EP0793708B1 - Procede de preparation par extrusion d' agents de lavage ou de nettoyage contenant des adjuvants de lavage hydrosolubles - Google Patents

Procede de preparation par extrusion d' agents de lavage ou de nettoyage contenant des adjuvants de lavage hydrosolubles Download PDF

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Publication number
EP0793708B1
EP0793708B1 EP95941007A EP95941007A EP0793708B1 EP 0793708 B1 EP0793708 B1 EP 0793708B1 EP 95941007 A EP95941007 A EP 95941007A EP 95941007 A EP95941007 A EP 95941007A EP 0793708 B1 EP0793708 B1 EP 0793708B1
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European Patent Office
Prior art keywords
weight
zeolite
water
carbonate
acid
Prior art date
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EP95941007A
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German (de)
English (en)
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EP0793708A1 (fr
Inventor
Volker Bauer
Hermann-Josef Welling
Kathrin Schnepp
Monika Böcker
Katrin Erbs
Wolfgang Seiter
Jörg Poethkow
Horst Upadek
Beatrix Kottwitz
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/04—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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent 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
    • C11D3/08—Silicates

Definitions

  • the invention relates to detergents or cleaning agents which are water-soluble contain inorganic builder substances, in particular a process for the preparation of extruded washing or cleaning agents, which contain water-soluble inorganic builder substances.
  • Modern, compressed washing or cleaning agents generally have the Disadvantage that they have a poorer because of their compact structure Show dissolving behavior in aqueous liquor than, for example, lighter, spray-dried washing or cleaning agents of the prior art. Washing or cleaning agents generally tend to do so lower dissolving speed in water, the higher their degree of compaction is. Zeolites used in detergents or cleaning agents as builders are usually included due to their water insolubility in addition to the deteriorated dissolving behavior.
  • a common part of conventional laundry or detergent has dilatant properties; they are alumosilicates used as builder and phosphate substitute such as Zeolite.
  • zeolite is insoluble in water and therefore helps that the dissolving speed of extruded washing or cleaning agents in water is less than that of conventional, lighter means of State of the art.
  • Spray-dried detergents are known from US Pat. No. 4,075,117 Substitutes for phosphates do not contain carbonates and silicates as builder components but zeolites. The agents described there have a comparable agent containing phosphates or superior cleaning performance. However, according to the teaching of No. 4,075,117 is not used in any particular form.
  • the object of the invention was to include washing or cleaning agents Provide bulk densities above 600 g / l, which are water soluble Builders contain to the extent that on zeolite from application technology View can be partially or completely omitted. Also existed another job in extruded washing or cleaning agents with bulk densities above 600 g / l and a process for their preparation to provide which the water-soluble builder substances in the Dimensions included that on zeolite not only for technical reasons but partially or completely waived from a procedural point of view can be.
  • the subject of the invention is a method of making extruded Detergents or cleaning agents with a bulk density above 600 g / l, which anionic and optionally nonionic surfactants as well as water-soluble Builder substances sodium carbonate and amorphous sodium silicate contain.
  • anionic and optionally nonionic surfactants as well as water-soluble Builder substances sodium carbonate and amorphous sodium silicate contain.
  • water-soluble Builder substances sodium carbonate and amorphous sodium silicate contain.
  • sodium carbonate and amorphous sodium silicate (based in each case on anhydrous active substance) in the sum between 10 to 40 wt .-% used, sodium carbonate and amorphous sodium silicate in a weight ratio of 5: 1 to 1:10 and that Sodium carbonate at least partially used in the form of granules with the proviso that the quantities refer to the obtain dried extrudate; in addition, the extrudate is optionally with other ingredients of washing and Prepared cleaning agents and zeolite in quantities less than 19% by weight (based on anhydrous active substance).
  • the carbonate Granulate a carbonate-silicate compound is used, which for example by spray drying or granulation and, if appropriate subsequent compaction, such as roller compaction, are produced can.
  • subsequent compaction such as roller compaction
  • the carbonate-containing granules used additionally contain amorphous silicate, in particular sodium silicate, with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5.
  • amorphous silicate in particular sodium silicate
  • Particularly preferred sodium silicates are those with a molar Na 2 O: SiO 2 weight ratio of 1: 2 to 1: 3.5, disilicates and silicates with a Na 2 O: SiO 2 molar ratio of 1: 2.8 being particularly advantageous are.
  • Such carbonate and silicate-containing granules can be produced by conventional methods such as spray drying, granulation and compacting, for example roller compaction.
  • Some granules containing carbonate and silicate which can be used according to the invention are commercially available, for example, under the names Nabion 15 (R) (commercial product from Rhône-Poulenc), Gransil (R) (commercial product from Colin Stewart) or Dizzil (R) G (commercial product from Akzo & Nobel) available.
  • Carbonate-silicate granules of this type are preferred which have a weight ratio of carbonate to silicate of 3: 1 to 1: 9 and in particular of 2.5: 1 to 1: 5.
  • the synthetic zeolite used is preferably finely crystalline and contains bound water.
  • Zeolite A for example, but also zeolite X and zeolite P and mixtures of A, X and / or P are suitable.
  • 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 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 , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. It is also possible to use zeolite suspensions and zeolite powder. Suitable zeolite powders have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the laundry detergents produced according to the invention contain or cleaning agent 10 to 16 wt .-% zeolite (based on anhydrous Active substance) and 10 to 30 wt .-% of a carbonate and silicate-containing Compounds (based on anhydrous active substance).
  • those produced according to the invention contain Washing or cleaning agents, however, 0 to 5 wt .-% zeolite (based on anhydrous active substance) and 15 to 40 wt .-% of a carbonate and silicate-containing Compounds (based on anhydrous active substance).
  • Washing or cleaning agents which are produced according to the invention are particularly preferred here contain a granulate or extrudate that is free inside the grain of zeolite.
  • Crystalline layered silicates can also be used as substitutes for the zeolite and / or conventional phosphates are used. However, it is preferred that phosphates only in small amounts, in particular up to a maximum 10% by weight are contained in the washing or cleaning agents produced according to the invention.
  • Crystalline layered silicates are, in particular, crystalline, layered sodium silicates of the general formula (I) 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 suitable.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline sheet silicates of the formula (I) are those in which M represents sodium and x assumes the values 2 or 3. In particular, both are Sodium disilicate Na 2 Si 2 O 5 .yH 2 O is preferred.
  • these crystalline layered silicates are preferably only contained in the agents produced according to the invention in amounts of not more than 10% by weight, in particular less than 8% by weight, advantageously not more than 5% by weight.
  • organic ones can also be used Builder substances are used.
  • Usable organic builders are, for example, those preferably used in the form of their sodium salts
  • Polycarboxylic acids such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use 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 this.
  • 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.
  • 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. Particularly preferred are also biodegradable terpolymers, for example those that according to DE-A-43 00 772 as monomer salts of acrylic acid and Maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to the DE-C-42 21 381 as monomer salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
  • copolymers are those that are described in German patent applications DE-A-43 03 320 and P 44 17 734.8 are described and as monomers preferably acrolein and Have acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • Suitable builder systems are oxidation products from carboxyl-containing polyglucosans and / or their water-soluble Salts such as those used in the international patent application WO-A-93/08251 are described or their production, for example, in of international patent application WO-A-93/16110.
  • polyacetals which by reaction of dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and have at least 3 hydroxyl groups, for example as in European Patent application EP-A-0 280 223 can be obtained.
  • Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the washing or Cleaning agents as organic cobuilders, polymeric polycarboxylates and / or salts of polycarboxylic acids, preferably in amounts of 2 to 20 % By weight and in particular from 5 to 15% by weight.
  • zeolite is not only made from process engineering Partly or entirely due to the carbonate-containing granules can be replaced, but also the washing properties the extruded according to the invention Detergents or cleaning agents can be improved. So point the detergents produced according to the invention not only have an equally good primary washing performance like the conventional detergents containing zeolite without the carbonate-containing granules and in particular without the carbonate and silicate-containing compounds, but with preferred embodiments significantly improved primary washing performance is even achieved. The same applies to the graying inhibition.
  • ingredients of the washing or cleaning agents produced according to the invention come in particular surfactants, especially anionic surfactants, and optionally nonionic surfactants, but also cationic, amphoteric or zwitterionic surfactants.
  • Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • Alkanesulfonates made from C 12 -C 18 alkanes are also suitable. for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids are also suitable, for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • suitable anionic surfactants are the ⁇ -sulfofatty acids obtainable by ester cleavage of the ⁇ -sulfofatty acid alkyl esters or their di-salts.
  • the mono-salts of the ⁇ -sulfofatty acid alkyl esters are obtained in their industrial production as an aqueous mixture with limited amounts of di-salts.
  • the disalt content of such surfactants is usually below 50% by weight of the anionic surfactant mixture, for example up to about 30% by weight.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which represent mono-, di- and triesters and their mixtures as they do in the production 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 Glycerin can be obtained.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 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.
  • the agents prepared according to the invention 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.
  • saturated alkyl sulfates not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
  • Mixtures of saturated sulfonated fatty alcohols predominantly consisting of C 16 and unsaturated sulfated fatty alcohols predominantly consisting of C 18 are particularly preferred, for example those derived from solid or liquid HD-Ocenol (R) fatty alcohol mixtures (commercial product of the applicant) .
  • Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.
  • 2,3-alkyl sulfates which, for example, according to the US patents 3,234,258 or 5,075,041 are manufactured and sold as commercial products Shell Oil Company can be obtained under the name DAN (R) suitable anionic surfactants.
  • 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. 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.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent 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 thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • the agents can also contain soaps, preferably in amounts of 0.2 to 5% by weight.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the anionic surfactants and soaps can be 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 are preferably located Surfactants in the form of their sodium or potassium salts, especially in the form of Sodium salts.
  • Preferred anionic surfactants are alkylbenzenesulfonates and alk (en) ylsulfates, especially alkyl sulfates in the specified C chain range.
  • alk (en) ylsulfates especially alkyl sulfates in the specified C chain range.
  • washing or cleaning agents produced according to the invention are therefore particularly preferred extruded washing or cleaning agents according to the invention, which 10 to 30 wt .-% anionic surfactants, preferably at least 3 wt .-% sulfatic surfactants and - based on the anionic Total surfactants - at least 15% by weight, especially 20 to 100% by weight contain sulfate surfactants.
  • Agents manufactured according to the invention have 30 to 90 % By weight, based on the anionic surfactants present, of sulfate surfactants, contained especially on alkyl sulfates, as particularly advantageous proven.
  • means are provided which is an extruded component that contains the carbonate Contains granules and at least one other surfactant-containing component having the major part of the total brought into the means Contains alkyl sulfate.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow 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 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • 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 58/217598 are described or which are preferably according to the in the international patent application WO-A-90/13533 getting produced.
  • 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.
  • 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, especially not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (II), 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 that usually 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 can be obtained.
  • the polyhydroxy fatty acid amides are preferably derived from reducing agents Sugars with 5 or 6 carbon atoms, especially from that Glucose.
  • the agents produced according to the invention can also contain components which and grease washability from textiles positively. This effect becomes particularly clear when a textile that is already soiled is soiled previously several times with a detergent prepared 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 known from the prior art Phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers from ethylene glycol terephthalates and / or Polyethylene glycol terephthalates or anionic and / or nonionic modified Derivatives of these.
  • 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 known from the prior art Phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers from
  • the agents produced according to the invention can also contain constituents which have solubility of the heavy granules further improve.
  • Such components and The introduction of such components is, for example, in the international Patent application WO-A-93/02176 and in the German patent application DE 42 03 031.
  • the preferred ingredients include in particular fatty alcohols with 20 to 80 moles Ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol with 30 EO and tallow fatty alcohol with 40 EO, but also fatty alcohols with 14 E0 as well Polyethylene glycols with a molecular weight between 200 and 2000.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents produced according to the invention is preferably 5 to 25% by weight and in particular 10 to 20% by weight, wherein perborate monohydrate is advantageously used.
  • Percarbonate is also preferred as an ingredient. However, percarbonate is preferably not co-extruded, but optionally mixed in subsequently.
  • bleach activators can be incorporated into the preparations produced according to the invention.
  • these are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239.
  • the bleach activator content of the bleach-containing agents produced according to the invention is 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'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
  • Suitable 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-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone and / 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.
  • Enzymes come from the class of proteases, lipases or lipolytic acting enzymes, amylases, cellulases or mixtures thereof in question.
  • Bacterial strains or fungi such as are particularly well suited Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola Insolens obtained enzymatic agents.
  • Bacillus subtilis Bacillus licheniformis
  • Streptomyces griseus and Humicola Insolens obtained enzymatic agents.
  • Subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic acting enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or protease, lipase and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytic acting enzymes of particular interest.
  • lipolytic acting enzymes are the well-known cutinases. Peroxidases too or oxidases have been found to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition.
  • the amount the enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.
  • the stabilizers come in particular for per-compounds and enzymes Salts of polyphosphonic acids, especially 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or Ethylenediaminetetramethylenephosphonic acid into consideration.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DETPMP diethylenetriaminepentamethylenephosphonic acid
  • Ethylenediaminetetramethylenephosphonic acid into consideration.
  • the agents produced according to the invention can also contain further enzyme stabilizers.
  • enzyme stabilizers for example, 0.5 to 1% by weight sodium formate can be used.
  • 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 (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
  • Graying inhibitors have the task of removing 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 or aldehyde starches. Polyvinylpyrrolidone is also useful.
  • 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 their Mixtures and polyvinylpyrrolidone, for example in amounts from 0.1 to 5 % By weight, based on the agents produced according to the invention, are used.
  • the agents produced according to the invention can be derivatives of diaminostilbenedisulfonic acid as optical brighteners 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 finished washing or cleaning agents can consist of granules or extrudates which contain the above-mentioned ingredients.
  • the granules or extrudates are processed with further ingredients of washing or cleaning agents. This can be such that the detergents or cleaning agents are obtained from a mixture of several different granules, of which the main constituent is that produced according to the invention.
  • Bleach activators for example N, N'-tetraacylated diamines such as N, N, N ', N'-tetraacetylethylenediamine, enzyme granules containing enzymes, in particular protease and / or lipase and / or cellulase and / or amylase, with mixtures of 2 or 3 enzymes can be particularly beneficial, and perfume added afterwards.
  • the extrudates produced according to the invention can also be prepared with further finely divided dry powders before the enzymes and the other constituents are added. Examples include zeolite, silicas and salts of fatty acids, for example calcium stearate, bleach activators or mixtures of zeolite with one of the other powders mentioned.
  • zeolite and silicas which are available on the market, for example, as Aerosil (R) , are particularly preferred.
  • the weight ratios of zeolite to silica are advantageously above 1, in particular in a range from 200: 1 to 2: 1. It has also been shown that the foaming behavior for detergents can be positively influenced if the foam inhibitor, for example organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide, at least partially does not extrude , but is subsequently mixed with the extrudate.
  • the foam inhibitor for example organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide
  • the surface of the extrudate produced according to the invention is first covered, for example, with zeolite or a mixture containing zeolite and then with a foam inhibitor.
  • zeolite or a mixture containing zeolite
  • foam inhibitor Such measures enable a further improvement in the induction behavior of the extrudates produced according to the invention.
  • the agent produced has, in particular the extrudate produced accordingly by subsequent treatment the surface of fine-particle ingredients of detergents or cleaning agents in amounts of up to 5% by weight, based on the agent produced, in particular that treated extrudate, and in particular 0.1 to 2 wt .-% finely divided Zeolite on. The same applies to non-extruded washing or cleaning agents.
  • the bulk density of the granules or extrudates produced according to the invention and the finished washing or cleaning agent is preferably between 700 and 1200 g / l, bulk densities between 700 and 1000 g / l and in particular between 750 and 950 g / l are particularly preferred.
  • Embodiment of the invention is preferably the premix continuously a 2-screw extruder with co-rotating or fed counter-rotating screw guide, its housing and Extruder pelletizing head heated to the predetermined extrusion temperature could be.
  • a rotating knife reduced to approximately spherical to cylindrical granules.
  • the production of granules succeeds essentially uniformly Predeterminable particle size, with the absolute Particle sizes can be adapted to the intended application.
  • extrudates are then subjected to a drying step, for example, fed to a fluidized bed dryer.
  • a drying step for example, fed to a fluidized bed dryer.
  • the extruded granules which are peroxy bleaches, for example Perborate monohydrate, included, at supply air temperatures between 80 and 150 ° C can be dried without loss of active oxygen.
  • zeolite based on anhydrous active substance
  • the amounts given on the optionally obtain dried extrudate, and sodium carbonate and sodium silicate in particular as granules or compound in the quantities in it Processes are introduced that the weight ratio - based in each case on anhydrous active substances - zeolite to the sum of carbonate and silicate 2: 1 to 1: 2 and preferably 1.5: 1 to 1: 1.5.
  • zeolite used only in amounts of 0 to 5 wt .-%. It is possible and in some cases may also be preferred that Zeolite co-extruded only partially or not at all, but subsequently is added to the crude extrudate. Overall, it is preferred to use the crude extrudate Add dry powder as a powder in amounts of up to 5% by weight where zeolite (anhydrous active substance) preferably in quantities from 0.1 to 2% by weight is used. The addition of powdering agents can doing this before, during or after the drying that may have been carried out take place, but preferably the addition after completion of the optionally carried out shaping processing step, for example is carried out in a commercial rounding machine.
  • Example 1 Partial exchange of zeolite in the extrudate grain
  • the crude extrudates were each before mixing with a mixture of zeolite and silica powdered in a weight ratio of 4: 1.
  • the compositions of the finished compositions in parts by weight were listed in Table 1.
  • the Bulk density of the finished agents was between 720 and 780 g / l.
  • the invention produced means had over all soiling tested at 60 ° C and a water hardness of 16 ° d a significantly better primary washing ability as the comparison means V1.
  • the Nabion 15 (R) used in the agents produced according to the invention is a commercial product from Rhönen-Poulenc and consisted of 55% by weight sodium carbonate, 29% by weight sodium disilicate and 16% by weight water.
  • the residue behavior of the agents was tested as follows. In a bowl, 32 g of the respective agent were pre-dissolved in 4 1 of water (16 ° d) at a temperature of 30 ° C for 15 seconds by hand. Then a Nicki sweater was submerged three times, pressed and turned by 90 °. After a minute, the sweater was removed from the soapy water and wrung out. The wash liquor was decanted off, the residues were transferred to a sieve and dried at 40 ° C. The residues determined in each case are given in% of the quantity weighed in Table 2.
  • compositions of agents M1 to M3 and V1 (in parts by weight) V1 M1 M2 M3 C 9 -C 13 alkylbenzenesulfonate 13.6 13.6 9.4 9.2 C 12 -C 18 alkyl sulfate 3.9 3.9 8.0 7.9 C 12 -C 18 alcohol with 5 EO 3.6 3.6 3.6 2.4 C 12 -C 18 fatty acid soap 0.7 0.7 0.8 0.5 Polyethylene glycol with a molecular weight of 400 1.5 1.5 1.5 1.5 2.4 Zeolite (anhydrous active substance) 22.3 17.6 17.6 17.0 sodium 6.3 ---- ---- 1.6 Nabion 15 (R) (anhydrous active substance) ---- 12.0 12.0 14.1 Acrylic acid-maleic acid copolymer (sodium salt) 3.5 3.5 3.5 2.3 amorphous sodium disilicate 1.5 1.5 1.5 1.0 Perborate monohydrate 17.4 17.4 17.4 17.7 Phosphonate 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5
  • Example 2 Full exchange of zeolite in the extrudate grain
  • the comparison agent V1 and the Agents M4 to M10 produced according to the invention are produced, the agents according to the invention manufactured means M4 to M10 distinguished from V1 in that they instead of the zeolite, the sodium carbonate and the acrylic acid-maleic acid polymer had the builder combinations given in Table 3.
  • the extrusion mixtures of agents M4 to M10 could be processed without process technology Extrude problems even though the blends to be extruded did not contain any zeolite.
  • the primary washability of the agents M4 to M10 produced according to the invention was on Fat / pigment stains, protein-containing stains and high-fat stains Soiling significantly better than that of the comparative example V1 (Table 4). Only on bleachable stains (red wine and tea) were the performances of the agents M4 to M10 according to the invention compared to V1 right up to only slightly improved. So was the graying of the fabrics, that had been washed with agents M4 to M10, much less than when using V1. Surprisingly, some tissues were detected 25 washes with the agents M4 to M10 produced according to the invention even better remission values on than before the washes (Table 5). In addition, after 25 washes also determined the ash content of individual textile samples (table 6). The ash values for those washed with the agents produced according to the invention Tissues were not significantly worse than that for all tissues fabric washed with V1.
  • the application test was carried out under practical conditions in household washing machines. For this purpose, the machines with 3.0 kg clean laundry and 0.5 kg of test fabric loaded, the test fabric impregnated with conventional test soiling to test the primary washing ability was and to test the graying inhibition and the ash determination consisted of white fabric. Streaks were used as white test fabric made from standardized cotton fabric (Krefeld laundry research institute, WFK), nettle (BN), knitwear (cotton jersey; B) and terry fabric (FT) used.

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  • 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)

Claims (5)

  1. Procédé de préparation par extrusion d'un agent de lavage ou de nettoyage ayant une masse volumique apparente supérieure à 600 g/litre, contenant des tensioactifs anioniques et facultativement, non ioniques ainsi que du carbonate de sodium et du silicate de sodium amorphe comme adjuvant de lavage inorganique hydrosoluble, où un mélange préalable solide et meuble est comprimé en forme de cordon à des pressions de jusqu'à 200 bar, le cordon est découpé après sa sortie de la filière, au moyen d'un dispositif de coupe, à la dimension choisie du granulé, on conduit l'extrudat brut encore plastique, éventuellement humide vers une autre étape de façonnage et ensuite, on sèche, caractérisé en ce que le carbonate de sodium et le silicate de sodium amorphe (chacun sur base de la substance active anhydre) sont introduits en la somme comprise dans l'intervalle allant de 10 à 40% en poids, où l'on introduit le carbonate de sodium et le silicate de sodium amorphe dans un rapport pondéral compris entre 5:1 et 1:10 et le carbonate de sodium est au moins partiellement, sous forme d'un granulé, avec la condition que les données en quantité se rapportent à l'extrudat facultativement séché, l'extrudat est facultativement traité avec d'autres composants d'agents de lavage ou de nettoyage et celui-ci contient la zéolite en des quantités inférieures à 19% en poids (sur base de la substance active anhydre).
  2. Procédé suivant la revendication 1, caractérisé en ce que l'on introduit comme granulé carbonaté, un compound carbonate-silicate qui est préparé par séchage par atomisation ou granulation et facultativement, ensuite compactage.
  3. Procédé suivant la revendication 1 ou 2, caractérisé en ce que la zéolite (sur base de la substance active anhydre) est introduite en des quantités comprises dans l'intervalle allant de 10 à 16% en poids et de 10 à 30% en poids d'un compound carbonaté et silicaté (sur base de la substance active anhydre).
  4. Procédé suivant la revendication 1 ou 2, caractérisé en ce que la zéolite (sur base de la substance active anhydre) est introduite en des quantités comprises dans l'intervalle allant de 0 à 5% en poids.
  5. Procédé suivant l'une quelconque des revendications 1 à 4, caractérisé en ce que l'on ajoute à l'extrudat brut une poudre sèche comme agent de poudrage, en des quantités allant jusqu'à 5% en poids, où la zéolite (substance active anhydre) est introduite de préférence, en des quantités comprises dans l'intervalle allant de 0,1 à 2% en poids.
EP95941007A 1994-12-02 1995-11-23 Procede de preparation par extrusion d' agents de lavage ou de nettoyage contenant des adjuvants de lavage hydrosolubles Expired - Lifetime EP0793708B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4442977A DE4442977A1 (de) 1994-12-02 1994-12-02 Wasch- oder Reinigungsmittel mit wasserlöslichen Buildersubstanzen
DE4442977 1994-12-02
PCT/EP1995/004627 WO1996017045A1 (fr) 1994-12-02 1995-11-23 Agents de lavage ou de nettoyage contenant des adjuvants de lavage hydrosolubles

Publications (2)

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EP0793708A1 EP0793708A1 (fr) 1997-09-10
EP0793708B1 true EP0793708B1 (fr) 1999-01-13

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EP (1) EP0793708B1 (fr)
AT (1) ATE175717T1 (fr)
DE (2) DE4442977A1 (fr)
ES (1) ES2128793T3 (fr)
WO (1) WO1996017045A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19525378A1 (de) * 1995-07-12 1997-01-16 Henkel Kgaa Amorphes Alkalisilicat-Compound
GB9609699D0 (en) * 1996-05-09 1996-07-10 Unilever Plc Detergent compositions
MXPA01003100A (es) * 1998-09-25 2001-10-01 Zayeed Alam Composiciones detergen
JP2002525422A (ja) * 1998-09-25 2002-08-13 ザ、プロクター、エンド、ギャンブル、カンパニー 洗剤組成物
DE19936613B4 (de) 1999-08-04 2010-09-02 Henkel Ag & Co. Kgaa Verfahren zur Herstellung eines Waschmittels mit löslichem Buildersystem
DE10134309A1 (de) * 2001-07-14 2003-02-06 Henkel Kgaa Coextrusion von Wasch- und Reinigungsmitteln

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US4075117A (en) * 1973-10-15 1978-02-21 Witco Chemical Corporation Built detergent compositions
MY102396A (en) * 1986-11-07 1992-06-17 Unilever Plc Detergent granules and a process for their preparation
KR927003783A (ko) * 1989-08-09 1992-12-18 게오르그 차이트 세제용 압축과립의 제조방법
DE4235646A1 (de) * 1992-10-22 1994-04-28 Henkel Kgaa Verfahren zur Herstellung wasch- und reinigungsaktiver Extrudate
DE4320358A1 (de) * 1993-06-21 1994-12-22 Henkel Kgaa Verfahren zur Herstellung wasch- oder reinigungsaktiver Extrudate
DE4405511A1 (de) * 1994-02-22 1995-08-24 Henkel Kgaa Waschmittel mit amorphen silikatischen Buildersubstanzen

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WO1996017045A1 (fr) 1996-06-06
ES2128793T3 (es) 1999-05-16
DE4442977A1 (de) 1996-06-05
ATE175717T1 (de) 1999-01-15
DE59504841D1 (de) 1999-02-25
EP0793708A1 (fr) 1997-09-10

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