EP1032645B1 - Niedrigkonzentrierte höherviskose flüssigwaschmittel - Google Patents

Niedrigkonzentrierte höherviskose flüssigwaschmittel Download PDF

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EP1032645B1
EP1032645B1 EP98964403A EP98964403A EP1032645B1 EP 1032645 B1 EP1032645 B1 EP 1032645B1 EP 98964403 A EP98964403 A EP 98964403A EP 98964403 A EP98964403 A EP 98964403A EP 1032645 B1 EP1032645 B1 EP 1032645B1
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European Patent Office
Prior art keywords
weight
liquid detergents
water
based liquid
contain
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EP98964403A
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German (de)
English (en)
French (fr)
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EP1032645A1 (de
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Dieter Legel
Josef Penninger
Theodor Völkel
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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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • 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
    • C11D3/042—Acids
    • 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
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3726—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions

Definitions

  • the present invention relates to low-concentration, higher-viscosity liquid detergents through the use of a thickening system under a wide variety of climatic conditions are stable in storage and viscosity, are not subject to phase separation and also at Show color stability.
  • liquid detergents such as agar agar, carrageenan, tragacanth, gum arabic, alginates, pectins, Polyoses, guar flour, locust bean gum, starch, dextrins, gelatin, casein, carboxymethyl cellulose et al Cellulose ether, hydroxyethyl and.
  • Liquid detergents with viscosities between 500 to 20,000 mPas, preferably from 2,000 to 10,000 mPas, in which lamellar surfactant droplets are dispersed in an aqueous electrolyte phase are described in European patent application EP-A 691 399 (Colgate). These agents contain 10 to 45% by weight of surfactant (s), at least one builder and 0.01 to 5% by weight of a mercapto-terminated polymer with an average molecular weight of between 1500 and 50,000 gmol -1 .
  • boron compounds in aqueous liquid detergents contain the boron compounds and a polyol as an enzyme stabilization system for a mixture. from proteolytic and lipolytic enzymes, preferred stabilization systems consisting of a sorbitol / borax mixture. None is said in this document about the viscosity and stability of liquid detergents.
  • Liquid, aqueous detergent concentrates which maintain or increase their viscosity when diluted with water are described in EP-A 724 013 (Colgate). This effect is achieved through the use of two surfactants with different resistance to electrolytes and the addition of a dissolved electrolyte, whereby the concentrate has a viscosity of less than 2500 mPas and loses its micellar structure in favor of the formation of a lamellar phase when diluted with water.
  • WO96 / 01305 (Unilever) describes an aqueous cleaning and liquid detergent which, when diluted with at least twice the amount of water, forms a microemulsion which has particle sizes of 10 to 100 nm.
  • the agent contains 20 to 70 wt .-% water, 15 to 40 wt .-% of a surfactant system, the at least one nonionic surfactant from the group of alkoxylated alcohols and not more than 20 wt .-% anion, cation, ampho- or zwitterionic Contains surfactants, 5 to 30 wt .-% solvent and 5 to 20 wt .-% water-insoluble oil.
  • EP 786 516 (Unilever) describes isotropic liquid detergents which contain special dirt-dispersing polymers. In this document, too, there is no information on particularly effective and advantageous thickening systems.
  • liquid detergents with the property profile mentioned can be made if you have a thickening system made of polyurethane or modified Polyacrylates, a boron compound and complexing agents are incorporated into the agents.
  • the first component of the thickening system is a polyurethane or a modified one Polyacrylate, which, based on the total agent, is used in amounts of 0.2 to 5% by weight becomes.
  • Polyurethanes are produced by polyaddition from dihydric and higher alcohols and isocyanates and can be described by the general formula I.
  • R 1 is a low molecular weight or polymeric diol radical
  • R 2 is an aliphatic or aromatic group
  • n is a natural number.
  • R ' is preferably a linear or branched C 2-12 alk (en) yl group, but can also be a residue of a higher alcohol, whereby cross-linked polyurethanes are formed which differ from the above formula I in that the R 1 further -O-CO-NH groups are bound.
  • TDI 2,4- or 2,6-toluenediisocyanate
  • MDI C 6 H 4 -CH 2 -C 6 H 4
  • HMDI, R 2 (CH 2 ) 6 ].
  • polyurethane-based thickeners are, for example, under the names Acrysol® PM 12 V (mixture of 3-5% modified starch and 14-16% PUR resin in water, Rohm & Haas), Borchigel® L75-N (non-ionic PUR dispersion, 50% in water, Borchers), Coatex® BR-100-P (PUR dispersion, 50% in water / butylglycol, Dimed), Nopco® DSX-1514 (PUR dispersion, 40% in water) butyltrigylcol, Henkel- Nopco), thickener QR 1001 (20% PUR emulsion in water / digylcol ether, Rohm & Haas) and Rilanit® VPW-3116 (PUR dispersion, 43% in water, Henkel) available.
  • Acrysol® PM 12 V mixture of 3-5% modified starch and 14-16% PUR resin in water, Rohm & Haas
  • Borchigel® L75-N non-
  • Preferred liquid detergents contain 0.2 to 4% by weight, preferably 0.3 to 3% by weight and in particular 0.5 to 1.5% by weight of a polyurethane.
  • Modified polyacrylates which can be used in the context of the present invention are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula II in which R 3 is H or a branched or unbranched C 1-4 alk (en) yl radical, X is NR 5 or O, R 4 is an optionally alkoxylated branched or unbranched, possibly substituted C 8-22 alk (en ) yl radical, R 5 is H or R 4 and n is a natural number.
  • Such modified polyacrylates are generally esters or amides of acrylic acid or an ⁇ -substituted acrylic acid. Preferred among these polymers are those in which R 3 represents H or a methyl group.
  • the two hydrocarbon radicals which are bonded to the N atom being independent of one another can be selected from optionally alkoxylated branched or unbranched C 8-22 alk (en) yl radicals.
  • the designation of the radicals bound to X represents a statistical mean, which can vary in individual cases with regard to chain length or degree of alkoxylation.
  • Formula II only provides formulas for idealized homopolymers. However, copolymers in which the proportion of monomer units which satisfy the formula II is at least 30% by weight can also be used in the context of the present invention. For example, copolymers of modified polyacrylates and acrylic acid or salts thereof which still have acidic H atoms or basic --COO - groups can also be used.
  • Modified polyacrylates which are preferably used in the context of the present invention are polyacrylate-polymethacrylate copolymers which satisfy the formula IIa in which R 4 is a preferably unbranched, saturated or unsaturated C 8-22 alk (en) yl radical, R 6 and R 7 independently of one another are H or CH 3 , the degree of polymerization n is a natural number and the degree of alkoxylation a is a natural number is between 2 and 30, preferably between 10 and 20.
  • Products of the formula IIa are commercially available, for example, under the name Acusol® 820 (Rohm & Haas) in the form of 30% by weight dispersions in water.
  • R 4 is a stearyl radical
  • R 6 is a hydrogen atom
  • R 7 is H or CH 3 and the degree of ethoxylation a is 20.
  • Preferred liquid detergents contain 0.2 to 4% by weight, based on the total detergent. preferably 0.3 to 3% by weight and in particular 0.5 to 1.5% by weight of a modified Polyacrylate of formula II.
  • the second component of the thickening system in the agents according to the invention is one Boron compound, which is used in amounts of 0.5 to 7 wt .-%.
  • Boron compounds which can be used in the context of the present invention are boric acid, Boron oxide, alkali borates such as ammonium, sodium and potassium ortho, meta and pyroborates, Borax in its various hydration levels and polyborates such as Alkali metal pentaborate.
  • Organic boron compounds such as esters of boric acid are also used.
  • Preferred liquid detergents contain 0.5 to 4% by weight, preferably 0.75 to 3 wt .-% and in particular 1 to 2 wt .-% boric acid or sodium tetraborate.
  • the liquid detergents according to the invention contain the third component of the thickening system 1 to 8% by weight of a complexing agent.
  • complexing agent are in the context of the present application low molecular weight hydroxycarboxylic acids understood as citric acid, tartaric acid, malic acid, or gluconic acid or its salts.
  • liquid detergents contain as component c) Thickening system citric acid or sodium citrate, with liquid detergent preferred which are 2.0 to 7.5% by weight, preferably 3.0 to 6.0% by weight and in particular 4.0 to 5.0 % By weight contain sodium citrate.
  • the inventive ones contain Liquid detergent surfactant (s), being anionic, nonionic, cationic and / or amphoteric surfactants are used.
  • Liquid detergent surfactant being anionic, nonionic, cationic and / or amphoteric surfactants are used.
  • the proportion of anionic Surfactants should be greater than the proportion of nonionic surfactants.
  • the total surfactant content the liquid detergent is, as described above, preferably below 30% by weight, based on the total Liquid detergent.
  • 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 12-14 alcohols with 3 EO, 4 EO or 7 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-18 alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12- 18 alcohol with 7 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.
  • Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention.
  • block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • mixed alkoxylated nonionic surfactants can also be used, in which EO and PO units are not distributed in blocks but statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as them are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533 .
  • 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 can be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula III, in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 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.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula IV, in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical is or an oxyalkyl group having 1 to 8 carbon atoms, wherein C 1- 4 alkyl or phenyl groups being preferred, and [Z] is a linear polyhydroxyalkyl residue, whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest.
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl
  • [Z] is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted, for example according to the teaching of international application WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired polyhydroxy fatty acid amides.
  • the content of preferred liquid detergents in nonionic surfactants is 5 to 20% by weight, preferably 7 to 15% by weight and in particular 9 to 14% by weight, in each case based on the entire mean.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably C 9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12-18 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are in the Manufactured by esterification of a monoglycerin with 1 to 3 moles of fatty acid or the transesterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained.
  • preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 up 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) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are 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 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 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 which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 18 fatty alcohol radicals 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.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated ones are suitable and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, (hydrogenated) erucic acid and behenic acid and in particular from natural fatty acids, e.g. Coconut, palm kernel, olive oil or tallow fatty acids, derived Soap mixtures.
  • the anionic surfactants including the 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, available.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.
  • the content of preferred liquid detergents in anionic surfactants is 5 to 25% by weight, preferably 7 to 22% by weight and in particular 10 to 20% by weight, in each case based on the entire mean.
  • the viscosity of the agents according to the invention can be determined using customary standard methods (for example Brookfield viscometer LVT-II measured at 20 rpm and 20 ° C, spindle 3) are and is preferably in the range of 500 to 5000 mPas. Have preferred means Viscosities from 1000 to 4000 mPas, with values between 1300 and 3000 mPas particularly are preferred.
  • the agents according to the invention can contain other ingredients that are technical and / or aesthetic Further improve the properties of the liquid detergent.
  • the agents according to the invention can contain preferred agents in addition to the thickening system and surfactant (s) one or more substances from the group of builders, bleaching agents, bleach activators, Enzymes, electrolytes, non-aqueous solvents, pH adjusting agents, fragrances, perfume carriers, Fluorescent agents, dyes, hydrotopes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, Color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating agents, Swelling and anti-slip agents as well as UV absorbers.
  • silicates As builders that can be contained in the liquid detergents according to the invention, are in particular silicates, aluminum silicates (in particular zeolites), carbonates, salts organic di- and polycarboxylic acids and mixtures of these substances.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 .y 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 is 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514 .
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171 .
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates do not give sharp X-ray reflections in X-ray diffraction experiments, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 .
  • Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na 2 O. (1-n) K 2 O. Al 2 O 3 . (2 - 2.5) SiO 2 .
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • bleaching agents that serve as bleaching agents and supply H 2 O 2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • bleach activators can be incorporated into the liquid detergent.
  • Bleach activators can be compounds that are aliphatic under perhydrolysis conditions
  • Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used.
  • Suitable are substances that contain O- and / or N-acyl groups of the number of carbon atoms mentioned and / or where appropriate carry substituted benzoyl groups.
  • Multi-acylated alkylenediamines are preferred, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • TAED tetraacety
  • Bleaching catalysts are incorporated into the liquid detergent.
  • these Fabrics are bleach-enhancing transition metal salts or transition metal complexes how for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V, and Cu complexes with nitrogenous tripod ligands as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.
  • Enzymes include, in particular, those from the classes of hydrolases such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or others Glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases wear in the laundry to remove stains such as protein, fat or starchy Stains and graying. Cellulases and other glycosyl hydrolases can furthermore by removing pilling and microfibrils for color preservation and Contribute to increasing the softness of the textile. To bleach or inhibit the Color transfer can also use oxireductases.
  • hydrolases such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or others Glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases wear in the laundry to remove stains such as protein, fat or starchy Stains and graying. Cellulases and other glycosyl hydrolases can furthermore by
  • proteases of the subtilisin type and in particular proteases derived from Bacillus lentus won, used.
  • Enzyme mixtures for example of protease and Amylase or protease and lipase or lipolytic enzymes or protease and Cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, Amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease and / or lipase-containing Mixtures or mixtures with lipolytically active enzymes of particular Interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and Pectinases.
  • Cellobiohydrolases, endoglucanases and ⁇ -glucosidases are preferably used as cellulases, which are also called cellobiases, or mixtures of these are used. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases become.
  • the enzymes can be adsorbed on carriers or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or Enzyme granules can, for example, 0.1 to 5 wt .-%, preferably 0.12 to 2 wt .-% be.
  • a wide number of different salts can be used as electrolytes from the group of inorganic salts.
  • Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl 2 in the agents according to the invention is preferred.
  • the proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.
  • Non-aqueous solvents which are used in the agents according to the invention can, for example, come from the group of mono- or polyhydric alcohols, alkanolamines or glycol ether, provided they are in the specified concentration range with water are miscible.
  • the solvents are preferably selected from ethanol, n- or i-propanol, Butanols, glycol, propane or butanediol, glycerin, diglycol, propyl or Butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, Ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, Propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl, or ethyl ether, diisopropylene glycol monomethyl or
  • the use of steep pH agents may be indicated. All known ones can be used here Acids or alkalis, provided that their use does not result from application technology or for ecological reasons or for reasons of consumer protection. Usually The amount of these adjusting agents does not exceed 5% by weight of the total formulation.
  • suitable dyes are colored.
  • Preferred dyes their selection to the expert no difficulty, have a high storage stability and insensitivity compared to the other ingredients of the agents and against light and no pronounced Substantivity towards textile fibers so as not to stain them.
  • Suitable anti-redeposition agents also known as should be called repellents are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose containing methoxy groups 15 to 30 wt .-% and of hydroxypropyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ether and the polymers known from the prior art phthalic acid and / or terephthalic acid or their derivatives, in particular polymers from ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these.
  • Optical brighteners can be added to the agents according to the invention to remove graying and yellowing of the treated textiles. These substances absorb on the fiber and cause a lightening and pretend Bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light convert, the ultraviolet light absorbed from the sunlight being slightly bluish Fluorescence is emitted and with the yellow tone of the grayed or yellowed laundry pure white results.
  • Suitable compounds come from the substance classes, for example 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenylene, Methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, Naphthalimide, benzoxazole, benzisoxazole and benzimidazole systems as well as by Heterocycle-substituted pyrene derivatives.
  • the optical brighteners are usually in Amounts between 0.05 and 0.3 wt .-%, based on the finished agent, used.
  • Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening.
  • water-soluble colloids mostly of an organic nature, are suitable, for example glue, gelatin, Salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters cellulose or starch.
  • water-soluble containing acidic groups Polyamides are suitable for this purpose. Soluble starch preparations and use starch products other than the above, e.g. degraded starch, aldehyde starches etc. Polyvinyl pyrrolidone is also useful.
  • cellulose ethers are preferred 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 in amounts of 0.1 to 5 wt .-%, based on the Means used
  • the inventive Agents contain synthetic anti-crease agents. These include, for example, synthetic Products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
  • the agents according to the invention can be antimicrobial Contain active ingredients.
  • Important substances from these groups are, for example, benzalkonium chlorides, Alkylarlyl sulfonates, halophenols and phenol mercuric acetate, with the inventive These compounds can also be dispensed with entirely.
  • the Contain antioxidants To unwanted, caused by oxygen and other oxidative processes To prevent changes to the agents and / or the treated textiles, the Contain antioxidants.
  • This class of compounds includes, for example, substituted ones Phenols, hydroquinones, pyrocatechols and aromatic amines and organic Sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve.
  • External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
  • silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes, in which the alkyl groups have one to five carbon atoms and in whole or in part are fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which may be derivatized can be and are then amino-functional or quaternized or Si-OH-, Si-H- and / or Si-Cl bonds.
  • the viscosities of the preferred silicones are included 25 ° C in the range between 100 and 100,000 mPas, the silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.
  • the agents according to the invention can also contain UV absorbers which act on the treated textiles and improve the lightfastness of the fibers.
  • Links, which have these desired properties are, for example, those by radiationless deactivation effective compounds and derivatives of benzophenone with Substituents in the 2- and / or 4-position.
  • Substituted benzotriazoles are also in the 3-position Phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in 2-position, salicylates, organic Ni complexes as well as natural substances such as umbelliferone and the body's own urocanic acid.
  • suitable Heavy metal complexing agents are, for example, the alkali salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic Polyelectrolytes such as polymaleates and polysulfonates.
  • EDTA ethylenediaminetetraacetic acid
  • NTA nitrilotriacetic acid
  • alkali metal salts of anionic Polyelectrolytes such as polymaleates and polysulfonates.
  • a preferred class of complexing agents are the phosphonates, which are used in preferred liquid detergents in amounts of 0.01 to 1.5% by weight, preferably 0.02 to 1% by weight and in particular from 0.03 to 0.5% by weight are contained.
  • phosphonates include in particular organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), Aminotri (methylenephosphonic acid) (ATMP), Diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts become.
  • organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), Aminotri (methylenephosphonic acid) (ATMP), Diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2,4-
  • Particularly preferred liquid detergents contain as component c) of the thickening system 1-hydroxyethane-1,1-diphosphonic acid in the form of its ammonium or alkali metal salts.
  • the agents according to the invention are produced by simply mixing the constituents in stirred tanks, where water, non-aqueous solvents and surfactant (s) are expedient are presented and the other ingredients are added in portions become. Separate heating during manufacture is not required if desired the temperature of the mixture should not exceed 80 ° C.
  • liquid detergents E1 and E2 according to the invention and the comparative examples V1 to V4, the composition of which is given in Table 1, were prepared by mixing the individual constituents.
  • Viscosity after manufacture and after 16 weeks of storage [mPas] V1 V2 V3 V4 E1 E2 after manufacture 1850 1900 1870 1800 1970 1980 Summer climate (25 - 40 ° C) 1100 1020 1200 1790 2050 2000 Autumn climate (10 - 30 ° C) 1080 1130 1090 1680 2080 2040 Winter climate (0 - 10 ° C) 1200 1210 1180 1700 1940 1960

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
EP98964403A 1997-11-26 1998-11-17 Niedrigkonzentrierte höherviskose flüssigwaschmittel Expired - Lifetime EP1032645B1 (de)

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DE19752163A DE19752163A1 (de) 1997-11-26 1997-11-26 Niedrigkonzentrierte höherviskose Flüssigwaschmittel
DE19752163 1997-11-26
PCT/EP1998/007344 WO1999028430A1 (de) 1997-11-26 1998-11-17 Niedrigkonzentrierte höherviskose flüssigwaschmittel

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EP1032645B1 true EP1032645B1 (de) 2002-03-06

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EP (1) EP1032645B1 (enExample)
JP (1) JP4361678B2 (enExample)
KR (1) KR100567607B1 (enExample)
AT (1) ATE214092T1 (enExample)
DE (2) DE19752163A1 (enExample)
ES (1) ES2173661T3 (enExample)
HU (1) HU228345B1 (enExample)
PL (1) PL187488B1 (enExample)
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JP2001525453A (ja) 2001-12-11
ATE214092T1 (de) 2002-03-15
JP4361678B2 (ja) 2009-11-11
PL187488B1 (pl) 2004-07-30
KR20010032541A (ko) 2001-04-25
EP1032645A1 (de) 2000-09-06
US6342472B1 (en) 2002-01-29
HU228345B1 (en) 2013-03-28
HUP0100078A3 (en) 2002-11-28
KR100567607B1 (ko) 2006-04-04
DE19752163A1 (de) 1999-05-27
PL340621A1 (en) 2001-02-12
DE59803303D1 (de) 2002-04-11
HUP0100078A2 (hu) 2001-05-28
ES2173661T3 (es) 2002-10-16

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