EP0647260A1 - Washing and cleaning agents in liquid to paste form. - Google Patents

Washing and cleaning agents in liquid to paste form.

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Publication number
EP0647260A1
EP0647260A1 EP93912976A EP93912976A EP0647260A1 EP 0647260 A1 EP0647260 A1 EP 0647260A1 EP 93912976 A EP93912976 A EP 93912976A EP 93912976 A EP93912976 A EP 93912976A EP 0647260 A1 EP0647260 A1 EP 0647260A1
Authority
EP
European Patent Office
Prior art keywords
fatty acid
weight
fatty
composition according
glycerol esters
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP93912976A
Other languages
German (de)
French (fr)
Other versions
EP0647260B1 (en
Inventor
Frank Wangemann
Brigitte Giesen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0647260A1 publication Critical patent/EP0647260A1/en
Application granted granted Critical
Publication of EP0647260B1 publication Critical patent/EP0647260B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to a washing and cleaning agent in liquid to pasty form which contains anionic surfactants which consist entirely or at least to a large extent of oleochemical and thus renewable raw materials.
  • oleochemical surfactant compounds which are obtained from renewable vegetable and / or animal raw materials and which have a high ecological compatibility, is of great and rapidly increasing importance.
  • oleochemical surfactant compounds with high environmental compatibility are the known fatty alcohol sulfates, which by sulfating fatty alcohols of vegetable and / or animal origin with predominantly 10 to 20 carbon atoms in the fatty alcohol molecule and subsequent neutralization to form water-soluble salts, in particular in particular the corresponding alkali metal salts, and the known ⁇ -sulfofatty acid alkyl esters (ester sulfonates), which by oc-sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with predominantly 10 to 20 carbon atoms in the fatty acid molecule and subsequent neutralization to form water-soluble ones Mono salts, in particular the corresponding alkali salts, are prepared, and their disalts obtainable by hydrolysis.
  • oleochemical surfactant compounds are sulfonated fatty acid glycerol esters, for example sulfonated unsaturated fatty acid glycerol esters as described in international patent application WO 91/6532, or sulfonation products of saturated fatty acid glycerol esters as described in international patent application WO 91/9009.
  • the anionic surfactant that is still economically most important today belongs to the surfactant class of alkylbenzenesulfonates.
  • a disadvantage of these alkylbenzenesulfonates is that they are obtained from petrochemical raw materials.
  • the object was therefore to create a washing and cleaning agent in liquid to pasty form which contains anionic surfactants which either consist entirely or at least to a large extent of native, that is to say renewable, base chemical substances.
  • anionic surfactants are said to be able to replace alkylbenzene sulfonates completely or at least partially in washing and cleaning agent formulations which are otherwise customary, without any loss in washing performance.
  • the invention accordingly relates to a detergent and cleaning agent in liquid to pasty form which contains anionic or anionic and nonionic surfactants, the surfactant content of the agent being 20 to 70% by weight and sulfonic fatty acid glycerol esters in amounts as anionic surfactants from 2 to 25% by weight are included.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. If one starts from fats and oils, that is to say natural mixtures of different fatty acid glycerol esters, their fatty acid component usually builds up partly from saturated and partly from unsaturated fatty acids.
  • Suitable sulfonated fatty acid glycerol esters are, for example, the sulfonation products of the unsaturated fatty acid glycerol esters which are obtained on the basis of coriander oil, sunflower oil, cottonseed oil, olive oil, peanut oil, linseed oil, fish oil, lard or lard oil or rape oil.
  • the sulfonation can be carried out in accordance with international patent application WO 91/6532.
  • preferred sulfated fatty acid glycerol esters are the sulfonated 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. If one again starts from fats and oils, that is to say natural mixtures of different fatty acid glycerol esters, it is necessary in this case to largely saturate the starting products with hydrogen in a manner known per se, ie to iodine numbers less than 5, advantageously to harden less than 2.
  • Suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, rapeseed oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or pork lard. Due to their high natural content of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow.
  • the sulfonation of the saturated fatty acids with 6 to 22 carbon atoms or the mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as described in of international patent application WO 91/9009.
  • the sulfonation products are a complex mixture that contains mono-, di- and triglyceride sulfonates with an internal and / or internal sulfonic acid grouping.
  • Sulfonated fatty acid salts, glyceride sulfates, glycerol sulfates, glycerol and soaps are formed as by-products. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid-glycerol ester mixtures, the proportion of the oc-sulfonated fatty acid disalts can, depending on the procedure, be about 60% by weight.
  • sulfated fatty acid glycerol esters are understood to mean in each case this complex reaction mixture, including the unsulfated and non-washing-active constituents, but without aqueous components.
  • the total surfactant content of the compositions is preferably 25 to 65% by weight and, in particular, concentrated liquid to pasty compositions which have at least 30% by weight of anionic and nonionic surfactants are preferred.
  • the agents preferably contain 5 to 20% by weight of sulfonated fatty acid glycerol esters, in particular fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, 10 to 65% by weight of nonionic surfactants and preferably further anionic ones
  • Surfactants for example alkyl sulfates, preferably fatty alkyl sulfates, alkane sulfonates, soaps or mixtures thereof.
  • the agents can also contain small amounts of alkylbenzenesulfonates, for example about 1 to 5% by weight of alkylbenzenesulfonate; especially preferred detergents and cleaning agents in liquid to pasty form are, however, free of alkylbenzenesulfonates.
  • the anionic surfactants used are preferably alkali metal salts, in particular sodium or potassium salts.
  • the anionic surfactants used in addition to the sulfonated fatty acid glycerol esters are preferably surfactants from the class of the sulfonates and sulfates.
  • sulfonates are sulfonates based on oleochemicals, such as the esters of oc-sulfo fatty acids, the sulfo group being in its salt form (mono salt), for example the ⁇ -sulfonated methyl esters, the hydrogenated coconut, palm kernel, or tallow fatty acids.
  • oleochemicals such as the esters of oc-sulfo fatty acids, the sulfo group being in its salt form (mono salt), for example the ⁇ -sulfonated methyl esters, the hydrogenated coconut, palm kernel, or tallow fatty acids.
  • the readily biodegradable alkanesulfonates which are obtained from Ci2-Ci8-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the sulfonate group is statistically distributed over the entire carbon chain, the secondary alkanesulfonates predom
  • alkanesulfonates are obtained from petrochemical raw materials. Their proportion in the liquid to pasty washing and cleaning agents according to the invention is therefore preferably not more than about 5 to 15% by weight. It has been found that agents which contain mixtures of alkanesulfonates and sulfonated fatty acid glycerol esters, the proportion of sulfated fatty acid glycerol esters in these mixtures being 10 to 80% by weight, have no loss in washing performance compared to only alkanesulfonate-containing mixtures.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols.
  • Suitable fatty alkyl sulfates are the sulfuric acid monoesters of the Ci2-Ci8 fatty alcohols, such as lauryl, myristyl, cetyl alcohol or stearyl alcohol, and those obtained from coconut oil, palm and palm kernel oil Fatty alcohol mixtures which may additionally contain fractions of unsaturated alcohols, for example oleyl alcohol.
  • Mixtures in which the proportion of the alkyl radicals is 50 to 70% by weight on C12, 18 to 30% by weight on C14, 5 to 15% by weight on Ciss, less than 3% by weight find a preferred use.
  • -% are distributed on C10 and less than 10% by weight on CQ.
  • the proportion of fatty alkyl sulfates in the compositions is preferably 1 to 20
  • anionic surfactants are the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain Cg to Ciß fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with restricted homolog distribution are particularly preferred.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts of 3 to 25% by weight, in particular in amounts of 5 to 20% by weight.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or taig fatty acids, derived soap mixtures.
  • the salts of saturated and unsaturated fatty acids with Ci2-Ciß chain lengths in the form of their mixtures are particularly suitable.
  • a preferred soap mixture is formed from sodium oleate and the sodium salts of the saturated C ⁇ -Clö ⁇ ettic acid mixtures.
  • the proportion of Ci2-Ci4 fatty acids in the saturated component is expediently at least 60% by weight, preferably at least 75% by weight (calculated as fatty acid). Suitable for this purpose are, for example, coconut fatty acids, from which the portions with 10 or fewer carbon atoms are largely separated.
  • the oleic acid and the coconut fatty acid still contain certain proportions of stearic acid, but their proportion, based on soap-forming fatty acids, should be at most 25% by weight, preferably less than 20% by weight.
  • a soap mixture of sodium oleate and the sodium salt of lauric acid is also preferred.
  • the weight ratio of the unsaturated to the saturated component is preferably 2: 1 to 1: 2.
  • Particularly preferred detergents and cleaning agents in liquid to pasty form contain 15 to 35% by weight of a mixture of sulfated fatty acid glycerol esters and further anionic surfactants in a weight ratio of 1: 3 to 3: 1.
  • anionic surfactant mixtures are preferred, which contain sulfated fatty acid glycerol esters, fatty alkyl sulfates and fatty acid soaps or sulfonated fatty acid glycerol esters, alkane sulfonates and fatty acid soaps.
  • the preferred nonionic surfactants are liquid ethoxylated and / or propoxylated, preferably ethoxylated fatty alcohols, in particular primary alcohols preferably having 9 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 is linear or in 2-position may be methyl branched, or may contain linear and methyl branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates are preferred which have an average of 2 to 8 EO.
  • the preferred ethoxylated alcohols include, for example, in particular Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cn alcohol with 7 EO, Ci3-Ci5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2 -Ci8 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C12-C j 4 alcohol with 3 EO and Ci2-Ci8 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a restricted homolog distribution (narrow range ethoxylates, NRE).
  • the liquid nonionic surfactants in the agents according to the invention are preferably 15 to 65% by weight.
  • alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical branched with methyl in the 2-position with 8 to 22, preferably 12 to 18 C atoms and G denotes 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.
  • the content of alkyl glycosides in the agents according to the invention is preferably 0.5 to 8% by weight and in particular 1 to 5% by weight.
  • the washing and cleaning agents according to the invention can contain, as organic solvents, mono- and / or polyfunctional alcohols with 1 to 6 carbon atoms, preferably with 1 to 4 carbon atoms.
  • Preferred alcohols are ethanol, 1,2-propanediol, glycerol and mixtures thereof.
  • the agents preferably contain 2 to 20 wt .-% and in particular 5 to 15 wt .-% ethanol or any mixture of ethanol and 1,2-propanediol or in particular ethanol and glycerol.
  • the detergents and cleaning agents according to the invention in liquid to pasty form either in addition to the mono- and / or polyfunctional alcohols having 1 to 6 carbon atoms or alone polyethylene glycol with a relative molecular weight between 200 and 2000, preferably up to 600 contained in amounts of 2 to 17 wt .-%.
  • the washing and cleaning agents according to the invention in liquid to pasty form can be aqueous or essentially water-free agents.
  • “essentially water-free” means that the agent preferably contains no free water that is not bound as crystal water or in a comparable form. In some cases, a small amount of free water can be tolerated, especially in amounts of up to 5% by weight.
  • Preferred essentially water-free detergents and cleaning agents in liquid to pasty form contain 20 to 65% by weight of liquid nonionic surfactants and water in amounts of 0 to 5% by weight.
  • the anionic surfactants mentioned and, for example, bleaches, thickeners, builders, inorganic salts, foam inhibitors, enzymes, optical brighteners and colorants can be used as further ingredients.
  • bleaching agents are, for example, peroxy carbonate, citrate perhydrates and H2O2-providing peracid salts of peracids, such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight.
  • the use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred.
  • hardened castor oil salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, Magnesium and titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used.
  • the latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polyethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50% to 10% maleic acid.
  • the relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolyers between 2000 and 200000, preferably between 50,000 and 120,000, based on the free acid.
  • Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above one million are also particularly suitable. Examples of these are the polymers obtainable under the name Carbopol ( R ) 940 and 941.
  • the crosslinked polyacrylates are preferably used in amounts of not more than 1% by weight, preferably in amounts of 0.2 to 0.7% by weight.
  • the water-containing liquid to pasty washing and cleaning agents are preferably free of peroxy bleaching agents. They preferably contain 5 to 35% by weight and in particular 10 to 35% by weight of nonionic surfactants and 20 to 55% by weight and in particular 25 to 45% by weight of water. In a preferred embodiment, liquid to pasty agents contain 10 to 20% by weight of ethoxylated fatty alcohols, preferably a primary C12-C18 fatty alcohol with an average of 1 to 12 moles of ethylene oxide per mole of alcohol.
  • liquid to pasty concentrates containing 20 to 35% by weight of nonionic surfactants: in particular 22 to 32% by weight of a primary Ci2-Ci8 fatty alcohol with an average of 1 to 12 moles of ethylene oxide per mole of fatty alcohol, 28 to 40 wt .-% water and 5 to 17 wt .-% mono- and / or polyfunctional alcohols containing 2 to 4 carbon atoms.
  • the agents can additionally contain about 5 to 20% by weight of a partially esterified copolymer, as described in European patent application 367 049.
  • This partially esterified Poly mers are prepared by copolymerization of (a) at least one fin or C4-C28-01 e mixtures of at least one C4-C28-01efin with up to 20 mol% C ⁇ -C28-alkyl vinyl ethers and (b) ethylenically unsaturated dicarboxylic anhydrides having from 4 to 8 carbon atoms in a molar ratio 1: 1 to Copolymeris2011en having K values from 6 to 100 and subsequent partial esterification of the Copolymeris helpfule with reaction products such as C ⁇ -Ci3-alcohols, C8-C22 _ f r e t tklaren, C ⁇ - Ci2-alkylphenols, secondary C2-C3o ⁇ amines or mixtures thereof with at least one C2-C4-alkylene oxide or tetrahydrofuran and hydrolysis of the anhydride groups of the copolymers to give carboxyl groups, the partial esterification of the cop
  • Preferred copolymers contain maleic anhydride as the ethylenically unsaturated dicarboxylic acid anhydride.
  • the partially esterified copolymers can be present either in the form of the free acid or preferably in partially or completely neutralized form.
  • the copolymers are advantageously used in the form of an aqueous solution, in particular in the form of a 40 to 50% by weight solution.
  • the copolymers not only make a contribution to the primary and secondary washing performance of the liquid washing and cleaning agent, but also bring about a desired reduction in the viscosity of the concentrated liquid washing agent.
  • the use of these partially esterified copolymers gives concentrated aqueous liquid detergents which are flowable under the sole influence of gravity and without the action of other shear forces.
  • the concentrated ones include aqueous liquid detergents partially esterified copolymers in amounts of 5 to 15 wt .-% and in particular in amounts of 8 to 12 wt .-%.
  • the pH of the concentrated and particularly preferred agents according to the invention is generally 7 to 10.5, preferably 7 to 9.5 and in particular 7 to 8.5. Higher pH values, for example above 9, can be set by using small amounts of sodium hydroxide solution or alkaline salts such as sodium carbonate or sodium silicate.
  • the washing and cleaning agents according to the invention generally have viscosities between 150 and 10,000 mPas (Brookfield viscometer, spindle 1, 20 revolutions per minute, 20 ° C.). Viscosities between 150 and 5000 mPas are preferred for the essentially water-free agents.
  • the viscosity of the aqueous compositions is preferably below 2000 mPas and in particular between 150 and 1000 mPas.
  • the aqueous compositions can contain known additives commonly used in detergents and cleaning agents, for example salts of polycarboxylic acids, for example citric acid, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filler salts and dye - and contain fragrances, opacifiers or pearlescent agents.
  • salts of polycarboxylic acids for example citric acid, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filler salts and dye - and contain fragrances, opacifiers or pearlescent agents.
  • the salts of polyphosphonic acids which are preferably used are the neutral reacting sodium salts of, for example, l-hydroxyethane-l, l, -diphosphonate in amounts of 0.1 to 1.5% by weight.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Their proportion can be about 0.2 to about 2% by weight. The enzymes can be adsorbed on carrier substances and / or embedded in Hü11 substances in order to protect them against premature decomposition. In addition to the mono- and polyfunctional alcohols and the phosphates, the agents can contain further enzyme stabilizers.
  • sodium formate 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous.
  • Suitable foam inhibitors contain, for example, known organopolysiloxanes, paraffins or waxes. As mentioned above, preference is also given to the use of sulfonated unsaturated fatty acid glycerol esters.
  • the sulfur trioxide was expelled from a corresponding amount of 65% by weight oleum by heating, diluted to a concentration of 2% by volume with nitrogen and blown in at the side of the reactor head.
  • the crude sulfonation product was subjected to a post-reaction at 80 ° C. for 30 minutes.
  • the acidic sulfonation product was then continuously neutralized to pH 6.5 to 7.5 using aqueous 25% strength by weight sodium hydroxide solution.
  • Table 1 Average composition of the fatty acid glycerol esters used after curing, in% by weight
  • HK hardened coconut oil
  • HPK hardened palm kernel oil
  • Washing program Colored washing program (without prewash) at 40 ° C Dosage: 180 g or 200 g per machine Water hardness: 16 ° d Textile samples: 3.5 kg clean laundry (normal household laundry) Determinations: 3 times Measurement conditions: artificial soiling: RFC 3/24 (465 nm, suppression of the brightener effect) natural soiling: length device (Y-filter) reflectance differences of 2% and more are to be regarded as significant.
  • the stains were:
  • compositions of the aqueous liquid detergents were (details in% by weight):
  • the agents M2 / V, M2 / 1 and M2 / 2 were tested against each other at a dosage of 180 g per machine. The results are shown in Table 3.

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  • Engineering & Computer Science (AREA)
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Abstract

Described are liquid to pasty washing and cleaning agents containing anionic or anionic and non-ionic surfactants in quantities from 20 to 70 % by wt., and including as anionic surfactants 2 to 25 % by wt. of sulphonated fatty-acid glycerin esters. Such washing and cleaning agents suffer no loss in washing performance compared with liquid to pasty washing- and cleaning-agent formulations usually containing surfactants. The invention enables alkylbenzene sulphonates to be completely or at least partly replaced. Preferred agents contain as anionic surfactants a mixture of sulphonated fatty-acid glycerin esters, fatty-alkyl sulphate and fatty-acid soaps or a mixture of sulphonated fatty-acid glycerin esters, alkane sulphonate and fatty-acid soaps.

Description

"Wasch- und Reinigungsmittel in flüssiger bis pastöser Form" "Detergents and cleaning agents in liquid to pasty form"
Die Erfindung betrifft ein Wasch- und Reinigungsmittel in flüssiger bis pastöser Form, das anionische Tenside enthält, die ganz oder zumindest zu einem hohen Anteil aus fettchemischen und somit nachwachsenden Rohstoffen bestehen.The invention relates to a washing and cleaning agent in liquid to pasty form which contains anionic surfactants which consist entirely or at least to a large extent of oleochemical and thus renewable raw materials.
Dem Einsatz fettchemischer Tensidverbindungen, die aus nachwachsenden pflanzlichen und/oder tierischen Rohstoffen gewonnen werden und die eine hohe ökologische Verträglichkeit aufweisen, kommt große und dabei stark zunehmende Bedeutung zu. Beispiele für derartige fettchemische Tensidver¬ bindungen mit hoher Umwelt erträglichkeit sind die bekannten Fettalkohol¬ sulfate, die durch Sulfatierung von Fettalkoholen pflanzlichen und/oder tierischen Ursprungs mit überwiegend 10 bis 20 C-Atomen im Fettalkoholmo¬ lekül und nachfolgende Neutralisation zu wasserlöslichen Salzen, insbe¬ sondere den entsprechenden Alkalisalzen, hergestellt werden, sowie die bekannten α-Sulfofettsäurealkylester (Estersulfonate), die durch oc-Sulfo- nierung der Methylester von Fettsäuren pflanzlichen und/oder tierischen Ursprungs mit überwiegend 10 bis 20 C-Atomen im Fettsäuremolekül und nachfolgende Neutralisation zu wasserlöslichen Mono-Salzen, insbesondere den entsprechenden Alkalisalzen, hergestellt werden, und deren durch Hy¬ drolyse erhältlichen Disalze.The use of oleochemical surfactant compounds, which are obtained from renewable vegetable and / or animal raw materials and which have a high ecological compatibility, is of great and rapidly increasing importance. Examples of such oleochemical surfactant compounds with high environmental compatibility are the known fatty alcohol sulfates, which by sulfating fatty alcohols of vegetable and / or animal origin with predominantly 10 to 20 carbon atoms in the fatty alcohol molecule and subsequent neutralization to form water-soluble salts, in particular in particular the corresponding alkali metal salts, and the known α-sulfofatty acid alkyl esters (ester sulfonates), which by oc-sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with predominantly 10 to 20 carbon atoms in the fatty acid molecule and subsequent neutralization to form water-soluble ones Mono salts, in particular the corresponding alkali salts, are prepared, and their disalts obtainable by hydrolysis.
Beispiele für weitere fettchemische Tensidverbindungen sind sulfierte Fettsäureglycerinester, beispielsweise sulfierte ungesättigte Fettsäure- glycerinester, wie sie in der internationalen Patentanmeldung WO 91/6532 beschrieben sind, oder Sulfierprodukte gesättigter Fettsäureglycerinester, wie sie in der internationalen Patentanmeldung WO 91/9009 beschrieben sind.Examples of other oleochemical surfactant compounds are sulfonated fatty acid glycerol esters, for example sulfonated unsaturated fatty acid glycerol esters as described in international patent application WO 91/6532, or sulfonation products of saturated fatty acid glycerol esters as described in international patent application WO 91/9009.
Das in heutiger Zeit immer noch wirtschaftlich bedeutendste Aniontensid gehört der Tensidklasse der Alkylbenzolsulfonate an. Ein Nachteil dieser Alkylbenzolsulfonate besteht darin, daß sie aus petroche isehen Grund¬ stoffen gewonnen werden. Es bestand daher die Aufgabe, ein Wasch- und Reinigungsmittel in flüssiger bis pastöser Form zu schaffen, das Aniontenside enthält, die entweder vollständig oder doch zu einem hohen Anteil aus nativen, also nachwach¬ senden fettchemischen Grundstoffen bestehen. Diese Aniontenside sollen in ansonsten üblichen Wasch- und Reinigungsmittelformulierungen Alkylbenzol¬ sulfonate ohne Einbußen in der Waschleistung vollständig oder zumindest teilweise ersetzen können.The anionic surfactant that is still economically most important today belongs to the surfactant class of alkylbenzenesulfonates. A disadvantage of these alkylbenzenesulfonates is that they are obtained from petrochemical raw materials. The object was therefore to create a washing and cleaning agent in liquid to pasty form which contains anionic surfactants which either consist entirely or at least to a large extent of native, that is to say renewable, base chemical substances. These anionic surfactants are said to be able to replace alkylbenzene sulfonates completely or at least partially in washing and cleaning agent formulations which are otherwise customary, without any loss in washing performance.
Gegenstand der Erfindung ist demnach ein Wasch- und Reinigunsmittel in flüssiger bis pastöser Form, das anionische oder anionische und nichtio¬ nische Tenside enthält, wobei der Gehalt des Mittels an Tensiden 20 bis 70 Gew.-% beträgt und als anionische Tenside sulfierte Fettsäureglycerinester in Mengen von 2 bis 25 Gew.-% enthalten sind.The invention accordingly relates to a detergent and cleaning agent in liquid to pasty form which contains anionic or anionic and nonionic surfactants, the surfactant content of the agent being 20 to 70% by weight and sulfonic fatty acid glycerol esters in amounts as anionic surfactants from 2 to 25% by weight are included.
Unter Fettsäureglycerinestern sind die Mono-, Di- und Triester sowie deren Gemische zu verstehen, wie sie bei der Herstellung durch Veresterung durch ein Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden. Geht man von Fetten und Ölen, also natürlichen Gemischen unterschiedlicher Fettsäure¬ glycerinester aus, so baut sich deren Fettsäurekomponente üblicherweise teilweise aus gesättigten und teilweise aus ungesättigten Fettsäuren auf. Geeignete sulfierte Fettsäureglycerinester sind beispielsweise die Sul- fierprodukte der ungesättigten Fettsäureglycerinester, die auf Basis von Korianderöl, Sonnenblumenöl, Baumwollsaatöl, Olivenöl, Erdnußöl, Leinöl, Fischöl, Schweineschmalz oder ölsäurereiehern Rüböl gewonnen werden. Die Sulfierung kann gemäß der internationalen Patentanmeldung WO 91/6532 er¬ folgen.Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. If one starts from fats and oils, that is to say natural mixtures of different fatty acid glycerol esters, their fatty acid component usually builds up partly from saturated and partly from unsaturated fatty acids. Suitable sulfonated fatty acid glycerol esters are, for example, the sulfonation products of the unsaturated fatty acid glycerol esters which are obtained on the basis of coriander oil, sunflower oil, cottonseed oil, olive oil, peanut oil, linseed oil, fish oil, lard or lard oil or rape oil. The sulfonation can be carried out in accordance with international patent application WO 91/6532.
Bevorzugte sulfierte Fettsäureglycerinester sind jedoch die Sulfierpro- dukte von gesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen, bei¬ spielsweise der Capronsäure, Caprylsäure, Caprinsäure, Myristinsäure, Laurinsäure, Palmitinsäure, Stearinsäure oder Behensäure. Geht man dabei wiederum von Fetten und Ölen, also natürlichen Gemischen unterschiedlicher Fettsäureglycerinester aus, so ist es in diesem Fall erforderlich, die Einsatzprodukte vor der Sulfierung in an sich bekannter Weise mit Wasser¬ stoff weitgehend abzusättigen, d.h. auf Iodzahlen kleiner 5, vorteil- hafterweise kleiner 2 zu härten. Typische Beispiele geeigneter Einsatz¬ stoffe sind Palmöl, Palmkernöl, Palmstearin, Olivenöl, Rüböl, Korianderöl, Sonnenblumenöl, Baumwollsaatöl, Erdnußöl, Leinöl, Lardöl oder Schweine¬ schmalz. Aufgrund ihres hohen natürlichen Anteils an gesättigten Fettsäu¬ ren hat es sich jedoch als besonders vorteilhaft erwiesen, von Kokosöl, Palmkernöl oder Rindertalg auszugehen. Die Sulfierung der gesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen oder der Mischungen aus Fett¬ säureglycerinestern mit Iodzahlen kleiner 5, die Fettsäuren mit 6 bis 22 Kohlenstoffatomen enthalten, erfolgt vorzugsweise durch Umsetzung mit gasförmigem Schwefeltrioxid und anschließender Neutralisierung mit wä߬ rigen Basen, wie sie in der internationalen Patentanmeldung WO 91/9009 angegeben ist.However, preferred sulfated fatty acid glycerol esters are the sulfonated 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. If one again starts from fats and oils, that is to say natural mixtures of different fatty acid glycerol esters, it is necessary in this case to largely saturate the starting products with hydrogen in a manner known per se, ie to iodine numbers less than 5, advantageously to harden less than 2. Typical examples of suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, rapeseed oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or pork lard. Due to their high natural content of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow. The sulfonation of the saturated fatty acids with 6 to 22 carbon atoms or the mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, as described in of international patent application WO 91/9009.
Die Sulfierprodukte stellen ein komplexes Gemisch dar, das Mono-, Di- und Triglyceridsulfonate mit -ständiger und/oder innenständiger Sulfonsäure- gruppierung enthält. Als Nebenprodukte bilden sich sulfonierte Fettsäure¬ salze, Glyceridsulfate, Glycerinsulfate, Glycerin und Seifen. Geht man bei der Sulfierung von gesättigten Fettsäuren oder gehärteten Fettsäure- glycerinestergemisehen aus, so kann der Anteil der oc-sulfonierten Fettsäure-Disalze je nach Verfahrensführung durchaus b s etwa 60 Gew.-% betragen. Im Rahmen dieser Erfindung wird unter sulfierten Fett¬ säureglycerinestern jeweils dieses komplexe Reaktionsgemisch, einschlie߬ lich der unsulfierten und nicht waschaktiven Bestandteile, jedoch ohne wäßrige Anteile verstanden.The sulfonation products are a complex mixture that contains mono-, di- and triglyceride sulfonates with an internal and / or internal sulfonic acid grouping. Sulfonated fatty acid salts, glyceride sulfates, glycerol sulfates, glycerol and soaps are formed as by-products. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid-glycerol ester mixtures, the proportion of the oc-sulfonated fatty acid disalts can, depending on the procedure, be about 60% by weight. In the context of this invention, sulfated fatty acid glycerol esters are understood to mean in each case this complex reaction mixture, including the unsulfated and non-washing-active constituents, but without aqueous components.
Der Gehalt der Mittel an Tensiden insgesamt beträgt vorzugsweise 25 bis 65 Gew.-% und insbesondere sind konzentrierte flüssige bis pastöse Mittel bevorzugt, welche mindestens 30 Gew.-% an anionischen und nichtionischen Tensiden aufweisen. Dabei enthalten die Mittel vorzugsweise 5 bis 20 Gew.-% sulfierte Fettsäureglycerinester, insbesondere Fettsäureglycerin¬ ester mit Iodzahlen kleiner 5, die Fettsäuren mit 6 bis 22 Kohlenstoff¬ atomen enthalten, 10 bis 65 Gew.-% nichtionische Tenside sowie vorzugs¬ weise weitere anionische Tenside, beispielsweise Alkylsulfate, vorzugs¬ weise Fettalkylsulfate, Alkansulfonate, Seifen oder Mischungen aus diesen. Die Mittel können auch geringe Mengen an Alkylbenzolsulfonaten, bei¬ spielsweise etwa 1 bis 5 Gew.-% Alkylbenzolsulfonat, enthalten; besonders bevorzugte Wasch- und Reinigungsmittel in flüssiger bis pastöser Form sind jedoch frei von Alkylbenzolsulfonaten.The total surfactant content of the compositions is preferably 25 to 65% by weight and, in particular, concentrated liquid to pasty compositions which have at least 30% by weight of anionic and nonionic surfactants are preferred. The agents preferably contain 5 to 20% by weight of sulfonated fatty acid glycerol esters, in particular fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, 10 to 65% by weight of nonionic surfactants and preferably further anionic ones Surfactants, for example alkyl sulfates, preferably fatty alkyl sulfates, alkane sulfonates, soaps or mixtures thereof. The agents can also contain small amounts of alkylbenzenesulfonates, for example about 1 to 5% by weight of alkylbenzenesulfonate; especially preferred detergents and cleaning agents in liquid to pasty form are, however, free of alkylbenzenesulfonates.
Die eingesetzten anionischen Tenside sind vorzugsweise Alkalimetallsalze, insbesondere Natrium- oder Kaliumsalze. Die zusätzlich zu den sulfierten Fettsäureglycerinester eingesetzten Aniontenside sind vorzugsweise Tenside aus der Klasse der Sulfonate und Sulfate.The anionic surfactants used are preferably alkali metal salts, in particular sodium or potassium salts. The anionic surfactants used in addition to the sulfonated fatty acid glycerol esters are preferably surfactants from the class of the sulfonates and sulfates.
Als Sulfonate eignen sich insbesondere Sulfonate auf fettchemischer Basis wie die Ester von oc-Sulfofettsäuren, wobei die Sulfogruppe in ihrer Salz- Form vorliegt (Monosalz), zum Beispiel die α-sulfonierten Methylester, der hydrierten Kokos-, Palmkern, oder Taigfettsäuren. Geeignet sind außerdem auch die biologisch gut abbaubaren Alkansulfonate, die aus Ci2-Ci8-Alka en beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließen¬ der Hydrolyse bzw. Neutralisation gewonnen werden. Die Sulfonatgruppe ist über die gesamte Kohlenstoffkette statistisch verteilt, wobei die sekun¬ dären Alkansulfonate überwiegen. Als Nachteil der Alkansulfonate ist je¬ doch anzusehen, daß sie aus petroche isehen Rohstoffen gewonnen werden. Ihr Anteil in den erfindungsgemäßen flüssigen bis pastösen Wasch- und Reinigungsmitteln beträgt daher vorzugsweise nicht mehr als etwa 5 bis 15 Gew.-%. Dabei hat es sich gezeigt, daß Mittel, welche Mischungen aus Alkansulfonaten und sulfierten Fettsäureglycerinestern enthalten, wobei der Anteil der sulfierten Fettsäureglycerinester in diesen Mischungen 10 bis 80 Gew.-% beträgt, gegenüber nur Alkansulfonat-haltigen Mischungen keine Einbußen in der Waschleistung aufweisen. In Abhängigkeit von der Rezeptur ist es sogar möglich, Alkansulfonate insgesamt durch sulfierte Fettsäureglycerinester zu ersetzen, ohne Einbußen in der Waschleistung in Kauf nehmen zu müssen. Analoges gilt auch für die oben erwähnten Alkylbenzolsulfonate und Mischungen aus Alkylbenzolsulfonaten und su1fierten Fettsäureglycerinestern.Particularly suitable sulfonates are sulfonates based on oleochemicals, such as the esters of oc-sulfo fatty acids, the sulfo group being in its salt form (mono salt), for example the α-sulfonated methyl esters, the hydrogenated coconut, palm kernel, or tallow fatty acids. Also suitable are the readily biodegradable alkanesulfonates which are obtained from Ci2-Ci8-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The sulfonate group is statistically distributed over the entire carbon chain, the secondary alkanesulfonates predominating. A disadvantage of the alkanesulfonates, however, is that they are obtained from petrochemical raw materials. Their proportion in the liquid to pasty washing and cleaning agents according to the invention is therefore preferably not more than about 5 to 15% by weight. It has been found that agents which contain mixtures of alkanesulfonates and sulfonated fatty acid glycerol esters, the proportion of sulfated fatty acid glycerol esters in these mixtures being 10 to 80% by weight, have no loss in washing performance compared to only alkanesulfonate-containing mixtures. Depending on the recipe, it is even possible to replace alkane sulfonates as a whole with sulfated fatty acid glycerol esters without having to accept any loss in washing performance. The same applies analogously to the above-mentioned alkylbenzenesulfonates and mixtures of alkylbenzenesulfonates and unsaturated fatty acid glycerol esters.
Geeignete Tenside vom Sulfat-Typ sind die Schwefelsäuremonoester aus pri¬ mären Alkoholen natürlichen und synthetischen Ursprungs, insbesondere aus Fettalkoholen. Als Fettalkylsulfate eignen sich die Schwefelsäuremonoester der Ci2-Ci8-Fettalkohole, wie Lauryl-, Myristyl-, Cetylalkohol- oder Stearylalkohol, und der aus Kokosöl, Palm- und Palmkernöl gewonnenen Fettalkoholgemische, die zusätzlich noch Anteile an ungesättigten Alko¬ holen, z.B. an Oleylalkohol, enthalten können. Eine bevorzugte Verwendung finden dabei Gemische, in denen der Anteil der Alkylreste zu 50 bis 70 Gew.-% auf C12, zu 18 bis 30 Gew.-% auf C14, zu 5 bis 15 Gew.-% auf Ciß, unter 3 Gew.-% auf C10 und unter 10 Gew.-% auf C Q verteilt sind. Der An¬ teil an Fettalkylsulfaten in den Mitteln beträgt vorzugsweise 1 bis 20Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols. Suitable fatty alkyl sulfates are the sulfuric acid monoesters of the Ci2-Ci8 fatty alcohols, such as lauryl, myristyl, cetyl alcohol or stearyl alcohol, and those obtained from coconut oil, palm and palm kernel oil Fatty alcohol mixtures which may additionally contain fractions of unsaturated alcohols, for example oleyl alcohol. Mixtures in which the proportion of the alkyl radicals is 50 to 70% by weight on C12, 18 to 30% by weight on C14, 5 to 15% by weight on Ciss, less than 3% by weight find a preferred use. -% are distributed on C10 and less than 10% by weight on CQ. The proportion of fatty alkyl sulfates in the compositions is preferably 1 to 20
Gew.-% und insbesondere 3 bis 15 Gew.*% By weight and in particular 3 to 15% by weight *
Weitere bevorzugte Aniontenside sind die Salze der Alkylsulfobernstein- säure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester be¬ zeichnet werden und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten Cg- bis Ciß-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen (Beschreibung siehe unten). Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit einge¬ schränkter HomologenVerteilung ableiten, besonders bevorzugt.Further preferred anionic surfactants are the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cg to Ciß fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with restricted homolog distribution are particularly preferred.
Als weitere anionische Tenside kommen insbesondere Seifen, vorzugsweise in Mengen von 3 bis 25 Gew.-%, insbesondere in Mengen von 5 bis 20 Gew.-%, in Betracht. Geeignet sind gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure oder Stearinsäure, sowie insbe¬ sondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern- oder Taigfett¬ säuren, abgeleitete Seifengemische.Other suitable anionic surfactants are, in particular, soaps, preferably in amounts of 3 to 25% by weight, in particular in amounts of 5 to 20% by weight. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or taig fatty acids, derived soap mixtures.
Insbesondere sind die Salze von gesättigten und ungesättigten Fettsäuren mit Ci2-Ciß-Kettenlängen in Form ihrer Gemische geeignet. Ein bevorzugt verwendetes Seifengemisch wird aus Natriumoleat und den Natriumsalzen der gesättigten C^-Clö^ettsäuregemische gebildet. Der Anteil an Ci2-Ci4-Fettsäuren in der gesättigten Komponente beträgt zweckmäßigerweise mindestens 60 Gew.-%, vorzugsweise mindestens 75 Gew.-% (gerechnet als Fettsäure). Geeignet hierfür sind z.B. Kokosfettsäuren, von denen die An¬ teile mit 10 und weniger C-Atomen weitgehend abgetrennt sind. Wie bei technischen Fettsäureschnitten üblich, können die Ölsäure sowie die Kokosfettsäure noch gewisse Anteile an Stearinsäure enthalten, jedoch soll deren Anteil, bezogen auf seifenbildende Fettsäuren, höchstens 25 Gew.-%, vorzugsweise weniger als 20 Gew.-% betragen. Ebenso bevorzugt ist ein Seifengemisch aus Natriumoleat und dem Natriumsalz der Laurinsäure. Das GewichtsVerhältnis der ungesättigten zur gesättigten Komponente beträgt vorzugsweise 2 : 1 bis 1 : 2.The salts of saturated and unsaturated fatty acids with Ci2-Ciß chain lengths in the form of their mixtures are particularly suitable. A preferred soap mixture is formed from sodium oleate and the sodium salts of the saturated C ^ -Clö ^ ettic acid mixtures. The proportion of Ci2-Ci4 fatty acids in the saturated component is expediently at least 60% by weight, preferably at least 75% by weight (calculated as fatty acid). Suitable for this purpose are, for example, coconut fatty acids, from which the portions with 10 or fewer carbon atoms are largely separated. As usual with technical fatty acid cuts, the oleic acid and the Coconut fatty acid still contain certain proportions of stearic acid, but their proportion, based on soap-forming fatty acids, should be at most 25% by weight, preferably less than 20% by weight. A soap mixture of sodium oleate and the sodium salt of lauric acid is also preferred. The weight ratio of the unsaturated to the saturated component is preferably 2: 1 to 1: 2.
Besonders bevorzugte Wasch- und Reinigungsmittel in flüssiger bis pastöser Form enthalten 15 bis 35 Gew.-% einer Mischung aus sulfierten Fettsäure¬ glycerinestern und weiteren anionischen Tensiden im Gewichtsverhältnis 1 : 3 bis 3 : 1. Dabei sind insbesondere anionische Tensidmischungen bevor¬ zugt, die sulfierte Fettsäureglycerinester, Fettalkylsulfate und Fettsäu¬ reseifen oder sulfierte Fettsäureglycerinester, Alkansulfonate und Fett¬ säureseifen enthalten.Particularly preferred detergents and cleaning agents in liquid to pasty form contain 15 to 35% by weight of a mixture of sulfated fatty acid glycerol esters and further anionic surfactants in a weight ratio of 1: 3 to 3: 1. In particular, anionic surfactant mixtures are preferred, which contain sulfated fatty acid glycerol esters, fatty alkyl sulfates and fatty acid soaps or sulfonated fatty acid glycerol esters, alkane sulfonates and fatty acid soaps.
Als nichtionische Tenside werden vorzugsweise flüssige ethoxylierte und/oder propoxylierte mit Bevorzugung der ethoxylierten Fettalkohole, insbesondere primäre Alkohole mit vorzugsweise 9 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder in 2-Stellung methylverzweigt sein kann, bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind Alkoholethoxylate bevorzugt, die durchschnittlich 2 bis 8 EO aufweisen. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise insbeson¬ dere Ci2-Ci4-Alkohole mit 3 EO oder 4 EO, Cg-Cn-Alkohol mit 7 EO, Ci3-Ci5-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, Ci2-Ci8-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12- Cj4-Alkohol mit 3 EO und Ci2-Ci8-Alkohol mit 5 EO eingesetzt.The preferred nonionic surfactants are liquid ethoxylated and / or propoxylated, preferably ethoxylated fatty alcohols, in particular primary alcohols preferably having 9 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 is linear or in 2-position may be methyl branched, or may contain linear and methyl branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, alcohol ethoxylates are preferred which have an average of 2 to 8 EO. The preferred ethoxylated alcohols include, for example, in particular Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cn alcohol with 7 EO, Ci3-Ci5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2 -Ci8 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C12-C j 4 alcohol with 3 EO and Ci2-Ci8 alcohol with 5 EO.
Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeschränkte Homolo¬ genverteilung auf (narrow ränge ethoxylates, NRE). Der Gehalt der er¬ findungsgemäßen Mittel an flüssigen nichtionischen Tensiden beträgt vor¬ zugsweise 15 bis 65 Gew.-%. Außerdem können als weitere nichtionische Tenside auch Alkylglykoside der allgemeinen Formel R0(G)x eingesetzt werden, in der R einen primären geradkettigen oder in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Mono- glykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4. Der Gehalt der erfindungsgemäßen Mittel an Alkylglykosiden beträgt vorzugsweise 0,5 bis 8 Gew.-% und insbesondere 1 bis 5 Gew.-%.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 restricted homolog distribution (narrow range ethoxylates, NRE). The liquid nonionic surfactants in the agents according to the invention are preferably 15 to 65% by weight. In addition, alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical branched with methyl in the 2-position with 8 to 22, preferably 12 to 18 C atoms and G denotes 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. The content of alkyl glycosides in the agents according to the invention is preferably 0.5 to 8% by weight and in particular 1 to 5% by weight.
Die erfindungsgemäßen Wasch- und Reinigungsmittel können als organische Lösungsmittel mono- und/oder polyfunktionelle Alkohole mit 1 bis 6 Koh- lenstoffatomen, vorzugsweise mit 1 bis 4 Kohlenstoffatomen, enthalten. Bevorzugte Alkohole sind Ethanol, 1,2-Propandiol, Glycerin sowie deren Gemische. Die Mittel enthalten vorzugsweise 2 bis 20 Gew.-% und insbeson¬ dere 5 bis 15 Gew.-% Ethanol oder ein beliebiges Gemisch aus Ethanol und 1,2-Propandiol oder insbesondere aus Ethanol und Glycerin. Ebenso ist es möglich, daß die erfindungsgemäßen Wasch- und Reinigungsmittel in flüs¬ siger bis pastöser Form entweder zusätzlich zu den mono- und/oder polyfunktionellen Alkoholen mit 1 bis 6 Kohlenstoffatomen oder allein Polyethylenglykol mit einer relativen Molekülmasse zwischen 200 und 2000, vorzugsweise bis 600 in Mengen von 2 bis 17 Gew.-% enthalten.The washing and cleaning agents according to the invention can contain, as organic solvents, mono- and / or polyfunctional alcohols with 1 to 6 carbon atoms, preferably with 1 to 4 carbon atoms. Preferred alcohols are ethanol, 1,2-propanediol, glycerol and mixtures thereof. The agents preferably contain 2 to 20 wt .-% and in particular 5 to 15 wt .-% ethanol or any mixture of ethanol and 1,2-propanediol or in particular ethanol and glycerol. It is also possible that the detergents and cleaning agents according to the invention in liquid to pasty form either in addition to the mono- and / or polyfunctional alcohols having 1 to 6 carbon atoms or alone polyethylene glycol with a relative molecular weight between 200 and 2000, preferably up to 600 contained in amounts of 2 to 17 wt .-%.
Bei den erfindungsgemäßen Wasch- und Reinigungsmitteln in flüssiger bis pastöser Form kann es sich um wäßrige oder um im wesentlichen wasserfreie Mittel handeln. Dabei bedeutet "im wesentlichen wasserfrei" im Rahmen dieser Erfindung, daß das Mittel vorzugsweise kein freies, nicht als Kri- stallwasser oder in vergleichbarer Form gebundenes Wasser enthält. In ei¬ nigen Fällen sind geringe Menge an freiem Wasser tolerierbar, insbesondere in Mengen bis zu 5 Gew.-%. Bevorzugte im wesentlichen wasserfreie Wasch- und Reinigungsmittel in flüssiger bis pastöser Form enthalten 20 bis 65 Gew.-% flüssige nichtionische Tenside und Wasser in Mengen von 0 bis 5 Gew.-%. Als weitere Inhaltsstoffe können die genannten Aniontenside sowie beispielsweise Bleichmittel, Verdickungs ittel, Gerüstsubstanzen, anorga¬ nische Salze, Schauminhibitoren, Enzyme, optische Aufheller, sowie Färb- und Duftstoffe enthalten sein, so wie sie beispielsweise in der inter¬ nationalen Patentanmeldung WO 92/2610 beschrieben sind. Unter den als Peroxy-Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen ha¬ ben das Natriumperborat-Tetrahydrat und das Natriumperborat-Monohydrat eine besondere Bedeutung. Weitere Bleichmittel sind beispielsweise Peroxycarbonat, Citratperhydrate sowie H2O2-liefernde persaure Salze der Persäuren, wie Perbenzoate, Peroxyphthalate oder Diperoxydodecandisäure. Sie werden üblicherweise in Mengen von 8 bis 25 Gew.-% eingesetzt. Bevor¬ zugt ist der Einsatz von Natriumperborat-Monohydrat in Mengen von 10 bis 20 Gew.-% und insbesondere von 10 bis 15 Gew.-%. Durch seine Fähigkeit, unter Ausbildung des Tetrahydrats freies Wasser binden zu können, trägt es zur Erhöhung der Stabilität des Mittels bei. Als Verdickungs ittel können beispielsweise gehärtetes Rizinusöl, Salze von langkettigen Fettsäuren, die vorzugsweise in Mengen von 0 bis 5 Gew.-% und insbesondere in Mengen von 0,5 bis 2 Gew.-%, beispielsweise Natrium-, Kalium-, Aluminium-, Ma¬ gnesium- und Titan-Stearate oder die Natrium- und/oder Kaliumsalze der Behensäure, sowie weitere polyere Verbindungen eingesetzt werden. Zu den letzteren gehören bevorzugt Polyvinylpyrrolidon, Urethane und die Salze polymerer Polycarboxylate, beispielsweise homopolymerer oder copolymerer Polyacrylate, Poly ethacrylate und insbesondere Copolymere der Acrylsäure mit Maleinsäure, vorzugsweise solche aus 50 % bis 10 % Maleinsäure. Die relative Molekülmasse der Homopolymeren liegt im allgemeinen zwischen 1000 und 100000, die der Copolyeren zwischen 2000 und 200000, vorzugsweise zwischen 50000 bis 120000, bezogen auf die freie Säure. Insbesondere sind auch wasserlösliche Polyacrylate geeignet, die beispielsweise mit etwa 1 % eines Polyallylethers der Sucrose quervernetzt sind und die eine relative Molekülmasse oberhalb einer Million besitzen. Beispiele hierfür sind die unter dem Namen Carbopol(R) 940 und 941 erhältlichen Polymere. Die quer¬ vernetzten Polyacrylate werden vorzugsweise in Mengen nicht über 1 Gew.-%, vorzugsweise in Mengen von 0,2 bis 0,7 Gew.-% eingesetzt.The washing and cleaning agents according to the invention in liquid to pasty form can be aqueous or essentially water-free agents. In the context of this invention, “essentially water-free” means that the agent preferably contains no free water that is not bound as crystal water or in a comparable form. In some cases, a small amount of free water can be tolerated, especially in amounts of up to 5% by weight. Preferred essentially water-free detergents and cleaning agents in liquid to pasty form contain 20 to 65% by weight of liquid nonionic surfactants and water in amounts of 0 to 5% by weight. The anionic surfactants mentioned and, for example, bleaches, thickeners, builders, inorganic salts, foam inhibitors, enzymes, optical brighteners and colorants can be used as further ingredients. and fragrances, such as are described, for example, in international patent application WO 92/2610. Among the compounds which serve as peroxy bleaching agents and supply H2O2 in water, the sodium perborate tetrahydrate and the sodium perborate monohydrate are of particular importance. Other bleaching agents are, for example, peroxy carbonate, citrate perhydrates and H2O2-providing peracid salts of peracids, such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight. The use of sodium perborate monohydrate in amounts of 10 to 20% by weight and in particular 10 to 15% by weight is preferred. Due to its ability to bind free water with the formation of the tetrahydrate, it contributes to increasing the stability of the agent. For example, hardened castor oil, salts of long-chain fatty acids, preferably in amounts of 0 to 5% by weight and in particular in amounts of 0.5 to 2% by weight, for example sodium, potassium, aluminum, Magnesium and titanium stearates or the sodium and / or potassium salts of behenic acid, and other polymeric compounds are used. The latter preferably include polyvinylpyrrolidone, urethanes and the salts of polymeric polycarboxylates, for example homopolymeric or copolymeric polyacrylates, polyethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50% to 10% maleic acid. The relative molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolyers between 2000 and 200000, preferably between 50,000 and 120,000, based on the free acid. Water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a relative molecular weight above one million are also particularly suitable. Examples of these are the polymers obtainable under the name Carbopol ( R ) 940 and 941. The crosslinked polyacrylates are preferably used in amounts of not more than 1% by weight, preferably in amounts of 0.2 to 0.7% by weight.
Die wasserhaltigen flüssigen bis pastösen Wasch- und Reinigungsmittel sind vorzugsweise frei von Peroxy-Bleichmitteln. Sie enthalten vorzugsweise 5 bis 35 Gew.-% und insbesondere 10 bis 35 Gew.-% an nichtionischen Tensiden sowie 20 bis 55 Gew.-% und insbesondere 25 bis 45 Gew.-% Wasser. In einer bevorzugten Ausführungsform enthalten flüssige bis pastöse Mittel 10 bis 20 Gew.-% ethoxylierte Fettalkohole, vorzugsweise einen primären C12-C18- Fettalkohol mit durchschnittlich 1 bis 12 Mol Ethylenoxid pro Mol Alkohol. Besonders bevorzugt sind flüssige bis pastöse Konzentrate, die 20 bis 35 Gew.-% an nichtionischen Tensider: insbesondere 22 bis 32 Gew.-% eines primären Ci2-Ci8-Fettalkohols mit durchschnittlich 1 bis 12 Mol Ethylen¬ oxid pro Mol Fettalkohol, 28 bis 40 Gew.- Wasser sowie 5 bis 17 Gew.-% mono- und/oder polyfunktionelle Alkohole mit 2 bis 4 Kohlenstoffatomen enthält. Dabei können die Mittel zusätzlich etwa 5 bis 20 Gew.-% eines partiell veresterten Copolymerisats enthalten, wie es in der europäischen Patentanmeldung 367 049 beschrieben ist. Diese partiell veresterten Poly¬ mere werden durch Copolymerisation von (a) mindestens einem C4-C28-01efin oder Mischungen aus mindestens einem C4-C28-01efin mit bis zu 20 Mol-% Cι-C28-Alkylvinylethern und (b) ethylenisch ungesättigten Dicarbonsäure- anhydriden mit 4 bis 8 Kohlenstoffatomen im Molverhältnis 1 : 1 zu Copolymerisäten mit K-Werten von 6 bis 100 und anschließende partielle Veresterung der Copolymerisäte mit Umsetzungsprodukten wie Cι-Ci3-Alkoholen, C8-C22_frettsäuren, Cι-Ci2-Alkylphenolen, sekundären C2-C3o~Aminen oder deren Mischungen mit mindestens einem C2-C4-Alkylenoxid oder Tetrahydrofuran sowie Hydrolyse der Anhydridgruppen der Copolymerisate zu Carboxylgruppen erhalten, wobei die partielle Veresterung der Copolymerisate soweit geführt wird, daß 5 bis 50 % der Carboxylgruppen der Copolymerisate verestert sind. Bevorzugte Copolymerisate enthalten als ethylenisch ungesättigtes Dicarbonsäureanhydrid Maleins- reanhydrid. Die partiell veresterten Copolymerisate können entweder in Form der freien Säure oder vorzugsweise in partiell oder vollständig neutralisierter Form vorliegen. Vorteilhaft¬ erweise werden die Copolymerisate in Form einer wäßrigen Lösung, insbe¬ sondere in Form einer 40 bis 50 Gew.-%igen Lösung eingesetzt. Die Co¬ polymerisate leisten nicht nur einen Beitrag zur Primär- und Sekundär¬ waschleistung des flüssigen Wasch- und Reinigungsmittels, sondern bewirken auch eine gewünschte Viskositätserniedrigung der kon∑ -rrrierten flüssigen Waschmittel. Durch den Einsatz dieser partiell verestt, cen Copolymerisate werden konzentrierte wäßrige Flüssigwaschmittel erhalten, die unter dem alleinigen Einfluß der Schwerkraft und ohne Einwirkung sonstiger Scher¬ kräfte fließfähig sind. Vorzugsweise beinhalten die konzentrierten wäßrigen Flüssigwaschmittel partiell veresterte Copolymerisate in Mengen von 5 bis 15 Gew.-% und insbesondere in Mengen von 8 bis 12 Gew.-%.The water-containing liquid to pasty washing and cleaning agents are preferably free of peroxy bleaching agents. They preferably contain 5 to 35% by weight and in particular 10 to 35% by weight of nonionic surfactants and 20 to 55% by weight and in particular 25 to 45% by weight of water. In a preferred embodiment, liquid to pasty agents contain 10 to 20% by weight of ethoxylated fatty alcohols, preferably a primary C12-C18 fatty alcohol with an average of 1 to 12 moles of ethylene oxide per mole of alcohol. Particularly preferred are liquid to pasty concentrates containing 20 to 35% by weight of nonionic surfactants: in particular 22 to 32% by weight of a primary Ci2-Ci8 fatty alcohol with an average of 1 to 12 moles of ethylene oxide per mole of fatty alcohol, 28 to 40 wt .-% water and 5 to 17 wt .-% mono- and / or polyfunctional alcohols containing 2 to 4 carbon atoms. The agents can additionally contain about 5 to 20% by weight of a partially esterified copolymer, as described in European patent application 367 049. This partially esterified Poly mers are prepared by copolymerization of (a) at least one fin or C4-C28-01 e mixtures of at least one C4-C28-01efin with up to 20 mol% Cι-C28-alkyl vinyl ethers and (b) ethylenically unsaturated dicarboxylic anhydrides having from 4 to 8 carbon atoms in a molar ratio 1: 1 to Copolymerisäten having K values from 6 to 100 and subsequent partial esterification of the Copolymerisäte with reaction products such as Cι-Ci3-alcohols, C8-C22 _ f r e t tsäuren, Cι- Ci2-alkylphenols, secondary C2-C3o ~ amines or mixtures thereof with at least one C2-C4-alkylene oxide or tetrahydrofuran and hydrolysis of the anhydride groups of the copolymers to give carboxyl groups, the partial esterification of the copolymers being carried out to such an extent that 5 to 50% of the carboxyl groups the copolymers are esterified. Preferred copolymers contain maleic anhydride as the ethylenically unsaturated dicarboxylic acid anhydride. The partially esterified copolymers can be present either in the form of the free acid or preferably in partially or completely neutralized form. The copolymers are advantageously used in the form of an aqueous solution, in particular in the form of a 40 to 50% by weight solution. The copolymers not only make a contribution to the primary and secondary washing performance of the liquid washing and cleaning agent, but also bring about a desired reduction in the viscosity of the concentrated liquid washing agent. The use of these partially esterified copolymers gives concentrated aqueous liquid detergents which are flowable under the sole influence of gravity and without the action of other shear forces. Preferably the concentrated ones include aqueous liquid detergents partially esterified copolymers in amounts of 5 to 15 wt .-% and in particular in amounts of 8 to 12 wt .-%.
Der pH-Wert der erfindungsgemäßen und insbesondere bevorzugten konzen¬ trierten Mittel beträgt im allgemeinen 7 bis 10,5, vorzugsweise 7 bis 9,5 und insbesondere 7 bis 8,5. Die Einstellung höherer pH-Werte, beispiels¬ weise oberhalb von 9, kann durch den Einsatz geringer Mengen an Natron¬ lauge oder an alkalischen Salzen wie Natriumcarbonat oder Natriumsilikat erfolgen. Die erfindungsgemäßen Wasch- und Reinigungsmittel weisen im allgemeinen Viskositäten zwischen 150 und 10000 mPas (Brookfield-Viskosi- meter, Spindel 1, 20 Umdrehungen pro Minute, 20 °C). Dabei sind bei den im wesentlichen wasserfreien Mitteln Viskositäten zwischen 150 und 5000 mPas bevorzugt. Die Viskosität der wäßrigen Mittel liegt vorzugsweise unter 2000 mPas und liegt insbesondere zwischen 150 und 1000 mPas.The pH of the concentrated and particularly preferred agents according to the invention is generally 7 to 10.5, preferably 7 to 9.5 and in particular 7 to 8.5. Higher pH values, for example above 9, can be set by using small amounts of sodium hydroxide solution or alkaline salts such as sodium carbonate or sodium silicate. The washing and cleaning agents according to the invention generally have viscosities between 150 and 10,000 mPas (Brookfield viscometer, spindle 1, 20 revolutions per minute, 20 ° C.). Viscosities between 150 and 5000 mPas are preferred for the essentially water-free agents. The viscosity of the aqueous compositions is preferably below 2000 mPas and in particular between 150 and 1000 mPas.
Außer den genannten Inhaltsstoffen können die wäßrigen Mittel bekannte, in Wasch- und Reinigungsmitteln üblicherweise eingesetzte Zusatzstoffe, bei¬ spielsweise Salze von Polycarbonsäuren, beispielsweise der Citronensäure, Salze von Polyphosphonsäuren, optische Aufheller, Enzyme, Enzymstabilisa¬ toren, geringe Mengen an neutralen Füllsalzen sowie Färb- und Duftstoffe, Trübungsmittel oder Perlglanzmittel enthalten.In addition to the ingredients mentioned, the aqueous compositions can contain known additives commonly used in detergents and cleaning agents, for example salts of polycarboxylic acids, for example citric acid, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filler salts and dye - and contain fragrances, opacifiers or pearlescent agents.
Als Salze von Polyphosphonsäuren werden vorzugsweise die neutral reagie¬ renden Natriumsalze von beispielsweise l-Hydroxyethan-l,l,-diphosphonat in Mengen von 0,1 bis 1,5 Gew.- verwendet.The salts of polyphosphonic acids which are preferably used are the neutral reacting sodium salts of, for example, l-hydroxyethane-l, l, -diphosphonate in amounts of 0.1 to 1.5% by weight.
Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen, Cellulasen bzw. deren Gemische in Frage. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus licheni- formis und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Vor¬ zugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Ihr Anteil kann etwa 0,2 bis etwa 2 Gew.-% betragen. Die Enzyme können an Trägerstoffen adsor¬ biert und/oder in Hü11Substanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen. Zusätzlich zu den mono- und polyfunktionellen Alkoholen und den Phos- phonaten können die Mittel weitere Enzymstabilisatoren enthalten. Bei¬ spielsweise können 0,5 bis 1 Gew.-% Natriumformiat eingesetzt werden. Möglich ist auch der Einsatz von Proteasen, die mit löslichen Calciu - salzen und einem Calciu gehalt von vorzugsweise etwa l,2-Gew.-%, bezogen auf das Enzym, stabilisiert sind. Besonders vorteilhaft ist jedoch der Einsatz von Borverbindungen, beispielsweise von Borsäure, Boroxid, Borax und anderen Alkalimetallboraten wie den Salzen der Orthoborsäure (H3BO3), der Metaborsäure (HBO2) und der Pyroborsäure (Tetraborsäure H2B4O7).Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Their proportion can be about 0.2 to about 2% by weight. The enzymes can be adsorbed on carrier substances and / or embedded in Hü11 substances in order to protect them against premature decomposition. In addition to the mono- and polyfunctional alcohols and the phosphates, the agents can contain further enzyme stabilizers. For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. However, the use of boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7), is particularly advantageous.
Beim Einsatz im maschinellen Waschverfahren kann es von Vorteil sein, den Mitteln übliche Schauminhibitoren zuzusetzen. Geeignete Schauminhibitoren enthalten beispielsweise bekannte Organopolysiloxane, Paraffine oder Wachse. Bevorzugt ist auch - wie oben genannt - der Einsatz sulfierter ungesättigter Fettsäureg1ycerinester. When used in the machine washing process, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors contain, for example, known organopolysiloxanes, paraffins or waxes. As mentioned above, preference is also given to the use of sulfonated unsaturated fatty acid glycerol esters.
B e s p i e l eB e s p i e l e
Herstellung von sulfierten gesättigten Fettsäureglycerinestern mit Iodzahlen kleiner 5.Production of sulfated saturated fatty acid glycerol esters with iodine numbers less than 5.
In einem kontinuierlich arbeitenden Fallfilmreaktor (Länge 120 cm, Quer¬ schnitt 1 cm, Eduktdurchsatz 600 g/h) mit Mantelkühlung und seitlicher S03-Begasung wurden etwa 5 Mol eines Fettsäureglycerinesters mit einer Iodzahl kleiner 5 (siehe Tabelle 1) bei 80 °C mit etwa 15 Mol gasförmigem Schwefeltrioxid zur Reaktion gebracht. Der Fettsäureglycerinester wurde dabei über eine Düse mit einer Öffnung von 0,2 cm derartig in den Reaktor gesprüht, daß das Edukt entlang der Rohrwandung einen kontinuierlichen feinen Film mit einer Schichtdicke von weniger als 0,1 cm bildete. Das Schwefeltrioxid wurde durch Erhitzen aus einer entsprechenden Menge 65 Gew.-%igen Oleums ausgetrieben, mit Stickstoff auf eine Konzentration von 2 Vol.-% verdünnt und am Reaktorkopf seitlich eingeblasen. Das rohe Sulfierprodukt wurde nach Verlassen des Sulfierreaktors über 30 Minuten einer Nachreaktion bei 80 °C unterworfen. Anschließend wurde das saure Sulfierprodukt kontinuierlich mit wäßriger, 25 Gew.-%iger Natronlauge auf pH 6,5 bis 7,5 neutralisiert. In a continuously working falling film reactor (length 120 cm, cross section 1 cm, educt throughput 600 g / h) with jacket cooling and lateral SO3 gassing, about 5 moles of a fatty acid glycerol ester with an iodine number less than 5 (see Table 1) at 80 ° C. reacted about 15 moles of gaseous sulfur trioxide. The fatty acid glycerol ester was sprayed into the reactor through a nozzle with an opening of 0.2 cm in such a way that the starting material formed a continuous fine film with a layer thickness of less than 0.1 cm along the tube wall. The sulfur trioxide was expelled from a corresponding amount of 65% by weight oleum by heating, diluted to a concentration of 2% by volume with nitrogen and blown in at the side of the reactor head. After leaving the sulfonation reactor, the crude sulfonation product was subjected to a post-reaction at 80 ° C. for 30 minutes. The acidic sulfonation product was then continuously neutralized to pH 6.5 to 7.5 using aqueous 25% strength by weight sodium hydroxide solution.
Tabelle 1: Durchschnittliche Zusammensetzung der eingesetzten Fettsäureglycerinester nach Härtung Angaben in Gew.-%Table 1: Average composition of the fatty acid glycerol esters used after curing, in% by weight
Legende: HK = Gehärtetes KokosölLegend: HK = hardened coconut oil
HPK = Gehärtetes PalmkernölHPK = hardened palm kernel oil
Die nachfolgenden Beispiele beschreiben die zur Prüfung des Waschvermögens der erfindungsgemäßen Waschmittel in einer Haushaltswaschmaschine (Typ: Miele W 717) unter folgenden Bedingungen durchgeführten Versuche:The following examples describe the tests carried out to test the washing power of the detergents according to the invention in a household washing machine (type: Miele W 717) under the following conditions:
Waschprogramm: Buntwaschprogramm (ohne Vorwäsche) bei 40 °C Dosierung: 180 g oder 200 g pro Maschine Wasserhärte: 16 °d Textilproben: 3,5 kg saubere Füllwäsche (normale Haushaltswäsche) Bestimmungen: 3fach Meßtechnische Bedingungen: künstliche Anschmutzungen: RFC 3/24 (465 nm, Ausblendung des Aufheller- Effektes) natürliche Anschmutzungen: Länge-Gerät (Y-Filter) Remissionsunterschiede von 2 % und mehr sind als signifikant anzusehen.Washing program: Colored washing program (without prewash) at 40 ° C Dosage: 180 g or 200 g per machine Water hardness: 16 ° d Textile samples: 3.5 kg clean laundry (normal household laundry) Determinations: 3 times Measurement conditions: artificial soiling: RFC 3/24 (465 nm, suppression of the brightener effect) natural soiling: length device (Y-filter) reflectance differences of 2% and more are to be regarded as significant.
Die Anschmutzungen waren:The stains were:
SW-B Staub-Wollfett auf Baumwolle SH-BV Staub-Hautfett auf veredelter Baumwolle SH-P Staub-Hautfett auf PolyesterSW-B Dust-wool grease on cotton SH-BV Dust-skin fat on refined cotton SH-P Dust-skin fat on polyester
SH-PBV Staub-Hautfett auf einem Gemisch aus Polyester und veredelter BaumwolleSH-PBV Dust-skin fat on a mixture of polyester and refined cotton
BMR-B Blut, Milch und Ruß auf BaumwolleBMR-B blood, milk and soot on cotton
R-BV Rotwein auf veredelter BaumwolleR-BV red wine on refined cotton
T-BV Tee auf veredelter BaumwolleT-BV tea on refined cotton
LS-PBV Lippenstift auf einem Gemisch aus Polyester und veredelterLS-PBV lipstick on a mixture of polyester and refined
Baumwolle MU-PBV Make-up auf einem Gemisch aus Polyester und veredelterCotton MU-PBV make-up on a mixture of polyester and refined
Baumwollecotton
Die Grundzusammensetzungen der wäßrigen Flüssigwaschmittel lauteten (An¬ gaben jeweils in Gew.-%):The basic compositions of the aqueous liquid detergents were (details in% by weight):
Dabei bedeuteten "Aniontensid" in "Anionic surfactant" means in
- Ml/V, Ml/3 und M2/V Cg-Ci3-Alkylbenzolsulfat- Ml / V, Ml / 3 and M2 / V Cg-Ci3-alkylbenzenesulfate
- Ml/1 und M2/1 sulfiertes HK- Ml / 1 and M2 / 1 sulfated HK
- Ml/2 und M2/2 sulfiertes HPK und "Niotensid" in- Ml / 2 and M2 / 2 sulfated HPK and "nonionic surfactant" in
- Ml/V, Ml/1, Ml/2, M2/V, M2/1 und M2/2 Ci2-Ci8-Fettalkohol mit 7 EO- Ml / V, Ml / 1, Ml / 2, M2 / V, M2 / 1 and M2 / 2 Ci2-Ci8 fatty alcohol with 7 EO
- Ml/3 eine Mischung aus Ci2-Ci8-Fettalkohol mit 7 EO und sulfiertem HK im Gewichtsverhältnis 1 : 1- Ml / 3 a mixture of Ci2-Ci8 fatty alcohol with 7 EO and sulfated HK in a weight ratio of 1: 1
Beispiel 1:Example 1:
Die Mittel Ml/V, Ml/1 und Ml/2 wurden jeweils bei einer Dosierung von 180 g pro Maschine gegeneinander getestet. Die Ergebnisse sind in Tabelle 2 aufgeführt.The agents Ml / V, Ml / 1 and Ml / 2 were tested against each other at a dosage of 180 g per machine. The results are shown in Table 2.
Tabelle 2Table 2
Mittel % Remission bei AnschmutzungMedium% remission when soiled
SW-B SH-BV SH-PBV SH-P R-BV T-BV LS-PBV MU/PBVSW-B SH-BV SH-PBV SH-P R-BV T-BV LS-PBV MU / PBV
Beispiel 2:Example 2:
Die Mittel M2/V, M2/1 und M2/2 wurden jeweils bei einer Dosierung von 180 g pro Maschine gegeneinander getestet. Die Ergebnisse sind in Tabelle 3 aufgeführt.The agents M2 / V, M2 / 1 and M2 / 2 were tested against each other at a dosage of 180 g per machine. The results are shown in Table 3.
Tabelle 3:Table 3:
Mittel % Remission bei Anschmutzung SW-B SH-BV SH-PBV SH-P R-BV T-BV LS-PBV MU/PBVMedium% remission when soiled SW-B SH-BV SH-PBV SH-P R-BV T-BV LS-PBV MU / PBV
Beispiel 3:Example 3:
Die Mittel Ml/V und Ml/3 wurden jeweils nach 6 Wochen Lagerung bei 40 °C getestet. Die Ergebnisse sind in Tabelle 4 zusammengefaßt. Es zeigt sich, daß ein partieller Austausch von üblichen Niotensiden (50 %) durch sul¬ fierte Fettsäureglycerinester möglich ist, ohne Einbußen in der Waschlei- stung hinnehmen zu müssen. Im Launderometer waren die Effekte teilweise noch größer: hier führte in einigen Fällen sogar der Vollaustausch der Niotenside durch sulfierte Fettsäureglycerinester zu Mitteln, die eine gleich gute bis teilweise sogar leicht bessere Waschkraft aufwiesen.Ml / V and Ml / 3 were tested after storage for 6 weeks at 40 ° C. The results are summarized in Table 4. It has been shown that a partial replacement of conventional nonionic surfactants (50%) with sulfonated fatty acid glycerol esters is possible without having to accept a reduction in the washing performance. The effects were sometimes even greater in the launderometer: here, in some cases, even the full replacement of the nonionic surfactants with sulfated fatty acid glycerol esters led to detergents that had an equally good to sometimes slightly better detergency.
Tabelle 4: Maschinenversuche nach 6 Wochen Lagerung bei 40 °CTable 4: Machine tests after 6 weeks storage at 40 ° C
Mittel % Remission bei AnschmutzungMedium% remission when soiled
SW-B SH-P T-BV LS-PBV MU-PBV BMR-BSW-B SH-P T-BV LS-PBV MU-PBV BMR-B
Ml/V Ml/3 Ml / V Ml / 3

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Wasch- und Reinigungsmittel in flüssiger bis pastöser Form, das an¬ ionische oder anionische und nichtionische Tenside enthält, dadurch gekennzeichnet, daß der Gehalt des Mittels an Tensiden 20 bis 70 Gew.-% beträgt, wobei als anionische Tenside sulfierte Fettsäure¬ glycerinester in Mengen von 2 bis 25 Gew.-% enthalten sind.1. Detergent and cleaning agent in liquid to pasty form, which contains anionic or anionic and nonionic surfactants, characterized in that the surfactant content of the agent is 20 to 70% by weight, with sulfated fatty acid glycerol esters as anionic surfactants are contained in amounts of 2 to 25% by weight.
2. Mittel nach Anspruch 1, dadurch gekennzeichnet, daß es 5 bis 20 Gew.-% sulfierte Fettsäureglycerinester enthält, welche aus Fettsäuregly¬ cerinestern mit Iodzahlen kleiner 5, vorzugsweise aus Mono-, Di- und Triglyceriden oder deren Gemischen mit Iodzahlen kleiner 5, die Fett¬ säuren mit 6 bis 22 Kohlenstoffatomen enthalten, durch Umsetzung mit gasförmigem Schwefeltrioxid und anschließende Neutralisierung mit wäßrigen Basen erhalten werden.2. Composition according to claim 1, characterized in that it contains 5 to 20 wt .-% sulfonated fatty acid glycerol esters, which from fatty acid glycerol esters with iodine numbers less than 5, preferably from mono-, di- and triglycerides or mixtures thereof with iodine numbers less than 5, which contain fatty acids having 6 to 22 carbon atoms, can be obtained by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases.
3. Mittel nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Gehalt an nichtionischen Tensiden 10 bis 65 Gew.-% beträgt.3. Composition according to claim 1 or 2, characterized in that the content of nonionic surfactants is 10 to 65 wt .-%.
4. Mittel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß sie als organische Lösungsmittel mono- und/oder polyfunktionelle Al¬ kohole mit 1 bis 6 Kohlenstoffatomen in Mengen von 2 bis 20 Gew.-%, vorzugsweise 5 bis 15 Gew.-%, enthalten.4. Composition according to one of claims 1 to 3, characterized in that they are mono- and / or polyfunctional alcohols with 1 to 6 carbon atoms in amounts of 2 to 20 wt .-%, preferably 5 to 15 wt. As organic solvents. -%, contain.
5. Mittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es 20 bis 65 Gew.-% flüssige nichtionische Tenside und Wasser in Men¬ gen von 0 bis 5 Gew.-% enthält. 5. Composition according to one of claims 1 to 4, characterized in that it contains 20 to 65 wt .-% liquid nonionic surfactants and water in quantities of 0 to 5 wt .-%.
6. Mittel nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß es 5 bis 35 Gew.~%, vorzugsweise 10 bis 35 Gew.-% und insbesondere 20 bis 35 Gew.-% an nichtionischen Tensiden sowie 20 bis 55 Gew.-%, vor¬ zugsweise 25 bis 45 Gew.-% und insbesondere 28 bis 40 Gew.-% Wasser enthält.6. Composition according to one of claims 1 to 4, characterized in that it contains 5 to 35 wt.%, Preferably 10 to 35 wt.% And in particular 20 to 35 wt.% Of nonionic surfactants and 20 to 55 wt. %, preferably 25 to 45% by weight and in particular 28 to 40% by weight of water.
7. Mittel nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es frei von Alkylbenzolsulfonaten ist.7. Composition according to one of claims 1 to 6, characterized in that it is free of alkylbenzenesulfonates.
8. Mittel nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß es als weitere Aniontenside Alkylsulfate, vorzugsweise Fettalkylsul- fate, Alkansulfonate, Seife oder Mischungen aus diesen enthält.8. Composition according to one of claims 1 to 7, characterized in that it contains alkyl sulfates, preferably fatty alkyl sulfates, alkane sulfonates, soap or mixtures of these as further anionic surfactants.
9. Mittel nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß es 0,5 bis 8 Gew.-%, vorzugsweise 1 bis 5 Gew.-% Alkylglykosid ent¬ hält.9. Composition according to one of claims 1 to 8, characterized in that it contains 0.5 to 8 wt .-%, preferably 1 to 5 wt .-% alkyl glycoside ent.
10. Mittel nach einem der Ansprüche 1 bis 4 und 6 bis 9, dadurch gekenn¬ zeichnet, daß es 15 bis 35 Gew.-% einer Mischung aus sulfierten Fett¬ säureglycerinestern und weiteren anionischen Tensiden, insbesondere Seife, im Gewichtsverhältnis 1 : 3 bis 3 : 1 und 10 bis 20 Gew.-% ei¬ nes primären Ci2-Ci8-Fettalkohols mit durchschnittlich 1 bis 12 Mol Ethylenoxid enthält.10. Composition according to one of claims 1 to 4 and 6 to 9, characterized gekenn¬ characterized in that it contains 15 to 35 wt .-% of a mixture of sulfated fatty acid glycerol esters and other anionic surfactants, especially soap, in a weight ratio of 1: 3 to 3: 1 and 10 to 20 wt .-% of a primary Ci2-Ci8 fatty alcohol with an average of 1 to 12 moles of ethylene oxide.
11. Mittel nach einem der Ansprüche 1 bis 4 und 6 bis 9, dadurch gekenn¬ zeichnet, daß es 15 bis 35 Gew.-% einer Mischung aus sulfierten Fett¬ säureglycerinestern und weiteren anionischen Tensiden im Gewichtsver¬ hältnis 1 : 3 bis 3 : 1, 22 bis 32 Gew.-% eines primären Ci2-Ci8-Fettalkohols mit durchschnittlich 1 bis 12 Mol Ethylenoxid und 5 bis 17 Gew.-% mono- und/oder polyfunktionelle Alkohole mit 2 bis 4 Kohlenstoffatomen enthält. 11. Agent according to one of claims 1 to 4 and 6 to 9, characterized gekenn¬ characterized in that it contains 15 to 35 wt .-% of a mixture of sulfated fatty acid glycerol esters and other anionic surfactants in a weight ratio of 1: 3 to 3: 1, 22 to 32 wt .-% of a primary Ci2-Ci8 fatty alcohol with an average of 1 to 12 moles of ethylene oxide and 5 to 17 wt .-% mono- and / or polyfunctional alcohols containing 2 to 4 carbon atoms.
12. Mittel nach Anspruch 10 oder 11, dadurch gekennzeichnet, daß es als anionische Tenside eine Mischung aus sulfierten Fettsäureglycerin¬ estern, Fettalkylsulfat und Fettsäureseifen oder aus sulfierten Fett¬ säureglycerinestern, Alkansulfonat und Fettsäureseifen enthält. 12. Composition according to claim 10 or 11, characterized in that it contains a mixture of sulfated fatty acid glycerol esters, fatty alkyl sulfate and fatty acid soaps or of sulfated fatty acid glycerol esters, alkane sulfonate and fatty acid soaps as anionic surfactants.
EP93912976A 1992-06-22 1993-06-15 Washing and cleaning agents in liquid to paste form Expired - Lifetime EP0647260B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4220423A DE4220423A1 (en) 1992-06-22 1992-06-22 Detergents and cleaning agents in liquid to pasty form
DE4220423 1992-06-22
PCT/EP1993/001509 WO1994000543A1 (en) 1992-06-22 1993-06-15 Washing and cleaning agents in liquid to paste form

Publications (2)

Publication Number Publication Date
EP0647260A1 true EP0647260A1 (en) 1995-04-12
EP0647260B1 EP0647260B1 (en) 1996-07-10

Family

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Family Applications (1)

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Country Status (6)

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EP (1) EP0647260B1 (en)
JP (1) JPH07508054A (en)
AT (1) ATE140258T1 (en)
DE (2) DE4220423A1 (en)
ES (1) ES2089825T3 (en)
WO (1) WO1994000543A1 (en)

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Publication number Priority date Publication date Assignee Title
DE19635555C2 (en) * 1996-09-02 2000-06-08 Cognis Deutschland Gmbh Aqueous hand dishwashing liquid
GB0126280D0 (en) 2001-11-01 2002-01-02 Unilever Plc Liquid detergent compositions

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2243306A1 (en) * 1972-09-02 1974-03-21 Henkel & Cie Gmbh FOAM REGULATED DETERGENTS, ESPECIALLY FOR DRUM WASHING MACHINES
DE3941365A1 (en) * 1989-12-15 1991-06-20 Henkel Kgaa METHOD FOR PRODUCING SALTS OF SULFATED FATTY ACID GLYCERINESTER

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* Cited by examiner, † Cited by third party
Title
See references of WO9400543A1 *

Also Published As

Publication number Publication date
DE59303205D1 (en) 1996-08-14
EP0647260B1 (en) 1996-07-10
JPH07508054A (en) 1995-09-07
DE4220423A1 (en) 1993-12-23
ES2089825T3 (en) 1996-10-01
WO1994000543A1 (en) 1994-01-06
ATE140258T1 (en) 1996-07-15

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