WO1995003386A1 - Detergents pulverulents ou granulaires a pouvoir detergent secondaire renforce - Google Patents

Detergents pulverulents ou granulaires a pouvoir detergent secondaire renforce Download PDF

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Publication number
WO1995003386A1
WO1995003386A1 PCT/EP1994/002322 EP9402322W WO9503386A1 WO 1995003386 A1 WO1995003386 A1 WO 1995003386A1 EP 9402322 W EP9402322 W EP 9402322W WO 9503386 A1 WO9503386 A1 WO 9503386A1
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WIPO (PCT)
Prior art keywords
weight
builder
phosphates
salts
zeolite
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PCT/EP1994/002322
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German (de)
English (en)
Inventor
Jörg Poethkow
Beatrix Kottwitz
Birgit Stevermann
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Priority to EP94923737A priority Critical patent/EP0710273A1/fr
Publication of WO1995003386A1 publication Critical patent/WO1995003386A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—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
    • 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
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

  • the invention relates to a detergent with improved secondary washing ability, which contains a system of builder substances which is essentially water-soluble, and a builder compound which contains crystalline layered silicates.
  • detergents contained phosphates, in particular tripolyphosphates, as builder substances. Phosphate contents of up to 40% by weight and occasionally even more were not uncommon. Due to the property of the phosphates to contribute to the eutrophication of the waters, their content in the agents has been reduced continuously over the past 15 years and partially or completely replaced by other builder substances. Today it is possible to remove phosphates from the water in certain clarification stages, so that reduced amounts of phosphates appear acceptable again.
  • zeolites in particular zeolite NaA, and mixtures of zeolite with alkali silicates and alkali carbonates and (co) polymeric polycarboxylates were used as phosphate substitutes.
  • Zeolite has a high calcium binding capacity, but there is a disadvantage in that these are water-insoluble substances.
  • EP-B-164514 describes crystalline layered silicates as substitutes for phosphates and zeolites. These are substances which, at room temperature, have relatively long dissolving times, but already at elevated temperatures of 35 to 40 ° C., however, already have a substantially increased dissolving rate in water. Crystalline layered silicates are therefore counted among the water-soluble builder substances. However, it has been shown that the use of crystalline layered silicates as the sole builder in modern detergents is often not sufficient to achieve an acceptable secondary washing ability. For this reason, a large number of patent applications have already been published which disclose combinations of crystalline layered silicates with other builder substances.
  • the international patent application WO-A-92/079208 describes detergents which contain 31 to 60% by weight of builder substances from the group of zeolites, crystalline phyllosilicates and (co) polymeric polycarboxylates, the zeolite content being 60 to 96% by weight, of crystalline sheet silicates 2 to 25% by weight and of polymeric polycarboxylates 2 to 16% by weight, based in each case on the sum of zeolite, crystalline sheet silicates and (co) polymeric polycarboxylates , contain.
  • the detergents have an excellent secondary washability in particular when they are free from alkali carbonates.
  • the invention accordingly relates to a powdery or granular detergent which contains anionic and / or nonionic surfactants and one or more builder substances from the group of phosphates, zeolites, crystalline phyllosilicates, organic polycarboxylic acids or their salts and the (co) polymeric polycarboxylic acids or their salts, this agent containing at least crystalline phyllosilicates and phosphates as builder substances.
  • the crystalline layered silicates used are, in particular, crystalline, layered sodium silicates of the general formula (I) NaMSi x ⁇ 2 ⁇ + ⁇ «yH2 ⁇ , where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to Is 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline sheet silicates of the formula (I) are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and (-T-sodium disilicates N ⁇ 2Si2 ⁇ 5 * yH2 ⁇ are preferred.
  • the compositions preferably contain the crystalline layered silicates in amounts of 10 to 50% by weight and in particular in amounts of 20 to 40% by weight, quantities of 20 to 30% by weight can be particularly advantageous.
  • the phosphates with builder properties used are preferably tripolyphosphates and in particular sodium tripolyphosphates.
  • orthophosphates and pyrophosphates can also be present, but their content should not exceed 50% by weight, preferably 30% by weight, based on the total amount of phosphates.
  • details of amounts of phosphate are based on anhydrous active substances.
  • agents are preferred which contain 0.5 to 15% by weight and in particular 1 to 10% by weight of phosphates, especially tripolyphosphates.
  • the compositions contain at least one further builder substance.
  • a zeolite is preferred. However, since zeolite is a water-insoluble builder substance and the agents should essentially contain water-soluble builder substances, the zeolite is used in amounts of less than 10% by weight.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality. Suitable However, zeolite NaX and mixtures of NaA and NaX as well as, for example, zeolite P are also net.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
  • the zeolite may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 8 -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. In the context of this invention, however, the amounts with respect to zeolite always relate to the anhydrous active substance.
  • the phosphate and zeolite content of the agents is restricted. Surprisingly, it was found that the use of relatively small amounts of both phosphates and zeolites leads to synergies with regard to the secondary washability in builder systems containing crystalline phyllosilicate.
  • the phosphate and zeolite content of the agents is therefore always less than their crystalline layered silicate content. Amounts of 1 to 15% by weight, preferably 2 to 12% by weight and in particular 5 to 10% by weight of phosphate and zeolite have proven to be particularly advantageous. The synergistic effect is particularly evident when phosphate and zeolite are used in a weight ratio of 1: 3 to 3: 1, preferably 1: 2 to 2: 1 and in particular around 1: 1 in the agent according to the invention.
  • the agents can also contain other known cobuilders.
  • (Co) polymeric polycarboxylates such as, for example, the sodium salts of polyacrylic acid or polyethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid), are particularly suitable.
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been found to be particularly suitable Maleic acid proven to contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid.
  • the relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, 20 up to 55% by weight aqueous solutions are preferred.
  • terpolymers for example those which, as monomers, salts of acrylic acid and maleic acid, and vinyl alcohol or vinyl alcohol derivatives, for example those according to German patent application P 43 00772.4, or which, as monomers, salts of acrylic acid and 2-alkylallyl - Sulfonic acid and sugar derivatives, for example those according to German patent application P 42 21 381.9, contain.
  • the content of (co) polymeric polycarboxylates or terpolymers in the compositions is preferably 0.5 to 10% by weight, advantageously 1 to 8% by weight and in particular 2 to 5% by weight.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0280 223 .
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is used for ecological reasons is not objectionable, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Their content in the agents according to the invention can be up to 20% by weight, with amounts of 0.5 to 20% by weight, in particular 5 to 15% by weight, being particularly preferred.
  • the detergents can contain known amounts of substances commonly used in detergents, for example surfactants, graying inhibitors and dye transfer inhibitors, foam inhibitors, inorganic alkaline salts, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers contain neutral filling salts as well as colorants and fragrances, opacifiers or pearlescent agents.
  • surfactants for example surfactants, graying inhibitors and dye transfer inhibitors, foam inhibitors, inorganic alkaline salts, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers contain neutral filling salts as well as colorants and fragrances, opacifiers or pearlescent agents.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Preferred surfactants of the sulfonate type are Cg-Ci3-alkylbenzenesulfonates, olefin sulfonates, i.e. Mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from Ci2-Ci8 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtained from C 1 -C 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids (ester sulfonates), e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, and their salts.
  • Other suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures, such as those produced 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 can be obtained.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • the salts of alkylsulfosuccinic acid can also be used.
  • Suitable sulfate-type surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • the alk (en) yl sulfates are the sulfuric acid half-esters of the Ci2-Ci8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ⁇ o-C2 ⁇ -Ox ° alcohols, and those second ⁇ dary alcohols of this chain length preferred.
  • Ci6-Ci8-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 Ci6-Ci8-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 with relatively low detergents temperatures of, for example, room temperature to 40 ° C.
  • the agents therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C12-Ci4-fatty alkyl sulfates or Ci2-Ci8-fatty alkyl sulfates with Ci6-Ci8-fatty alkyl sulfates and in particular Ci2-Ci6-fatty alkyl sulfates with Ci6-C ⁇ 8 fatty alkyl sulfates.
  • not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably CIOE to C22 are used.
  • the sulfuric acid monoesters of the straight-chain or branched C7 ⁇ C2i alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide (E0) or Ci2-Ci8 -Fe1-talkohole with 2 to 4 E0, are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts of up to 4% by weight.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or Stearic 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 Ci2-C24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • 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 30 moles of ethylene oxide (E0) per mole of alcohol in which the alcohol radical has a methyl or linear branching in the 2-position may be, or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 E0 per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 E0 or 4 E0, Cg-Cn alcohol with 7 E0, Ci3-Ci5 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, Ci2- i8- Alcohols with 3 E0, 5 E0 or 7 E0 and mixtures of these, such as mixtures of Ci2-Ci4 alcohol with 3 E0 and Ci2-Ci8 alcohol with 5 E0.
  • the degrees of ethoxylation given represent statistical mean values which can be an integer or a fraction for a special product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • nonionic surfactants are, in particular, tallow fatty alcohols with 11 E0, 14 E0 or 25 E0. It has been shown that these nonionic surfactants can be granulated or spray-dried together with anionic surfactants and thus lead to improved application properties of the finished compositions.
  • alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 ° C. -Atoms means and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligo erization 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 alkyl glycosides can be present in the premix in amounts of, for example, 1 to 5% by weight.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP-A-58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Other suitable surfactants which are able to replace alkyl glycosides or can be used in combination with them are polyhydroxy fatty acid aids of the formula (II),
  • 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.
  • alkali carbonate in particular sodium carbonate
  • alkali metal carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and optionally an additional carboxyl and / or amino group and / or salts thereof.
  • the alkali metal carbonates it is entirely possible for the alkali metal carbonates to be partially or completely replaced by glycine or glycinate.
  • amorphous silicates in particular amorphous alkali silicate, especially sodium silicate with a molar ratio Na2 ⁇ : S1O2 of 1: 1 to 1: 4.5, preferably 1: 2 to 1: 3.5, is used .
  • the amorphous sodium silicate content of the agents is generally up to 10% by weight and preferably between 1 and 8% by weight.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleach content of the premix is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose sepentaacetate.
  • the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion exhibit.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures —silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Strepto yces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, in particular, however, cellulase-containing mixtures of particular interest.
  • (Per) oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the salts of polyphosphonic acids are suitable as stabilizers, in particular for per-compounds and enzymes.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • Cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition, are preferred. used.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which contain an replace the morpholino group with a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl . ) -4 '- (2-sulfostyryl) diphenyl.
  • Mixtures of the aforementioned brighteners can also be used. It has been found that uniform white granules are obtained if, apart from the customary brighteners, the agents are used in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight.
  • a particularly preferred dye is Tinolu ⁇ ( R ) (commercial product from Ciba-Geigy).
  • the bulk density of the powdery to granular detergents according to the invention is generally 300 to 1200 g / 1, in particular 500 to 1100 g / 1. They can be produced by any of the known processes such as mixing, spray drying, granulating and extruding. It is also possible to incorporate the builder substances partially or even completely as a builder compound in the composition, which contains at least crystalline layered silicates and phosphates, preferably in a weight ratio of 1:10 to 10: 1. Such builder compounds, which are also the subject of this invention, can be produced, for example, by granulation, extrusion or roller compaction.
  • Preferred builder compounds are therefore in granular form and contain phosphates and crystalline phyllosilicates in a weight ratio of 1: 5 to 5: 1, in particular 1: 2 to 2: 1.
  • the builder compounds also contain at least one further builder substance, preferably zeolite, in particular zeolite in detergent quality.
  • those compounds which contain phosphate and zeolite in a weight ratio of 10: 1 to 1: 5, preferably up to 1: 2 have proven to be advantageous.
  • compounds should not contain zeolites in amounts above 50% by weight, preferably not above 30% by weight and in particular not above 20% by weight, based in each case on the sum of crystalline sheet silicate, phosphate and zeolite .
  • the builder compounds can also contain further ingredients, but their content is preferably not above 50% by weight, in particular not above 30% by weight, based in each case on the compound.
  • particularly suitable further ingredients are cobuilders such as organic polycarboxylic acids or their salts and / or (co) polymeric or terpolymeric polycarboxylic acids or their salts.
  • the compounds can optionally also contain ingredients without builder properties, for example surfactants or inorganic salts. However, their content in the compounds should preferably be less than 30% by weight and in particular less than 20% by weight.
  • Granular detergents of the compositions below were prepared. Due to the different raw materials, the funds had a different water content. The exchange took place over sodium sulfate.
  • SKS6 ( R ) a commercial product from Hoechst AG, was used as the crystalline layered silicate.
  • the terpolymer used was a biodegradable polymer which was a saponification product of a polymer from the units of acrylic acid, maleic acid and vinyl acetate and had been prepared in accordance with German patent application P 4300 772.4.
  • Table 1 Composition of funds Ml. M2. VI and V2 (in% by weight)
  • Ci2-C-L8 fatty acid soap 1 1 1 1 1 1 Ci2-Ci8 fatty alcohol with 5 EO 4.5 4.5 4.5 dough fatty alcohol with 5 EO 2 2 2 2 sodium carbonate 5 5 5 5 amorphous sodium disilicate 3 3 3 3 (Na2 ⁇ : Si ⁇ 21: 2.0) perborate monohydrate 16 16 16 16 tetraacetylethylenediamine 5.5 5.5 5.5 5.5 optical brightener 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 enzyme granules (protease, lipase) 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 silicone de
  • the machines were loaded with 3.5 kg of clean laundry and 0.5 kg of test fabric, some of the test fabric being impregnated with conventional test soiling (for testing the primary washing ability) and some consisting of white fabric (for testing the secondary washing ability) .
  • Strips of nettle (BN), knitwear (cotton tricot; B) and terry cloth (FT) were used as the white test fabric.
  • Washing conditions for primary washing ability tap water of 23 ° d (equivalent 230 mg Ca0 / 1), amount of detergent used per detergent and machine 98 g, washing temperature 60 ° C, liquor ratio (kg laundry: liter washing solution in the main wash cycle) 1: 5, 7, 3 rinsing with tap water, centrifuging and drying.
  • Soiling Dust-skin fat on refined cotton (SH)
  • Washing conditions for secondary washing capacity tap water of 23 ° d (equivalent to 230 mg CaO / l), amount of detergent used per detergent and machine 98 g, washing temperature 90 ° C, liquor ratio (kg of laundry: washing liquid in the main wash) 1: 5.7, 3 rinsing with tap water, centrifuging and drying, number of washes: 25.
  • the agents M1 and M2 according to the invention had a significantly better primary washing power (remission differences of more than 2 percentage points) at 60 ° C. over different soils than the comparative agents VI and V2 (Table 2) and an equally good to partially better primary washing agent like as a high quality detergent from the V3 trade, which contained a conventional builder system based on zeolite without crystalline layered silicates.
  • the copolymer polycarboxylate content of this commercial product was 5.5% by weight.
  • the results with regard to the improved secondary washing power of the agents M1 and M2 can be found in Table 3.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
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Abstract

L'invention vise à réaliser des détergents à pouvoir détergent secondaire renforcé qui contiennent essentiellement des adjuvants solubles dans l'eau. On utilise à cette fin des détergents qui contiennent des silicates en couches et des phosphates cristallins, la teneur en phosphate des agents n'excédant pas de préférence 15 % en poids. Les agents peuvent en outre contenir moins de 10 % en poids de zéolithes (par rapport au principe actif exempt d'eau). Les silicates et les phosphates cristallins peuvent être contenus dans les agents sous forme d'un mélange par exemple granulé.
PCT/EP1994/002322 1993-07-23 1994-07-14 Detergents pulverulents ou granulaires a pouvoir detergent secondaire renforce WO1995003386A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP94923737A EP0710273A1 (fr) 1993-07-23 1994-07-14 Detergents pulverulents ou granulaires a pouvoir detergent secondaire renforce

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4324807.1 1993-07-23
DE19934324807 DE4324807A1 (de) 1993-07-23 1993-07-23 Pulverförmige oder granulare Waschmittel mit verbessertem Sekundärwaschvermögen

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WO1995003386A1 true WO1995003386A1 (fr) 1995-02-02

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PCT/EP1994/002322 WO1995003386A1 (fr) 1993-07-23 1994-07-14 Detergents pulverulents ou granulaires a pouvoir detergent secondaire renforce

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EP (1) EP0710273A1 (fr)
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992007932A1 (fr) * 1990-10-26 1992-05-14 The Procter & Gamble Company Procede pour agglomerer des adjuvants detergents de silicate alumineux ou de silicate stratifie
WO1992018594A1 (fr) * 1991-04-23 1992-10-29 The Procter & Gamble Company Compositions de detergents particulaires

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992007932A1 (fr) * 1990-10-26 1992-05-14 The Procter & Gamble Company Procede pour agglomerer des adjuvants detergents de silicate alumineux ou de silicate stratifie
WO1992018594A1 (fr) * 1991-04-23 1992-10-29 The Procter & Gamble Company Compositions de detergents particulaires

Also Published As

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DE4324807A1 (de) 1995-01-26
EP0710273A1 (fr) 1996-05-08

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