EP1113067B1 - Préparation contenant des tensioactifs - Google Patents

Préparation contenant des tensioactifs Download PDF

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Publication number
EP1113067B1
EP1113067B1 EP00125075A EP00125075A EP1113067B1 EP 1113067 B1 EP1113067 B1 EP 1113067B1 EP 00125075 A EP00125075 A EP 00125075A EP 00125075 A EP00125075 A EP 00125075A EP 1113067 B1 EP1113067 B1 EP 1113067B1
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Prior art keywords
stands
acid
residue
formula
surfactant
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German (de)
English (en)
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EP1113067A2 (fr
EP1113067A3 (fr
Inventor
Ansgar Dr. Behler
Rene-Andres Dr. Artiga Gonzalez
Martina Dr. Kihn-Botulinski
Maria Dr. Liphard
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • 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
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—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
    • C11D3/02—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
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • 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
    • C11D1/662—Carbohydrates or derivatives

Definitions

  • the present invention relates to surfactant-containing particulate preparations suitable for incorporation into detergents and cleaners, to a process for the preparation of these preparations and to a detergent and cleaner containing these preparations.
  • Alkoxylated carboxylic acid esters are known nonionic surfactants, which are distinguished, in particular, by favorable ecological properties and low foaming. In powdered formulations they have only a low stability. Especially in the presence of alkaline compounds and in the presence of water or moisture, the alkoxylated carboxylic acid esters can rapidly decompose into the acid and the corresponding alcohol.
  • the alkoxylated carboxylic acid esters can be stabilized by being applied to a neutral substance coated carrier material, preferably a neutral carrier material. As part of solid detergents and cleaning agents, these can be stored for several weeks without the content of alkoxylated carboxylic acid esters being appreciably reduced.
  • the alkoxylated carboxylic acid esters used according to the invention are compounds known from the prior art which can be obtained, for example, by esterification of the alkoxylated carboxylic acids with alcohols.
  • the compounds are preferably prepared by reacting carboxylic acid esters with alkylene oxides using suitable catalysts, for example calcined hydrotalcite, by which carboxylic acid esters can be alkoxylated with both monohydric and polyhydric alcohols.
  • suitable catalysts for example calcined hydrotalcite, by which carboxylic acid esters can be alkoxylated with both monohydric and polyhydric alcohols.
  • Suitable compounds of the formula I are, in particular, those in which the radical R 1 CO is an acyl radical having 12 to 22 carbon atoms, R 2 is a C 1-4 -alkyl radical and R 3 is an ethylene or propylene radical.
  • n is preferably a number between 5 and 11, this number representing an average value.
  • Particularly preferred nonionic surfactants of the formula I are alkoxylated lauric acid methyl esters, coconut fatty acid methyl esters and tallow fatty acid methyl esters having on average 5, 6, 9 or 11 alkoxy units per molecule.
  • the nonionic surfactant of the formula I is applied according to the invention to a substrate coated with a neutral substance.
  • Suitable carrier materials are all substances which are solid at room temperature. A particularly good stability is obtained when the support material is neutral on its surface and particularly preferably the smallest possible proportion of water, chemically bound or as water of crystallization, has.
  • Suitable carrier materials are e.g. inorganic salts or builder materials. The known in the field of detergents and cleaning agents as builder materials substances are particularly preferably used because they develop an additional effect in a possible use of the surfactant-containing preparation in the cleaning cycle.
  • Examples of builder materials which can be used simultaneously as a carrier for the nonionic surfactants of the formula I are, in particular, the amorphous and crystalline zeolites, bentonites, silicates, carbonates, organic cobuilders and, if There are no environmental concerns about their use - even the phosphates.
  • the builders mentioned below are all suitable as support materials for the preparations according to the invention. These materials can not only be used as carriers for the nonionic surfactants of the formula I, but can also be used as separate preparations in the preparation of detergents and cleaners containing the preparations according to the invention as ingredients.
  • Suitable examples are crystalline, layered sodium silicates having the general formula NaMSi x O 2x + 1 ⁇ H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred Values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • Fine-crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® commercial product from Crosfield
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • zeolite X and zeolite A are cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula nNa 2 O • (1-n) K 2 O • Al 2 O 3 • (2 - 2.5) SiO 2 • (3.5-5.5) H 2 O can be described.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the alkali metal phosphates with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to high molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white, very soluble in water powders, which lose the water of crystallization when heated and at 200 ° C in the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below), go over.
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate potassium phosphate primary or monobasic potassium phosphate, KDP
  • KH 2 PO 4 is a white salt of 2.33 gcm -3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists without water and with 2 mol. (Density 2.066 gcm -3 , water loss at 95 °), 7 mol. (Density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water (density 1.52 gcm -3 , melting point 35 ° with the loss of 5 H 2 O), becomes anhydrous at 100 ° C. and on more intense heating passes into the diphosphate Na 4 P 2 O 7 .
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° under water loss) ,
  • decahydrate density 1.815-1.836 gcm -3 , melting point 94 ° under water loss
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4. Condensation of NaH 2 PO 4 or KH 2 PO 4 results in higher mol.
  • Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps). Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry.
  • sodium potassium tripolyphosphates which are also present in the Can be used within the scope of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH Na 3 K 2 P 3 O 10 + H 2 O
  • organic cobuilders it is possible in particular to use polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates in the dishwasher detergents according to the invention. These classes of substances are described below.
  • 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), if such use is not objectionable for ecological reasons, 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 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.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic 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.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives are particularly preferred.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • 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.
  • 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.
  • 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 derivatives of such 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.
  • oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • an oxidized oligosaccharide wherein a product oxidized at the C 6 of the saccharide ring may be particularly advantageous.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, 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.
  • 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 heavy metal binding capacity. Accordingly, especially if the agents also contain bleach, it may be preferred Aminoalkanphosphonate, in particular DTPMP use, or to use mixtures of said phosphonates.
  • the carriers have a neutral surface, wherein it is particularly preferred if they have no water on their surface, for. B. as water of crystallization or bound water.
  • a neutral surface wherein it is particularly preferred if they have no water on their surface, for. B. as water of crystallization or bound water.
  • anhydrous compounds are used, e.g. so-called over-dried substances, such as overdried zeolites and silicates.
  • the support materials are coated with a neutral substance which does not interfere with the stability of the nonionic surfactants of formula I.
  • Suitable coating materials are preferably those substances which are simultaneously suitable as active substances in detergents and cleaners. Examples of such substances are, for example, the nonionic surfactants known as so-called sugar surfactants, cellulose and cellulose derivatives, the salts of polycarboxylic acids already described above.
  • sugar surfactants in particular the alkyl and Alkenyloligoglycoside and Polyhydroxyfett Taramide are mentioned.
  • the alkyl and alkenyl oligoglycosides have the general formula R 4 O (G) x (II) in which R 4 is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched alkyl or alkenyl radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol that represents a glycose unit having 5 or 6 C atoms , preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • 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.
  • a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the sugar surfactants can be used in the form of aqueous solutions, as obtained from the preparation process, for application to the support material, the resulting product being dried simultaneously or later.
  • cellulose and cellulose derivatives cellulose, carboxycelluloses, cellulose esters, cellulose ethers, etc. can be used.
  • suitable derivatives are hydroxypropylmethylcellulose (HPMC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropylcellulose (HPC), methylcellulose (MC), ethylcellulose (EC), carboxymethylcellulose (CMC), carboxymethylmethylcellulose (CMMC), hydroxybutylcellulose (HBC), hydroxybutylmethylcellulose (HBMC), hydroxyethyl cellulose (HEC), hydroxyethyl carboxymethyl cellulose (HECMC), hydroxyethyl ethyl cellulose (HEEC), hydroxypropyl cellulose (HPC), hydroxypropyl carboxymethyl cellulose (HPCMC), Hydroxyethylmethylcellulose (HEMC), methylhydroxyethylcellulose (MHEC), methylhydroxyethylpropylcellulose (MHEPC), methylcellulose (MC) and propylcellulose
  • a preparation according to the invention contains from 10 to 50% by weight of surfactants of the formula I and of from 50 to 90% by weight of carrier material.
  • the coating is preferably applied in an amount of from 0.1% by weight to 10% by weight, particularly preferably from 1 to 5% by weight, based on the amount of carrier material.
  • Another object of the present invention relates to a process for the preparation of the particulate preparation according to the invention, wherein the carrier material is applied in a conventional manner with the surfactant of the formula I.
  • the application of the carrier material with the surfactant is carried out in a manner known per se, for example by impregnating the carrier material with the nonionic surfactant of the formula I, such as by spraying the liquid components onto the solid carrier or by mixing the solid and liquid components.
  • the carrier material is first coated with a neutral substance. This coating is carried out, for example, by first preparing a slurry of the carrier material with an aqueous solution of the coating material and then spray-drying it.
  • the preparation prepared according to the invention is particularly advantageous for incorporation in detergents and cleaners.
  • Another object of the present invention is accordingly a washing and cleaning agent containing the above-described preparation as well as optionally other surfactants and conventional ingredients.
  • the agents according to the invention may comprise all substances normally contained in detergents and cleaners, such as further surfactants, in particular anionic surfactants, and other builders, inorganic salts, bleaching agents, bleach activators, enzymes, enzyme stabilizers, grayness inhibitors, foam inhibitors, silicone oils, soil release compounds, dye transfer inhibitors, salts of polyphosphonic acids, optical brighteners, fluorescers, fragrances, dyes, antistatic agents, ironing aids, phobizers - And impregnating, swelling and anti-sliding agents, UV absorbers or mixtures thereof.
  • further surfactants in particular anionic surfactants, and other builders, inorganic salts, bleaching agents, bleach activators, enzymes, enzyme stabilizers, grayness inhibitors, foam inhibitors, silicone oils, soil release compounds, dye transfer inhibitors, salts of polyphosphonic acids, optical brighteners, fluorescers, fragrances, dyes, antistatic agents, ironing aids, phobizers - And impregnating, swelling and anti-s
  • compositions may contain, in addition to the formulations according to the invention in the form of the above-described preparations, further surfactants selected from the nonionic, anionic, cationic and amphoteric surfactants.
  • nonionic surfactants are e.g. unesterified alkoxylated fatty alcohols
  • the sugar surfactants already described as coating materials in particular dialkyl and alkenyl oligoglycosides and polyhydroxy fatty acid amides, and amine oxides.
  • nonionic surfactants are the usually present in liquid alkoxylated fatty alcohols.
  • alkoxylated, advantageously ethoxylated especially 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 linear and methyl-branched radicals may be present in the mixture as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alcohols 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 of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 7EO.
  • 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).
  • nonionic surfactants can also Fatty alcohols with more than 12 EO can be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • sugar surfactants already described are also suitable as further surfactants. They can be used in the form of aqueous solutions as obtained from the manufacturing process. Further forms of use are granules whose production process is described in WO97 / 03165 or vapor-dried products which can be obtained according to the process described in WO95 / 14519.
  • anionic surfactants for example, those of the sulfonate type and sulfates can be used.
  • Preferred surfactants of the sulfonate type are C 9-13- alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having an internal or double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example, the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated 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.
  • Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 -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 these chain lengths 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 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates prepared, for example, according to U.S. Patents 3,234,258 or 5,075,041, which can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration.
  • 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, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants including the soaps 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.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • detergents and cleaners according to the invention may contain builder substances. Examples of these substances have already been described above as suitable support materials for the surfactants of the formula I. They can be added as carriers for other ingredients or as individual substances to the compositions according to the invention.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, diperdodecanedioic acid or phthaloimino peracids, such as phthaliminoperacaproic acid.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular 1,3,4,6 -Tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, more particularly n-nonanoyl or isononanoyloxybenzenesulfonate (n - or iso-NOBS), carboxylic anhydrides, more particularly phthalic anhydride, isatoic anhydride and / or succinic anhydride, glycolide , acylated polyhydric alcohols, in particular triacetin, ethylene glycol
  • hydrophilic substituted acyl acetals known from German patent application DE-A-196 16 769 and the acyllactams described in German patent application DE-A-196 16 770 and international patent application WO-A-95/14075 are likewise preferably used.
  • the combinations of conventional bleach activators known from German patent application DE-A-44 43 177 can also be used.
  • nitrile derivatives such as cyanopyridines, nitrile quats and / or cyanamide derivatives can be used.
  • Preferred bleach activators are sodium 4- (octanoyloxy) benzotensulfonate, undecenoyloxybenzenesulfonate (UDOBS), sodium dodecanoyloxybenzenesulfonate (DOBS), decanoyloxybenzoic acid (DOBA, OBC 10) and / or N-methylmorpholine-acetonitrile (MMA).
  • Such bleach activators are contained in the usual amount range from 0.01 to 20 wt .-%, preferably in amounts of 0.1 to 15 wt .-%, in particular 1 wt .-% to 10 wt .-%, based on the total agent ,
  • the bleach activator can be coated in a known manner with coating substances or, optionally with the use of auxiliaries, in particular methylcelluloses and / or carboxymethylcelluloses, granulated or extruded / pelleted and, if desired, further additives, such as dye, containing the dye no coloring effect on the has washing textiles.
  • auxiliaries in particular methylcelluloses and / or carboxymethylcelluloses
  • Such a granulate preferably contains more than 70% by weight, in particular from 90 to 99% by weight, of bleach activator.
  • a bleach activator is used which forms peracetic acid under washing conditions.
  • the sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP-A-0 446 982 and EP-A-0 453 003 may also be present as so-called bleach catalysts.
  • the candidate transition metal compounds include in particular the known from German patent application DE-A-195 29 905 manganese, iron, cobalt, ruthenium or molybdenum-salene complexes and their N-analogues, which are known from German patent application DE-A No.
  • 3,608,682 discloses known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium described in German patent application DE-A-196 05688.
  • bleach activators and transition metal bleach catalysts are known, for example, from German Patent Application DE-A-196 13 103 and International Patent Application WO-A-95/27775.
  • 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.
  • Suitable enzymes are, in particular, those from the class of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains, and graying. cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer.
  • 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 enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • As cellulases are preferably cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof used. Since the different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the cellulases can be used to set the desired activities.
  • the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 3 wt .-%.
  • the support material was first a slurry of 70.6 wt .-% zeolite P (Crosfield), 3.0 wt .-% carboxymethylcellulose, 2.6 wt .-% APG600 (alkylpolyglycoside, manufacturer Cognis GmbH, Dusseldorf) and 23 7% by weight of water. This slurry was spray dried. Subsequently, the resulting material was impregnated with Stantex S6030 (Cognis GmbH) so that the carrier material contained 27% by weight of the ethoxylated fatty acid methyl ester (FMEO). The characteristics of the product obtained are shown in Table 1 below.

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Claims (10)

  1. Composition en forme de particules appropriée pour l'incorporation dans les agents de lavage et de nettoyage, contenant
    a) au moins un agent tensioactif présentant la formule (I)

            R1CO(OR3)nOR2     (I)

    dans laquelle
    R1CO représente un radical acyle aliphatique
    R2 représente un radical alkyle aliphatique
    R3 représente un radical alkylène aliphatique et
    n représente un nombre entre 3 et 15, ainsi que
    b) au moins un matériau support revêtu d'une substance neutre sur lequel est appliqué l'agent tensioactif de formule (I).
  2. Composition selon la revendication 1, caractérisée en ce que dans la formule (I) R1CO représente un radical acyle comprenant 12 à 22 atomes de carbone, R2 représente un radical alkyle en C1 à C4 et R3 représente un radical éthylène ou propylène.
  3. Composition selon la revendication 1 ou 2, caractérisée en ce que le matériau support est neutre en surface.
  4. Composition selon l'une quelconque des revendications 1 ou 2, caractérisée en ce que le matériau support est choisi parmi les zéolithes amorphes et cristallines, les silicates, les carbonates, les co-builders organiques et les phosphates.
  5. Composition selon la revendication 3, caractérisée en ce que le matériau support avec l'agent tensioactif non ionique est choisi parmi les agents tensioactifs de sucre, la cellulose ou un dérivé de cellulose ou le polycarboxylate.
  6. Composition selon la revendication 5, caractérisée en ce que l'agent tensioactif de sucre est choisi parmi les alkyloligoglycosides et les alcényloligoglycosides présentant la formule (II)

            R4O(G)x     (II)

    dans laquelle
    R4 signifie un radical alkyle ou alcényle primaire linéaire ou ramifié par méthyle, en particulier un radical alkyle ou alcényle ramifié par méthyle en 2ème position, comprenant 8 à 22 atomes de carbone, de préférence 12 à 18 atomes de carbone et G représente le symbole indiquant une unité glycose comprenant 5 ou 6 atomes de carbone, de préférence le glucose, le degré d'oligomérisation x, qui indique la répartition des monoglycosides et des oligoglycosides, est un nombre quelconque entre 1 et 10 ; de préférence, x vaut 1,2 à 1,4 ;
    et les amides d'acides gras polyhydroxy présentant la formule (III)
    Figure imgb0003
     dans laquelle
    R5CO représente un radical acyle comprenant 6 à 22 atomes de carbone, R6 représente hydrogène, un radical alkyle ou hydroxyalkyle comprenant 1 à 4 atomes de carbone et [Z] représente un radical polyhydroxyalkyle linéaire ou ramifié comprenant 3 à 10 atomes de carbone et 3 à 10 groupes hydroxyle.
  7. Composition selon l'une quelconque des revendications 1 à 6, caractérisée en ce qu'elle contient 10 à 50% en poids d'agents tensioactifs de formule (I) et 50 à 90% en poids de support.
  8. Procédé pour la préparation d'une composition sous forme de particules, contenant
    a) au moins un agent tensioactif présentant la formule (I)

            R1CO(OR3)nOR2     (I)

    dans laquelleR1CO représente un radical acyle aliphatique
    R2 représente un radical alkyle aliphatique
    R3 représente un radical alkylène aliphatique et
    n représente un nombre entre 3 et 15, ainsi que
    b) au moins un matériau support revêtu d'une substance neutre, dans lequel le matériau support est chargé de manière connue en soi par l'agent tensioactif présentant la formule (I).
  9. Agent de lavage et de nettoyage contenant une composition selon l'une quelconque des revendications 1 à 7 ainsi que des agents tensioactifs et d'autres constituants usuels.
  10. Agent selon la revendication 9, caractérisé en ce qu'il contient d'autres substances de type builder, des sels inorganiques, des agents de blanchiment, des activateurs de blanchiment, des enzymes, des stabilisateurs d'enzymes, des inhibiteurs du grisaillement, des inhibiteurs de mousse, des huiles de silicone, des agents anti-redépôt, des inhibiteurs de transfert de couleur, des sels d'acides polyphosphoniques, des azurants optiques, des agents de fluorescence, des parfums, des colorants, des agents antistatiques, des adjuvants de repassage, des agents d'hydrofugation et d'imprégnation, des agents gonflants et anti-glissement, des absorbants des UV ou leurs mélanges.
EP00125075A 1999-11-26 2000-11-17 Préparation contenant des tensioactifs Expired - Lifetime EP1113067B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19956960A DE19956960A1 (de) 1999-11-26 1999-11-26 Tensidhaltige Zubereitung
DE19956960 1999-11-26

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EP1113067A2 EP1113067A2 (fr) 2001-07-04
EP1113067A3 EP1113067A3 (fr) 2003-06-11
EP1113067B1 true EP1113067B1 (fr) 2006-04-26

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AT (1) ATE324427T1 (fr)
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3192469B2 (ja) * 1991-05-17 2001-07-30 花王株式会社 ノニオン洗剤粒子の製造方法
JP3172754B2 (ja) * 1992-10-05 2001-06-04 ライオン株式会社 高嵩密度粒状洗剤組成物
DE19509752A1 (de) * 1995-03-17 1996-09-19 Henkel Kgaa Verfahren zur Herstellung eines pulverförmigen Waschmittels
DE19624416A1 (de) * 1996-06-19 1998-01-02 Henkel Kgaa Verfahren zur Herstellung von festen Wasch- oder Reinigungsmitteln
DE19850223A1 (de) * 1998-10-31 2000-05-04 Clariant Gmbh Wasch- und Reinigungsmittel enthaltend alkoxylierte Fettsäurealkylester

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DE50012644D1 (de) 2006-06-01
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EP1113067A3 (fr) 2003-06-11
DE19956960A1 (de) 2001-05-31
ES2261140T3 (es) 2006-11-16

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