydrosolubles de granulométries spécifiques pour les compositions détergentes et les agents de nettoyage - Google Patents

Agents builders hydrosolubles de granulométries spécifiques pour les compositions détergentes et les agents de nettoyage Download PDF

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EP1416040B2
EP1416040B2 EP02024319A EP02024319A EP1416040B2 EP 1416040 B2 EP1416040 B2 EP 1416040B2 EP 02024319 A EP02024319 A EP 02024319A EP 02024319 A EP02024319 A EP 02024319A EP 1416040 B2 EP1416040 B2 EP 1416040B2
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Prior art keywords
detergent
builder
acid
builders
cleaning agent
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EP02024319A
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German (de)
English (en)
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EP1416040A1 (fr
EP1416040B1 (fr
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Bernhard Enders
Katja Fink
Werner Jagmann
Elke Dr. Philippsen-Neu
Thomas Tillmann
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Dalli Werke GmbH and Co KG
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Dalli Werke GmbH and Co KG
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Priority to DE50210858T priority Critical patent/DE50210858D1/de
Priority to EP02024319A priority patent/EP1416040B2/fr
Priority to AT02024319T priority patent/ATE372373T1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the present invention relates to a washing or cleaning agent containing a water-soluble builder, wherein the builder has a certain particle size distribution, are excluded in the grain sizes of 0.2 mm to less than 0.4 mm.
  • Builders or cobuilder systems are among the most important classes of substances for the construction of detergents or cleaners. They fulfill various tasks in the washing or cleaning agents, which include water softening, enhancing the washing effect, a grayness inhibition and the dirt dispersion.
  • the builders are expected to contribute to the alkalinity necessary for the washing process, to exhibit high absorbency for surfactants and / or other detergent additives, to improve the effectiveness of surfactants, and to contribute to the positive properties of solid products in powder form, for example, structure formation Control of the dust problem.
  • the different requirements can not be met with just one builder component alone, so in these cases, a system of builders and co-builders is used.
  • zeolite NaA Concurrently with the development of zeolite NaA as a builder, it has been proposed to use selected water-soluble amorphous sodium silicate compounds as builders in detergents or cleaners.
  • amorphous sodium silicate compounds are described as builders prepared by spray-drying aqueous waterglass solutions, then grinding and compacting with additional dehydration of the millbase.
  • the EP-A-0 444 415 describes a detergent having from 0.5 to 60% by weight of a builder, from 5 to 50% by weight of a surfactant and further customary auxiliary detergents, the builder comprising an amorphous, low-sodium disilicate having a water content of from 0.3 to 6% by weight. represents.
  • the preparation of these highly dehydrated amorphous disilicates is carried out in a multi-stage process, which initially provides for the preparation of a pulverulent amorphous sodium silicate with a water content of 15 to 23% by weight. This material is treated in a rotary kiln with flue gas at temperatures of 250 to 500 ° C.
  • the sodium disilicate emerging from the rotary kiln is comminuted to particle sizes of 0.1 to 12 mm with the aid of a mechanical crusher and then ground to particle sizes of 2 to 400 ⁇ m.
  • the Application WO 00/37595 describes a process for the co-processing of amorphous sodium silicates with other ingredients from detergents or cleaners, in which aqueous preparations of amorphous sodium silicate and a polymeric carboxylate are sprayed together with other detergents and / or cleansing ingredients in a drier, simultaneously with drying a granulation can take place, and the resulting basic detergent is then compacted, possibly after admixing other ingredients.
  • the detergents produced in this way have an improved secondary detergency with comparable primary washing behavior.
  • the problem of incrustation resulting from various detergent compositions or the problem of remaining detergent residues on laundered fabrics has hitherto been approached from different directions.
  • the pH of the wash liquor plays a significant role in the precipitation of silicates, so that with conventional detergents a certain alkalinity is necessary for a good washing result.
  • the pH range in conventional washing liquors is preferably above pH 10 for heavy-duty detergents and between pH 9 and 10 for fine and color detergents.
  • Another approach to counteract precipitation of the builders has hitherto been the use of a relatively large amount of cobuilders, eg. B. polymeric polycarboxylates.
  • the object of the present invention was to provide a detergent which has a lower incrustation or reduced detergent residues in an ecologically and economically improved manner.
  • a washing or cleaning agent containing a water-soluble builder which is selected from amorphous alkali metal silicates, characterized in that the builder has a particle size distribution, the grain sizes of 0.4 to 3 mm, but grain sizes from 0.2 to less than 0.4 mm.
  • a preferred particle size range for the use of the builder in the detergent is 0.4 to 3 mm.
  • any type of water-soluble builder described so far is suitable for use as water-soluble builders, in particular amorphous alkali silicates, layer silicates, cogranulates of silicates with polymeric polycarboxylates, carbonate / silicate compounds, cogranules of phyllosilicates / unneutralized polycarboxylates, only amorphous alkali metal silicates) are claimed according to the invention as water-soluble builders having a specific particle size distribution.
  • the water-soluble builders may be used alone, or in conjunction with other builder / co-builders, wherein the builders may be optimized to have a high binding capacity for divalent ions, e.g. Calcium ions and magnesium ions.
  • the calcium ion concentration, as well as the magnesium ion concentration in the wash liquor can be reduced by the use of suitable builders. Dissolves the water-soluble builder, eg. As silicate, in the wash liquor at low pH all too quickly, it may cause precipitation of insoluble calcium or magnesium silicate, which settles on the laundry. For this reason, the pH in the wash liquor has hitherto been kept in the clearly alkaline range, as has already been mentioned above, and until now a high builder / cobuilder concentration has been used in the detergent.
  • silicate eg. As silicate
  • Suitable co-builders which can optionally also be used as compounds with the water-soluble builders are, for example, polymeric polycarboxylates of polyacrylic acid or poly (meth) acrylic acid, or copolymers of these two having arbitrary molecular weights, but in particular having molecular weights above 10,000 g / mol, preferably molar masses of 20,000 to 120,000 g / mol, more preferably 30,000 to 80,000 g / mol.
  • suitable copolymeric carboxylates are those of acrylic acid or (meth) acrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • polymeric polycarboxylates are not essential to the invention, but in one embodiment the builder is present as a particle comprising silicate and polymeric polycarboxylate.
  • a builder is obtained by co-spraying an aqueous solution of water glass / soda with polymeric polycarboxylate in a spray tower and then drying.
  • water-soluble alkali metal silicate can also be sprayed and dried together with the polymer.
  • the builder and the co-builder can also be present individually, ie not as a compound, but according to a further embodiment of the invention are used side by side in the washing or cleaning agent.
  • the primary material obtained from the spray tower (builder or builder / cobuilder compound) can either be further processed directly or, if necessary, e.g. granulated in a compactor and then, e.g. are ground to the desired grain size in a hammer mill, wherein subsequent to the manufacturing process, a particle size of 0.2 to less than 0.4 mm is screened from the product thus prepared, before it is used in the washing or cleaning agent.
  • copolymers of ⁇ -olefins and maleic acid, polyaspartic acid, iminodisuccinates or carboxymethylinulines can be used as further co-builders in the detergent.
  • zeolite A, X, Y and / or P As additional inorganic builders fine crystalline, synthetic and bound water-containing zeolite, preferably zeolite A, X, Y and / or P, as well as crystalline layered silicates can be used, which are preferably also present only in small amounts. Suitable zeolites are also mixtures of A, X, Y and / or P.
  • the zeolite P for example, MAP (z. B. Doucil A24 ®, a product of Ineos company) is particularly preferred.
  • MAP z. B. Doucil A24 ®, a product of Ineos company
  • a co-crystallized sodium / potassium aluminum silicate of zeolite A and zeolite X which in the trade as VEGOBOND AX ® (from Condea Augusta SpA commercial product) is available.
  • the zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 microns (volume distribution, measuring method: Coulter Counter) and preferably contain 10 to 22 wt .-% of bound water.
  • crystalline, layered sodium silicates according to the general formula NaMSi x O 2x + 1 ⁇ yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are to be included in the compositions.
  • Such crystalline layered silicates are described, for example, in US Pat European Patent Application EP-A-0 164 514 described.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium 6 and x is 2 or 3. In particular, both ⁇ - and ⁇ -sodium disiliates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • phosphate-containing builders can also be used,
  • both zeolites and crystalline layered silicates and phosphate-containing builders are only of minor importance in the agents according to the invention. In preferred embodiments of the invention, less than 5% by weight of these substances are contained in total. It may even be preferred if they are completely absent, in particular zeolites are often used as a powdering agent on blended granules, and thus may be included in the agents to a small extent, although their use as a builder was not intended.
  • the agents according to the invention also contain alkali metal carbonates, in particular sodium carbonate, and also alkali hydrogen carbonates and their mixed salts (sesquicarbonate). It is advantageous for the practice of the invention if the weight ratio of alkali metal carbonate to amorphous sodium silicate in the range 1: 100 to 10: 1, preferably 1:50 to 5: 1, is located. In embodiments according to the invention, it may be particularly advantageous if the weight ratio of alkali metal carbonate to amorphous sodium silicate is less than 1.
  • compositions according to the invention may contain further organic builders.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), methylglycine diacetate (MGDA), if such use is not objectionable for ecological reasons, and mixtures thereof.
  • NTA nitrilotriacetic acid
  • MGDA methylglycine diacetate
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polyacetals which are prepared by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as described in US Pat European Patent Application EP-A-0 280 223 described, can be obtained.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • oxidized dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • oxidized dextrins and methods of their preparation are for example from European Patent Applications EP-A-0 232 202 .
  • EPO-A-0 472 042 and EP-A-0 542 496 as well as the international ones Patent Applications WO 92/18542 . WO 93/08251 . WO 93/16110 . WO 94/28030 . WO 95/07303 , WO 95/12619 and WO 95/20608 known. Also suitable is an oxidized oligosaccharide according to German patent application DE-A-196 00 018 , A product oxidized to C 6 of the saccharide ring may be particularly advantageous. Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders.
  • Ehtylendiamin-N, N'-disuccinate EDDS
  • EDDS Ehtylendiamin-N, N'-disuccinate
  • glycerol disuccinates and glycerol trisuccinates as described, for example, in the US Pat US 4,524,009 .
  • US 4,639,325 in the European Patent Application EP-A-0 150 930 and the Japanese Patent Application JP 93/339896 to be discribed.
  • Suitable amounts are in zeolith lotteryn and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or salts thereof, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such co-builders are used, for example, in the international Patent Application WO 95/20029 described.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced Schmermetallbindeabmögen. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • all compounds capable of forming complexes with alkaline earth ions can be used as co-builders.
  • Such organic cobuilders may be present in the compositions according to the invention in a total amount of up to 10% by weight, but preferably not more than 5% by weight.
  • the detergents and cleaners according to the invention may, in principle, contain all known ingredients common in such agents in addition to the builders mentioned.
  • the compositions contain from 10 to 50% by weight, preferably from 15 to 35% by weight, of surfactants, these surfactants being selected from the following groups.
  • a first group are the anionic surfactants, which should be present in at least 0.5% by weight in the compositions according to the invention or agents prepared according to the invention. These include in particular sulfonates and sulfates, but also soaps.
  • Preferred surfactants of the sulfonate type are C 9 -C 13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from C 12 - to C 18 -monoolefins having terminal or internal double bonds by sulfonation gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 10 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids (ester sulfonates), z.
  • esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), z.
  • ⁇ -sulfonated methyl esters of hydrogenated coconut palm kernel or tallow fatty acids prepared by ⁇ -sulfonation of methyl esters of fatty acids of plant and / or animal origin with 8 to 20 carbon atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts be considered.
  • ⁇ -sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids although sulfonated products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with not more than 4 C atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester.
  • MES ⁇ -sulfo fatty acids
  • Anionentenside are sulfated Fettklareglycerinester which mono-, di- and triesters and mixtures thereof, as in the preparation by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained.
  • Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 10 -C 18 fatty alcohols, for example, 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. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 10 -C 16 -alkyl sulfates and C 10 -C 15 -alkyl sulfates and C 12 -C 15 -alkyl sulfates are particularly preferred.
  • 2,3-alkyl sulfates which, for example, according to the U.S. Patents 3,234,258 or 5,075,041 are manufactured and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • sulfuric acid monoesters of straight-chain or branched C 7 -C 21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 -alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 -C 18 Fatty alcohols with 1 to 4 E0 are suitable. They are used in detergents due to their high foaming behavior only in relatively small amounts, for example in amounts of 1 to 5 wt .-%.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures of these.
  • Especially preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants (see description below).
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof, as well as ether sulfates (alkylene oxide sulfates) with C 10-18 and 1-7E0.
  • Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylclycine (sarcosides). Particularly preferred are the sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate.
  • anionic surfactants in particular soaps preferably in amounts of 0.2 to 5 wt .-% into consideration.
  • Particularly suitable are saturated fatty acid soaps, 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, for. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.
  • anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • anionic surfactants are in the form of their sodium or potassium salts, especially in the form of their sodium salts.
  • anionic surfactants are used in the compositions according to the invention or are used in the process according to the invention preferably in amounts of from 1 to 30% by weight and in particular in amounts of from 5 to 25% by weight.
  • nonionic surfactants are preferred.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 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 linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 E0 or 4 E0, C 9 -C 11 -alcohols with 7 E0, C 13 -C 15 -alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C 12 -C 18 -alcohols with 3 E0, 5 E0 or 7 E0 and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 E0 and C 12 -C 18 -alcohol with 7 E0.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 E0 can also be used. Examples are (tallow) fatty alcohols with 14 E0, 16 E0, 20 E0, 25 E0, 30 E0 or 40 E0.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x, in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is a Glykoseiki with 5 or 6 C-atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (I) in which R 1 is CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in the R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 5 is a linear, branched or cyclic alkyl radical or a Aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms; wherein C 1 -C 4 alkyl or phenyl radicals are preferred, and [Z] is a polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds may then be, for example, according to the teachings of the international Patent Application WO 95/07331 be converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettklaamide.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in the Japanese Patent Application JP 58/217598 are described or preferably according to the in the international patent application WO 90/13533 were prepared.
  • Preferred nonionic surfactants are C 12 -C 18 fatty acid methyl esters having on average from 3 to 15 EO, in particular having an average of from 5 to 12 EO, while, as binders, as described above, especially higher ethoxylated fatty acid methyl esters are advantageous.
  • C 12 -C 18 fatty acid methyl esters with 10 to 12 EO can be used both as surfactants and as binders.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • gemini surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophobic groups per molecule. These groups are usually separated by a so-called “spacer”. This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.
  • gemini surfactants are sulfated hydroxy mixed ethers according to US Pat German patent application DE-A-43 21 022 or dimer alcohol bis and trimeralcyl tris sulfates and ether sulfates according to the German patent application DE-A-195 03 061 , End-capped dimer or trimeric mixed ethers according to the German patent application DE-A-195 13 391 They are characterized by their bi- and multi-functionality. Thus, the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • gemini polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO-A-95/19955.
  • bleaching agents are, for example, peroxypyrophosphates, peroxophthalates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimido peracid, phthalimidoperoxohexanoic acid (PAP), or diperdodecanedioic acid. Salts of peracids, such as peroxymonosulfate can be used.
  • the content of the bleaching agents is from 0 to 30% by weight and in particular from 5 to 25% by weight, it being advantageous to use perborate monohydrate, tetrahydrate, percarbonate or PAP.
  • Bleach activators can be incorporated into the preparations.
  • N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably polyacylated alkylenediamines such as N, N'-tetraacylated diamines, acylated glucolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles , Triazines, urazoles, diketopiperazines, sulfuryl amides and cyanurates, as well as carboxylic acid esters such as p- (alkanoyl) benzenesulfonate, especially sodium isononoyloxybenzenesulfonate, and p- (alkenoyloxy) benzenesulfonates, also caprolactam derivatives, carboxylic anhydr
  • bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in US Pat European Patent Application EP-A-0 525 239 and acetylated pentaerythritol.
  • the content of the bleach-containing agents in bleach activators is in the usual range, preferably between 1 and 10 wt .-% and in particular between 3 and 8 wt .-%.
  • bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and actylated sorbitol-mannitol mixtures (SORMAN).
  • the bleach activator can be coated in a known manner with coating substances or, if appropriate with the use of auxiliaries, in particular methylcelluloses and / or carboxymethylcelluloses, granulated or extruded / pelletized and, if desired, further additives, for example dye.
  • Such a granulate preferably contains more than 70% by weight, in particular from 80 to 99% by weight, of bleach activator.
  • a bleach activator is used which forms peracetic acid under washing conditions. Quaternized aminoalkyl nitriles or acetonitrile derivatives can also be used as bleach activators.
  • Another preferred bleach activator is a morpholinonitrile quat, or a quaternized glycine nitrile, as described in the EP 0 941 299 is described.
  • the candidate transition metal compounds include in particular from German patent application DE 195 29 082 known manganese, iron, cobalt, ruthenium or molybdenum-salene complexes and their from the German patent application DE 196 20 267 known N-analogues derived from the German patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in the German patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands described in the German patent application DE 196 20 411 known cobalt, iron, copper and ruthenium ammine complexes, which are described in the German patent application DE 44 16 438 described manganese, copper and cobalt complexes, which in the European Patent Application EP 0 272 030 Cobalt complexes described in the European patent application EP 0 693 550 known manga
  • EP 0 544 490 and EP 0 544 519 described manganese complexes, combinations of bleach activators are for example from German patent application DE 196 13 103 and international Patent Application WO 95/27775 known.
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % to 0.25 wt .-% and particularly preferably from 0.01 wt .-% to 0.1 wt .-%, each based on the total agent used.
  • enzymes include proteases, amylases, pullulanases, cellulases, cutinases and / or lipases, for example proteases such as Properase®, Alcalase®, BLAP ®, Optimase ®, Opticlean ®, Maxacal ®, Maxapem ®, Durazym ® ®, Purafect ® OxP, Esperase ® and / or Savinase ®, amylases such as Termamyl ®, amylase LT, Maxamyl ®, Duramyl ®, Purastar® ®, Kenzym ®, Purastar® ® Ox Am, cellulases as Celluzyme ®, Carezyme ®, KAC ® and / or from international Patent Applications WO 96/34108 and WO 96/34092 known cellulases and / or lipases such as Lipolase ®, Lipomax ®
  • the enzymes used can, such as. B. in the international Patent Applications WO 92/11347 or WO 94/23005 be adsorbed to carriers and / or embedded in encapsulating substances to protect against premature inactivation. They are preferably present in detergents and cleaners according to the invention in amounts of up to 10% by weight, in particular from 0.05% by weight to 5% by weight, enzymes which are particularly preferably stabilized against oxidative degradation, as described, for example, in US Pat. B. from the international Patent Applications WO 94/02597 . WO 94/02618 . WO 94/18314 . WO 94/23053 or WO 95/07350 are known to be used.
  • compositions may also contain components that positively affect oil and grease washability from fabrics. This effect is particularly evident when a textile is dirty, which has been previously washed several times 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 methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30 wt .-% and to hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic Cellulose ethers, as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
  • foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide.
  • mixtures of different foam inhibitors are used, for. As those of silicones, paraffins or waxes.
  • foam inhibitors in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • a granular, water-soluble or dispersible carrier substance In particular, mixtures of paraffins and bistearylethylenediamides are preferred.
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • soluble starch preparations and other than the above-mentioned starch products can be used, for. As degraded starch, aldehyde levels, etc .. Graying inhibitors are usually used in amounts of 0.1 to 5 wt .-%, based on the means.
  • the textile detergent formulation according to the invention may comprise customary color transfer inhibitors in the quantities customary for this purpose (about 0.1 to 2% by weight).
  • color transfer inhibitors for example, homopolymers and copolymers of vinylpyrrolidone, of vinylimidazole, of vinyl oxazolidone and of 4-vinylpyridine N-oxide having molecular weights of from 15,000 to 100,000 and crosslinked finely divided polymers based on these monomers are used.
  • the use of such polymers mentioned here is known, cf. DE-B 22 32 353 .
  • DE-A 28 14 329 and DE-A 43 16 023 is known, cf. DE-B 22 32 353 .
  • polyvinylpyrrolidone in particular in the form of PVP granules, is preferred in the agents according to the invention.
  • cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.
  • the agents may contain as optical brighteners derivatives of Diaminostilbendisulfonklare or their alkali metal salts.
  • brighteners of the type of substituted Diphenylstyryle be present, for.
  • Example the alkali salts of 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brightener can be used.
  • compositions may also comprise other known additives customarily used in detergents, dishwashing detergents or cleaners, for example small amounts of neutral filler salts and also colorings and perfumes and opacifiers.
  • the other washing, cleaning and other ingredients of the detergent can be used as a powder, granules or cogranules, wherein the particle size is in a range of 1 to 2500 .mu.m, preferably from 5 to 1000 microns, or they can be added as a liquid component.
  • the washing or cleaning agent according to the invention may be present as a powder, as a granulate or as a compactate, moreover, the washing or cleaning agent may be provided in the form of a pressed molding.
  • a water-soluble builder / cobuilder selected from amorphous alkali metal silicates with a certain particle size distribution has the advantage that no precipitate or low detergent residues are found on the laundry after completion of the washing process. This is especially the case when the wash liquor has a pH below pH 10.
  • a preferred pH range for the use of the builders having the particle size distribution described herein is a range of pH 8 to pH 12.
  • Detergent formulations composition Various detergent formulations focusing on builders of any grain size and sieved builders. ingredients 1.1 1.2 1.3 1.4 1.5 Amorphous silicate 30 - "-: ⁇ 0.2 mm 30 - "-: 0,2 - 0,4 mm 30 - “-: 0.4 - 1.0 mm 30 - “-:> 1.0 mm 30 soda 5 5 5 5 5 5 sesquicarbonate citric acid 10 10 10 10 10 sulfate 25 25 25 25 25 25 25 25 25 25 25 25 25 25 alcohol ethoxylate 6 6 6 6 6 6 6 6 Fatty alcohol sulfate 14 14 14 14 14 14 14 14 14 polycarboxylate 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3
  • the washing powder is sewn in a dark terry bag (20 * 20cm / blue / black).
  • the following dosage is used: HBII / normally dirty, then the bag with 3.7 kg ballast wash in the normal program at 30 ° C is washed.
  • the water hardness of the tap water is 15 ° dH.
  • the terry bag is cut open, turned to the left and the amount of residue visually inspected.
  • protease is more effective the more effectively the Ca2 + and Mg2 + ions are removed from the wash liquor. The better a builder works, the more effectively these ions are removed from the wash liquor.
  • the wool pulp is one of the so - called keratins, which are essentially cross - linked proteins through cysteine disulfide bridges.
  • the basic building blocks of wool are amino acids that are linked together via peptide bonds.
  • the wool can be considered as a substrate for the protease.
  • the degradation efficiency of the peptide-cleaving enzymes is determined gravimetrically and indirectly reflects the activity of the protease. Protease activity is strongly influenced by builder performance. The better the builder works, the faster and stronger the wool will be decomposed by the protease.
  • the bleach inhibits protease activity, resulting in the test taking too long.
  • the test is carried out in the Linitest (laboratory tester), which is equipped with eight sample containers.
  • the product that causes the highest weight loss shows the best builder performance.
  • Detergent Formulations Compositions Various Detergent Formulations Focusing on: Different Concentrations of the Other Ingredients. ingredients 4.1 4.2 4.3 4.4 4.5 4.6 4.7 Amorphous silicate 30 30 30 25 20 15 25 sesquicarbonate 10 15 20 20 20 20 30 citric acid 10 10 10 10 10 10 sulfate 20 15 10 15 20 25 5 alcohol ethoxylate 6 6 6 6 6 6 6 6 Fatty alcohol sulfate 14 14 14 14 14 14 14 14 14 14 14 14 polycarboxylate 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (11)

  1. Produit de lavage ou de nettoyage contenant un adjuvant hydrosoluble choisi parmi les silicates amorphes alcalins, caractérisé en ce que l'adjuvant présente une répartition granulométrique qui comprend des granulométries allant de 0,4 à 3 mm, mais qui exclut les granulométries allant de 0,2 à moins de 0,4 mm.
  2. Produit de lavage ou de nettoyage selon la revendication 1, caractérisé en ce que l'adjuvant présente une répartition granulométrique allant de 0,4 à 3 mm.
  3. Produit de lavage ou de nettoyage selon la revendication 1 ou 2, caractérisé en ce que d'autres adjuvants et/ou co-adjuvants sont présents dans le produit de lavage ou de nettoyage en plus de l'adjuvant hydrosoluble.
  4. Produit de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 3, caractérisé en ce que les autres substances de lavage ou de nettoyage présentent une taille de particule atteignant 2500 µm et sont présents sous forme de poudre, de granulés ou de co-granulés.
  5. Produit de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le produit de lavage ou de nettoyage est présent sous forme de compacté.
  6. Produit de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 5, caractérisé en ce que le produit de lavage ou de nettoyage est présent sous forme d'un corps moulé par pression.
  7. Utilisation d'un adjuvant hydrosoluble dans un produit de lavage ou de nettoyage, où l'adjuvant hydrosoluble est choisi parmi les silicates amorphes alcalins, caractérisé en ce que l'adjuvant est ajouté au produit de lavage ou de nettoyage avec une répartition granulométrique qui comprend des granulométries allant de 0,4 à 3 mm, mais qui exclut les granulométries allant de 0,2 à moins de 0,4 mm.
  8. Utilisation selon la revendication 7, caractérisé en ce que l'adjuvant est ajouté avec une répartition granulométrique allant de 0,4 à 3 mm.
  9. Utilisation selon la revendication 7 ou 8, caractérisé en ce que, en plus de l'adjuvant hydrosoluble, d'autres adjuvants/co-adjuvants sont utilisés, éventuellement également sous forme de co-granulés avec l'adjuvant hydrosoluble.
  10. Procédé pour la fabrication d'un produit de lavage ou de nettoyage, caractérisé en ce que des adjuvants hydrosoluble choisi parmi les silicates amorphes alcalins avec une répartition granulométrique allant de 0,4 à 3 mm sont ajoutés au produit de lavage ou de nettoyage, mais en ce que les granulométries allant de 0,2 à moins de 0,4 mm sont exclues.
  11. Utilisation d'un produit de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 6 dans une plage de pH pour la lessive de pH 8 à pH 12.
EP02024319A 2002-11-02 2002-11-02 Agents builders hydrosolubles de granulométries spécifiques pour les compositions détergentes et les agents de nettoyage Expired - Lifetime EP1416040B2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE50210858T DE50210858D1 (de) 2002-11-02 2002-11-02 Wasserlösliche Builder von bestimmter Korngrösse in Wasch-und Reinigungsmitteln
EP02024319A EP1416040B2 (fr) 2002-11-02 2002-11-02 Agents builders hydrosolubles de granulométries spécifiques pour les compositions détergentes et les agents de nettoyage
AT02024319T ATE372373T1 (de) 2002-11-02 2002-11-02 Wasserlösliche builder von bestimmter korngrösse in wasch-und reinigungsmitteln

Applications Claiming Priority (1)

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EP02024319A EP1416040B2 (fr) 2002-11-02 2002-11-02 Agents builders hydrosolubles de granulométries spécifiques pour les compositions détergentes et les agents de nettoyage

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE501243T1 (de) 2006-10-16 2011-03-15 Procter & Gamble Verfahren zur sprühtrocknung zur herstellung von sprühgetrocknete stark wasserlösliche waschmittel mit geringer dichte und niedrigem buildergehalt.
EP1918362A1 (fr) 2006-10-16 2008-05-07 The Procter & Gamble Company Composition de lessive détergente solide de faible densité, hautement hydrosoluble et à faible teneur en adjuvant

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4473485A (en) * 1982-11-05 1984-09-25 Lever Brothers Company Free-flowing detergent powders
DE4004626A1 (de) * 1990-02-15 1991-08-22 Hoechst Ag Waschmittel
ES2090229T3 (es) * 1990-05-08 1996-10-16 Procter & Gamble Composiciones detergentes para lavanderia granulares de bajo ph que contienen mejoradores de la detergencia de aluminosilicato, de acido citrico y de carbonato.
JP2958506B2 (ja) * 1994-06-15 1999-10-06 花王株式会社 微粒子固体ビルダーの製造方法
JP3312816B2 (ja) * 1994-07-14 2002-08-12 株式会社トクヤマ 非晶質珪酸ナトリウム粉末及びその製造方法
US5658867A (en) * 1995-05-31 1997-08-19 The Procter & Gamble Company Cleaning compositions containing a crystalline builder material in selected particle size ranges for improved performance
DE19700775A1 (de) * 1997-01-13 1998-07-16 Henkel Kgaa Verfahren zur Herstellung aniontensidhaltiger wasch- und reinigungsaktiver Tensidgranulate
EP0970918B1 (fr) * 1998-07-08 2003-10-15 Clariant GmbH Disilicate de sodium cristallin finement divisé
GB2339194A (en) * 1998-07-08 2000-01-19 Procter & Gamble Layered crystalline silicate as detergent builder component
DE10061897A1 (de) * 2000-12-12 2002-06-13 Clariant Gmbh Wasch- und Reinigungsmittel, enthaltend mikrodisperse silikathaltige Partikel
DE10062007B4 (de) * 2000-12-13 2010-03-18 Henkel Ag & Co. Kgaa Feste waschaktive Zubereitung mit verbessertem Einspülverhalten

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EP1416040A1 (fr) 2004-05-06
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ATE372373T1 (de) 2007-09-15

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