EP0647260B1 - Washing and cleaning agents in liquid to paste form - Google Patents
Washing and cleaning agents in liquid to paste form Download PDFInfo
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- EP0647260B1 EP0647260B1 EP93912976A EP93912976A EP0647260B1 EP 0647260 B1 EP0647260 B1 EP 0647260B1 EP 93912976 A EP93912976 A EP 93912976A EP 93912976 A EP93912976 A EP 93912976A EP 0647260 B1 EP0647260 B1 EP 0647260B1
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- European Patent Office
- Prior art keywords
- weight
- fatty acid
- detergent
- fatty
- glycerol esters
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Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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 high ecological compatibility
- examples of such oleochemical surfactant compounds with high environmental compatibility are the known fatty alcohol sulfates, which are produced 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 the corresponding alkali metal salts, and the known ⁇ -sulfofatty acid alkyl esters (ester sulfonates), which are prepared by ⁇ -sulfonation of the methyl esters of fatty acids of plant and / or animal origin with predominantly 10 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts, in particular the corresponding alkali salts , and their disalts obtainable by hydrolysis.
- oleochemical surfactant compounds are sulfated fatty acid glycerol esters, for example sulfated 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.
- anionic surfactants which either consist entirely or at least to a large extent of native, that is to say renewable, fat-chemical raw materials.
- anionic surfactants are said to be able to completely or at least partially replace alkylbenzenesulfonates in otherwise customary detergent and cleaning agent formulations without sacrificing washing performance.
- the invention accordingly relates to a washing and cleaning agent in liquid to pasty form which contains anionic and nonionic surfactants, the surfactant content of the agent being 20 to 70% by weight, and sulfated fatty acid glycerol esters in amounts of 2 to 25 as anionic surfactants Wt .-% are included and the medium nonionic surfactants in amounts of 10 to 65 wt .-%.
- 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, natural mixtures of different fatty acid glycerol esters, their fatty acid components usually build 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 rape oil rich in oleic acid.
- the sulfonation can take place in accordance with international patent application W0 91/6532.
- preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. 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, that is to say iodine numbers less than 5, advantageously Harden less than 2.
- Suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, turnip oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or 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 the international patent application WO 91/9009 is specified.
- the sulfonation products are a complex mixture which contains mono-, di- and triglyceride sulfonates with an ⁇ -position and / or internal sulfonic acid grouping.
- sulfonated fatty acid salts As by-products, sulfonated fatty acid salts, glyceride sulfates, glycerine sulfates, glycerin and soaps are formed. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the ⁇ -sulfonated fatty acid disalts can be up to about 60% by weight, depending on the procedure.
- 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 as prescribed, and preferably further anionic 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 oleochemistry, such as the esters of ⁇ -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.
- sulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- the sulfonate group is statistically distributed over the entire carbon chain, with the secondary alkanesulfonates predominating.
- 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 C 12 -C 18 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 also contain proportions of unsaturated alcohols, for example oleyl alcohol.
- the proportion of the alkyl radicals is 50 to 70% by weight on C 12 , 18 to 30% by weight on C 14 , 5 to 15% by weight on C 16 , are preferred 3% by weight on C 10 and less than 10% by weight on C 18 are distributed.
- the proportion of fatty alkyl sulfates in the compositions is preferably 1 to 20% by weight and in particular 3 to 15% by weight.
- anionic surfactants are the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
- sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a 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 tallow fatty acids, derived soap mixtures.
- the salts of saturated and unsaturated fatty acids with C 12 -C 18 chain lengths in the form of their mixtures are particularly suitable.
- a preferably used soap mixture is formed from sodium oleate and the sodium salts of the saturated C 12 -C 16 fatty acid mixtures.
- the proportion of C 12 -C 14 fatty acids in the saturated component is advantageously 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 other anionic surfactants in a weight ratio of 1: 3 to 3: 1.
- anionic surfactant mixtures which contain sulfated fatty acid glycerol esters, fatty alkyl sulfates are preferred and fatty acid soaps or sulfated 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 C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohol with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 EO.
- the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alcohol ethoxylates have a restricted homolog distribution (narrow range ethoxylates, NRE).
- the content of liquid nonionic surfactants in the agents according to the invention is preferably 15 to 65% by weight.
- alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms branched in the 2-position 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 compositions preferably contain 2 to 20% by weight and in particular 5 to 15% by weight of ethanol or any mixture of ethanol and 1,2-propanediol or in particular of ethanol and glycerol.
- the washing and cleaning agents according to the invention in liquid to pasty form can be aqueous or essentially water-free agents.
- "essentially anhydrous" means that the agent preferably contains no free water which is not bound as water of crystallization or in a comparable form. In some cases, small amounts of free water are tolerable, especially in amounts 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 Fragrances may be included, as described, for example, in international patent application WO 92/2610.
- peroxy bleaching agents sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Further bleaching agents are, for example, peroxy carbonate, citrate perhydrates and H 2 O 2 -producing peracid salts of peracids, such as perbenzoates, peroxyphthalates or diperoxydodecanedioic acid. They are usually used in amounts of 8 to 25% by weight.
- 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.
- thickeners which can be used are 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, polymethacrylates 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 copolymers between 2000 and 200000, preferably between 50,000 to 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 not exceeding 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 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 C 12 -C 18 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 C 12 -C 18 fatty alcohol with an average of 1 to 12 moles of ethylene oxide per mole of fatty alcohol, 28 to Contains 40 wt .-% water and 5 to 17 wt .-% mono- and / or polyfunctional alcohols with 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.
- These partially esterified polymers are obtained by copolymerizing (a) at least one C 4 -C 28 olefin or mixtures of at least one C 4 -C 28 olefin with up to 20 mol% of C 1 -C 28 alkyl vinyl ethers and (b) ethylenically unsaturated dicarboxylic acid anhydrides with 4 to 8 carbon atoms in a molar ratio of 1: 1 to copolymers with K values from 6 to 100 and subsequent partial esterification of the copolymers with reaction products such as C 1 -C 13 alcohols, C 8 -C 22 fatty acids, C 1 -C 12 alkylphenols, secondary C 2 -C 30 amines or mixtures thereof with at least one C 2 -C 4 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 the extent that 5 to 50% of
- 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% strength by weight solution.
- the copolymers not only contribute 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 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 colorants and fragrances, Contain 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 colorants and fragrances, Contain opacifiers or pearlescent agents.
- the salts of polyphosphonic acids which are preferably used are the neutral sodium salts of, for example, 1-hydroxyethane-1,1-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. Enzymes 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 carriers and / or embedded in coating substances in order to protect them against premature decomposition.
- the agents can contain further enzyme stabilizers.
- 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.
- boron compounds for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
- Suitable foam inhibitors contain, for example, known organopolysiloxanes, paraffins or waxes. As mentioned above, the use of sulfonated unsaturated fatty acid glycerol esters is also preferred.
- a continuously working falling film reactor (length 120 cm, cross section 1 cm, educt throughput 600 g / h) with jacket cooling and lateral SO 3 gassing, about 5 mol of a fatty acid glycerol ester with an iodine number less than 5 (see Table 1) at 80 ° C with about 15 moles of gaseous sulfur trioxide reacted.
- 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.
- 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.
- the basic compositions of the aqueous liquid detergents were (data in% by weight): M1 M2 13.0 "Anionic surfactant” 5.0 15.0 "Non-ionic surfactant” 12.0 6.0 Oleic acid soap, technical 7.0 7.0 Coconut fatty acid soap 8.0 5.0 Triethanolamine --- 0.5 Citric acid (calculated as free acid) 0.5 7.0 Ethanol 7.0 5.0 Glycerin 5.0 rest water rest
- the agents M1 / V, M1 / 1 and M1 / 2 were tested against each other at a dosage of 180 g per machine. The results are shown in Table 2.
- Table 2 medium % Remission when soiled SW-B SH-BV SH-PBV SH-P R-BV T-BV LS-PBV MU / PBV M1 / V 57.2 76.1 69.1 72.4 42.2 39.1 38.6 68.3 M1 / 1 58.1 76.3 68.8 73.4 43.7 39.9 38.9 68.8 M1 / 2 58.6 77.4 68.5 71.9 43.5 41.8 42.7 70.1
- the agents M1 / V and M1 / 3 were tested after storage for 6 weeks at 40 ° C.
- the results are summarized in Table 4. It is shown that a partial replacement of conventional nonionic surfactants (50%) by sulfonated fatty acid glycerol esters is possible without having to accept a reduction in 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.
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Abstract
Description
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 Tensidverbindungen mit hoher Umweltverträglichkeit sind die bekannten Fettalkoholsulfate, die durch Sulfatierung von Fettalkoholen pflanzlichen und/oder tierischen Ursprungs mit überwiegend 10 bis 20 C-Atomen im Fettalkoholmolekül und nachfolgende Neutralisation zu wasserlöslichen Salzen, insbesondere den entsprechenden Alkalisalzen, hergestellt werden, sowie die bekannten α-Sulfofettsäurealkylester (Estersulfonate), die durch α-Sulfonierung 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 Hydrolyse erhältlichen Disalze.The use of oleochemical surfactant compounds, which are obtained from renewable vegetable and / or animal raw materials and which have 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 are produced 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 the corresponding alkali metal salts, and the known α-sulfofatty acid alkyl esters (ester sulfonates), which are prepared by α-sulfonation of the methyl esters of fatty acids of plant and / or animal origin with predominantly 10 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts, in particular the corresponding alkali salts , and their disalts obtainable by hydrolysis.
Beispiele für weitere fettchemische Tensidverbindungen sind sulfierte Fettsäureglycerinester, beispielsweise sulfierte ungesättigte Fettsäureglycerinester, 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 further oleochemical surfactant compounds are sulfated fatty acid glycerol esters, for example sulfated 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 petrochemischen Grundstoffen gewonnen werden.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.
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 nachwachsenden fettchemischen Grundstoffen bestehen. Diese Aniontenside sollen in ansonsten üblichen Wasch- und Reinigungsmittelformulierungen Alkylbenzolsulfonate ohne Einbußen in der Waschleistung vollständig oder zumindest teilweise ersetzen können.It was therefore the task of creating a detergent 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, fat-chemical raw materials. These anionic surfactants are said to be able to completely or at least partially replace alkylbenzenesulfonates in otherwise customary detergent and cleaning agent formulations without sacrificing washing performance.
Gegenstand der Erfindung ist demnach ein Wasch- und Reinigunsmittel in flüssiger bis pastöser Form, das anionische und nichtionische Tenside enthält, wobei der Gehalt des Mittels an Tensiden 20 bis 70 Gew.-% beträgt, als anionische Tenside sulfierte Fettsäureglycerinester in Mengen von 2 bis 25 Gew.-% enthalten sind und das mittel nichtionische Tenside in mengen von 10 bis 65 Gew.-% enthält.The invention accordingly relates to a washing and cleaning agent in liquid to pasty form which contains anionic and nonionic surfactants, the surfactant content of the agent being 20 to 70% by weight, and sulfated fatty acid glycerol esters in amounts of 2 to 25 as anionic surfactants Wt .-% are included and the medium nonionic surfactants in amounts of 10 to 65 wt .-%.
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 Fettsäureglycerinester aus, so baut sich deren Fettsäurekomponente üblicherweise teilweise aus gesättigten und teilweise aus ungesättigten Fettsäuren auf. Geeignete sulfierte Fettsäureglycerinester sind beispielsweise die Sulfierprodukte der ungesättigten Fettsäureglycerinester, die auf Basis von Korianderöl, Sonnenblumenöl, Baumwollsaatöl, Olivenöl, Erdnußöl, Leinöl, Fischöl, Schweineschmalz oder ölsäurereichem Rüböl gewonnen werden. Die Sulfierung kann gemäß der internationalen Patentanmeldung W0 91/6532 erfolgen.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, natural mixtures of different fatty acid glycerol esters, their fatty acid components usually build 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 rape oil rich in oleic acid. The sulfonation can take place in accordance with international patent application W0 91/6532.
Bevorzugte sulfierte Fettsäureglycerinester sind jedoch die Sulfierprodukte von gesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen, beispielsweise 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 Wasserstoff weitgehend abzusättigen, d.h. auf Iodzahlen kleiner 5, vorteilhafterweise kleiner 2 zu härten. Typische Beispiele geeigneter Einsatzstoffe sind Palmöl, Palmkernöl, Palmstearin, Olivenöl, Rüböl, Korianderöl, Sonnenblumenöl, Baumwollsaatöl, Erdnußöl, Leinöl, Lardöl oder Schweineschmalz. Aufgrund ihres hohen natürlichen Anteils an gesättigten Fettsäuren 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 Fettsäureglycerinestern mit Iodzahlen kleiner 5, die Fettsäuren mit 6 bis 22 Kohlenstoffatomen enthalten, erfolgt vorzugsweise durch Umsetzung mit gasförmigem Schwefeltrioxid und anschließender Neutralisierung mit wäßrigen Basen, wie sie in der internationalen Patentanmeldung WO 91/9009 angegeben ist.However, preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. 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, that is to say iodine numbers less than 5, advantageously Harden less than 2. Typical examples of suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, turnip oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or 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 the international patent application WO 91/9009 is specified.
Die Sulfierprodukte stellen ein komplexes Gemisch dar, das Mono-, Di- und Triglyceridsulfonate mit α-ständiger und/oder innenständiger Sulfonsäuregruppierung enthält. Als Nebenprodukte bilden sich sulfonierte Fettsäuresalze, Glyceridsulfate, Glycerinsulfate, Glycerin und Seifen. Geht man bei der Sulfierung von gesättigten Fettsäuren oder gehärteten Fettsäureglycerinestergemischen aus, so kann der Anteil der α-sulfonierten Fettsäure-Disalze je nach Verfahrensführung durchaus bis etwa 60 Gew.-% betragen. Im Rahmen dieser Erfindung wird unter sulfierten Fettsäureglycerinestern jeweils dieses komplexe Reaktionsgemisch, einschließlich der unsulfierten und nicht waschaktiven Bestandteile, jedoch ohne wäßrige Anteile verstanden.The sulfonation products are a complex mixture which contains mono-, di- and triglyceride sulfonates with an α-position and / or internal sulfonic acid grouping. As by-products, sulfonated fatty acid salts, glyceride sulfates, glycerine sulfates, glycerin and soaps are formed. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the α-sulfonated fatty acid disalts can be up to about 60% by weight, depending on the procedure. 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 Fettsäureglycerinester mit Iodzahlen kleiner 5, die Fettsäuren mit 6 bis 22 Kohlenstoffatomen enthalten, 10 bis 65 Gew.-% nichtionische Tenside wie vorgeschrieben sowie vorzugsweise weitere anionische Tenside, beispielsweise Alkylsulfate, vorzugsweise Fettalkylsulfate, Alkansulfonate, Seifen oder Mischungen aus diesen. Die Mittel können auch geringe Mengen an Alkylbenzolsulfonaten, beispielsweise 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 as prescribed, and preferably further anionic 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 α-Sulfofettsäuren, wobei die Sulfogruppe in ihrer Salz-Form vorliegt (Monosalz), zum Beispiel die α-sulfonierten Methylester, der hydrierten Kokos-, Palmkern, oder Talgfettsäuren. Geeignet sind außerdem auch die biologisch gut abbaubaren Alkansulfonate, die aus C12-C18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation gewonnen werden. Die Sulfonatgruppe ist über die gesamte Kohlenstoffkette statistisch verteilt, wobei die sekundären Alkansulfonate überwiegen. Als Nachteil der Alkansulfonate ist jedoch anzusehen, daß sie aus petrochemischen 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 sulfierten Fettsäureglycerinestern.Particularly suitable sulfonates are sulfonates based on oleochemistry, such as the esters of α-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 obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The sulfonate group is statistically distributed over the entire carbon chain, with the secondary alkanesulfonates predominating. A disadvantage of 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 sulfonated fatty acid glycerol esters.
Geeignete Tenside vom Sulfat-Typ sind die Schwefelsäuremonoester aus primären Alkoholen natürlichen und synthetischen Ursprungs, insbesondere aus Fettalkoholen. Als Fettalkylsulfate eignen sich die Schwefelsäuremonoester der C12-C18-Fettalkohole, wie Lauryl-, Myristyl-, Cetylalkohol- oder Stearylalkohol, und der aus Kokosöl, Palm- und Palmkernöl gewonnenen Fettalkoholgemische, die zusätzlich noch Anteile an ungesättigten Alkoholen, 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 C16, unter 3 Gew.-% auf C10 und unter 10 Gew.-% auf C18 verteilt sind. Der Anteil an Fettalkylsulfaten in den Mitteln beträgt vorzugsweise 1 bis 20 Gew.-% und insbesondere 3 bis 15 Gew.-%.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 C 12 -C 18 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 also contain proportions of unsaturated alcohols, for example oleyl alcohol. Mixtures in which the proportion of the alkyl radicals is 50 to 70% by weight on C 12 , 18 to 30% by weight on C 14 , 5 to 15% by weight on C 16 , are preferred 3% by weight on C 10 and less than 10% by weight on C 18 are distributed. The proportion of fatty alkyl sulfates in the compositions is preferably 1 to 20% by weight and in particular 3 to 15% by weight.
Weitere bevorzugte Aniontenside sind die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten C8- bis C18-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 eingeschränkter Homologenverteilung ableiten, besonders bevorzugt.Further preferred anionic surfactants are the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a 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 insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern- oder Talgfettsäuren, 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 tallow fatty acids, derived soap mixtures.
Insbesondere sind die Salze von gesättigten und ungesättigten Fettsäuren mit C12-C18-Kettenlängen in Form ihrer Gemische geeignet. Ein bevorzugt verwendetes Seifengemisch wird aus Natriumoleat und den Natriumsalzen der gesättigten C12-C16-Fettsäuregemische gebildet. Der Anteil an C12-C14-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 Anteile 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 C 12 -C 18 chain lengths in the form of their mixtures are particularly suitable. A preferably used soap mixture is formed from sodium oleate and the sodium salts of the saturated C 12 -C 16 fatty acid mixtures. The proportion of C 12 -C 14 fatty acids in the saturated component is advantageously 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 Fettsäureglycerinestern und weiteren anionischen Tensiden im Gewichtsverhältnis 1 : 3 bis 3 : 1. Dabei sind insbesondere anionische Tensidmischungen bevorzugt, die sulfierte Fettsäureglycerinester, Fettalkylsulfate und Fettsäureseifen oder sulfierte Fettsäureglycerinester, Alkansulfonate und Fettsäureseifen 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 other anionic surfactants in a weight ratio of 1: 3 to 3: 1. In particular, anionic surfactant mixtures which contain sulfated fatty acid glycerol esters, fatty alkyl sulfates are preferred and fatty acid soaps or sulfated 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 insbesondere C12-C14-Alkohole mit 3 EO oder 4 EO, C9-C11-Alkohol mit 7 EO, C13-C15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-C18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-C14-Alkohol mit 3 EO und C12-C18-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 C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohol with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 EO.
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 Homologenverteilung auf (narrow range ethoxylates, NRE). Der Gehalt der erfindungsgemäßen Mittel an flüssigen nichtionischen Tensiden beträgt vorzugsweise 15 bis 65 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 content of liquid nonionic surfactants in the agents according to the invention is preferably 15 to 65% by weight.
Außerdem können als weitere nichtionische Tenside auch Alkylglykoside der allgemeinen Formel RO(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 Monoglykosiden 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.-%.In addition, alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms branched in the 2-position 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 Kohlenstoffatomen, 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 insbesondere 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 erfindungsgemäBen Wasch- und Reinigungsmittel in flüssiger 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 compositions preferably contain 2 to 20% by weight and in particular 5 to 15% by weight of ethanol or any mixture of ethanol and 1,2-propanediol or in particular of 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 in amounts contain from 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 Kristallwasser oder in vergleichbarer Form gebundenes Wasser enthält. In einigen 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, Verdickungsmittel, Gerüstsubstanzen, anorganische Salze, Schauminhibitoren, Enzyme, optische Aufheller, sowie Farbund Duftstoffe enthalten sein, so wie sie beispielsweise in der internationalen Patentanmeldung WO 92/2610 beschrieben sind. Unter den als Peroxy-Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben 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. Bevorzugt 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 Verdickungsmittel 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-, Magnesium- und Titan-Stearate oder die Natrium- und/oder Kaliumsalze der Behensäure, sowie weitere polymere Verbindungen eingesetzt werden. Zu den letzteren gehören bevorzugt Polyvinylpyrrolidon, Urethane und die Salze polymerer Polycarboxylate, beispielsweise homopolymerer oder copolymerer Polyacrylate, Polymethacrylate 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 Copolymeren 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 quervernetzten 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 anhydrous" means that the agent preferably contains no free water which is not bound as water of crystallization or in a comparable form. In some cases, small amounts of free water are tolerable, especially in amounts 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 Fragrances may be included, as described, for example, in international patent application WO 92/2610. Among the compounds used as peroxy bleaching agents and providing H 2 O 2 in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents are, for example, peroxy carbonate, citrate perhydrates and H 2 O 2 -producing 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. Examples of thickeners which can be used are 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, polymethacrylates 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 copolymers between 2000 and 200000, preferably between 50,000 to 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 not exceeding 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 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 Tensiden, insbesondere 22 bis 32 Gew.-% eines primären C12-C18-Fettalkohols mit durchschnittlich 1 bis 12 Mol Ethylenoxid 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 Polymere werden durch Copolymerisation von (a) mindestens einem C4-C28-Olefin oder Mischungen aus mindestens einem C4-C28-Olefin mit bis zu 20 Mol-% C1-C28-Alkylvinylethern und (b) ethylenisch ungesättigten Dicarbonsäureanhydriden mit 4 bis 8 Kohlenstoffatomen im Molverhältnis 1 : 1 zu Copolymerisaten mit K-Werten von 6 bis 100 und anschließende partielle Veresterung der Copolymerisate mit Umsetzungsprodukten wie C1-C13-Alkoholen, C8-C22-Fettsäuren, C1-C12-Alkylphenolen, sekundären C2-C30-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 Maleinsäureanhydrid. Die partiell veresterten Copolymerisate können entweder in Form der freien Säure oder vorzugsweise in partiell oder vollständig neutralisierter Form vorliegen. Vorteilhafterweise werden die Copolymerisate in Form einer wäßrigen Lösung, insbesondere in Form einer 40 bis 50 Gew.-%igen Lösung eingesetzt. Die Copolymerisate leisten nicht nur einen Beitrag zur Primär- und Sekundärwaschleistung des flüssigen Wasch- und Reinigungsmittels, sondern bewirken auch eine gewünschte Viskositätserniedrigung der konzentrierten flüssigen Waschmittel. Durch den Einsatz dieser partiell veresterten Copolymerisate werden konzentrierte wäßrige Flüssigwaschmittel erhalten, die unter dem alleinigen Einfluß der Schwerkraft und ohne Einwirkung sonstiger Scherkräfte 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 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 C 12 -C 18 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 C 12 -C 18 fatty alcohol with an average of 1 to 12 moles of ethylene oxide per mole of fatty alcohol, 28 to Contains 40 wt .-% water and 5 to 17 wt .-% mono- and / or polyfunctional alcohols with 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. These partially esterified polymers are obtained by copolymerizing (a) at least one C 4 -C 28 olefin or mixtures of at least one C 4 -C 28 olefin with up to 20 mol% of C 1 -C 28 alkyl vinyl ethers and (b) ethylenically unsaturated dicarboxylic acid anhydrides with 4 to 8 carbon atoms in a molar ratio of 1: 1 to copolymers with K values from 6 to 100 and subsequent partial esterification of the copolymers with reaction products such as C 1 -C 13 alcohols, C 8 -C 22 fatty acids, C 1 -C 12 alkylphenols, secondary C 2 -C 30 amines or mixtures thereof with at least one C 2 -C 4 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 the extent that 5 to 50% of the carboxyl groups of 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% strength by weight solution. The copolymers not only contribute 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 konzentrierten Mittel beträgt im allgemeinen 7 bis 10,5, vorzugsweise 7 bis 9,5 und insbesondere 7 bis 8,5. Die Einstellung höherer pH-Werte, beispielsweise oberhalb von 9, kann durch den Einsatz geringer Mengen an Natronlauge oder an alkalischen Salzen wie Natriumcarbonat oder Natriumsilikat erfolgen. Die erfindungsgemäßen Wasch- und Reinigungsmittel weisen im allgemeinen Viskositäten zwischen 150 und 10000 mPas (Brookfield-Viskosimeter, 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 agents according to the invention, which are particularly preferred, 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, beispielsweise Salze von Polycarbonsäuren, beispielsweise der Citronensäure, Salze von Polyphosphonsäuren, optische Aufheller, Enzyme, Enzymstabilisatoren, geringe Mengen an neutralen Füllsalzen sowie Farb- 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 colorants and fragrances, Contain opacifiers or pearlescent agents.
Als Salze von Polyphosphonsäuren werden vorzugsweise die neutral reagierenden Natriumsalze von beispielsweise 1-Hydroxyethan-1,1,-diphosphonat in Mengen von 0,1 bis 1,5 Gew.-% verwendet.The salts of polyphosphonic acids which are preferably used are the neutral sodium salts of, for example, 1-hydroxyethane-1,1-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 licheniformis und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Vorzugsweise 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 adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen.Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes 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 carriers and / or embedded in coating substances in order to protect them against premature decomposition.
Zusätzlich zu den mono- und polyfunktionellen Alkoholen und den Phosphonaten können die Mittel weitere Enzymstabilisatoren enthalten. Beispielsweise können 0,5 bis 1 Gew.-% Natriumformiat eingesetzt werden. Möglich ist auch der Einsatz von Proteasen, die mit löslichen Calciumsalzen und einem Calciumgehalt von vorzugsweise etwa 1,2-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).In addition to the mono- and polyfunctional alcohols and the phosphonates, 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 (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), 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 Fettsäureglycerinester.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, the use of sulfonated unsaturated fatty acid glycerol esters is also preferred.
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, Querschnitt 1 cm, Eduktdurchsatz 600 g/h) mit Mantelkühlung und seitlicher SO3-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.
HPK = Gehärtetes Palmkernöl
HPK = 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:
- 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:
- Lange-Gerät (Y-Filter)
- Washing program:
- Color wash program (without prewash) at 40 ° C
- Dosage:
- 180 g or 200 g per machine
- Water hardness:
- 16 ° d
- Textile samples:
- 3.5 kg clean filling laundry (normal household laundry)
- Regulations:
- 3 times
- Measurement conditions:
- artificial soiling:
- RFC 3/24 (465 nm, suppression of the brightener effect)
- natural soiling:
- Lange device (Y filter)
Die Anschmutzungen waren:
- SW-B
- Staub-Wollfett auf Baumwolle
- SH-BV
- Staub-Hautfett auf veredelter Baumwolle
- SH-P
- Staub-Hautfett auf Polyester
- SH-PBV
- Staub-Hautfett auf einem Gemisch aus Polyester und veredelter Baumwolle
- BMR-B
- Blut, Milch und Ruß auf Baumwolle
- R-BV
- Rotwein auf veredelter Baumwolle
- T-BV
- Tee auf veredelter Baumwolle
- LS-PBV
- Lippenstift auf einem Gemisch aus Polyester und veredelter Baumwolle
- MU-PBV
- Make-up auf einem Gemisch aus Polyester und veredelter Baumwolle
- SW-B
- Dust-wool grease on cotton
- SH-BV
- Dust-skin fat on refined cotton
- SH-P
- Dust skin grease on polyester
- SH-PBV
- Dusty skin fat on a mixture of polyester and refined cotton
- BMR-B
- Blood, milk and soot on cotton
- R-BV
- Red wine on refined cotton
- T-BV
- Tea on refined cotton
- LS-PBV
- Lipstick on a mixture of polyester and refined cotton
- MU-PBV
- Make-up on a mixture of polyester and refined cotton
Die Grundzusammensetzungen der wäßrigen Flüssigwaschmittel lauteten (Angaben jeweils in Gew.-%):
Dabei bedeuteten "Aniontensid" in
- M1/V, M1/3 und M2/V C9-C13-Alkylbenzolsulfonat
- M1/1 und M2/1 sulfiertes HK
- M1/2 und M2/2 sulfiertes HPK
- M1/V, M1/1, M1/2, M2/V, M2/1 und M2/2 C12-C18-Fettalkohol mit 7 EO
- M1/3 eine Mischung aus C12-C18-Fettalkohol mit 7 EO und sulfiertem HK im Gewichtsverhältnis 1 : 1
- M1 / V, M1 / 3 and M2 / V C 9 -C 13 alkylbenzenesulfonate
- M1 / 1 and M2 / 1 sulfated HK
- M1 / 2 and M2 / 2 sulfated HPK
- M1 / V, M1 / 1, M1 / 2, M2 / V, M2 / 1 and M2 / 2 C 12 -C 18 fatty alcohol with 7 EO
- M1 / 3 a mixture of C 12 -C 18 fatty alcohol with 7 EO and sulfated HK in a weight ratio of 1: 1
Die Mittel M1/V, M1/1 und M1/2 wurden jeweils bei einer Dosierung von 180 g pro Maschine gegeneinander getestet. Die Ergebnisse sind in Tabelle 2 aufgeführt.
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.
Die Mittel M1/V und M1/3 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 sulfierte Fettsäureglycerinester möglich ist, ohne Einbußen in der Waschleistung 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.
Claims (11)
- A detergent in liquid to paste-like form containing anionic and nonionic surfactants, characterized in that the surfactant content of the detergent is 20 to 70% by weight, sulfonated fatty acid glycerol esters being present as anionic surfactants in quantities of 2 to 25% by weight and nonionic surfactants being present in quantities of 10 to 65 % by weight.
- A detergent as claimed in claim 1, characterized in that it contains 5 to 20% by weight of sulfonated fatty acid glycerol esters obtained from fatty acid glycerol esters with iodine values below 5, preferably from mono-, di- and triglycerides or mixtures thereof with iodine value below 5, which contain fatty acids with 6 to 22 carbon atoms, by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases.
- A detergent as claimed in any of claims 1 or 2, characterized in that it contains mono- and/or polyhydric alcohols with 1 to 6 carbon atoms in quantities of 2 to 20% by weight and preferably 5 to 15% by weight as organic solvents. 3
- A detergent as claimed in any of claims 1 to 3, characterized in that it contains 20 to 65% by weight of liquid nonionic surfactants and water in quantities of 0 to 5% by weight.
- A detergent as claimed in any of claims 1 to 3, characterized in that it contains 10 to 35% by weight and preferably 20 to 35% by weight of nonionic surfactants and 20 to 55% by weight, preferably 25 to 45% by weight and more preferably 28 to 40% by weight of water.
- A detergent as claimed in any of claims 1 to 5, characterized in that it is free from alkylbenzenesulfonates.
- A detergent as claimed in any of claims 1 to 6, characterized in that it contains alkylsulfates, preferably fatty alkylsulfates, alkanesulfonates, soap or mixtures thereof as further anionic surfactants.
- A detergent as claimed in any of claims 1 to 7, characterized in that it contains 0.5 to 8% by weight and preferably 1 to 5% by weight of alkyl glycoside.
- A detergent as claimed in any of claims 1 to 3 and 5 to 8, characterized in that it contains 15 to 35% by weight of a mixture of sulfonated fatty acid glycerol esters and other anionic surfactants, more particularly soap, in a ratio by weight of 1:3 to 3:1 and 10 to 20% by weight of a primary C12-18 fatty alcohol containing on average 1 to 12 moles of ethylene oxide.
- A detergent as claimed in any of claims 1 to 3 and 5 to 8, characterized in that it contains 15 to 35% by weight of a mixture of sulfonated fatty acid glycerol esters and other anionic surfactants in a ratio by weight of 1:3 to 3:1, 22 to 32% by weight of a primary C12-18 fatty alcohol containing on average 1 to 12 moles of ethylene oxide and 5 to 17% by weight of monohydric and/or polyhydric alcohols containing 2 to 4 carbon atoms.
- A detergent as claimed in claim 9 or 10, characterized in that it contains a mixture of sulfonated fatty acid glycerol esters, fatty alkylsulfate and fatty acid soaps or a mixture of sulfonated fatty acid glycerol esters, alkanesulfonate and fatty acid soaps as anionic surfactants.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4220423 | 1992-06-22 | ||
DE4220423A DE4220423A1 (en) | 1992-06-22 | 1992-06-22 | Detergents and cleaning agents in liquid to pasty form |
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 EP0647260A1 (en) | 1995-04-12 |
EP0647260B1 true EP0647260B1 (en) | 1996-07-10 |
Family
ID=6461563
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93912976A Expired - Lifetime EP0647260B1 (en) | 1992-06-22 | 1993-06-15 | Washing and cleaning agents in liquid to paste form |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0647260B1 (en) |
JP (1) | JPH07508054A (en) |
AT (1) | ATE140258T1 (en) |
DE (2) | DE4220423A1 (en) |
ES (1) | ES2089825T3 (en) |
WO (1) | WO1994000543A1 (en) |
Families Citing this family (2)
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 |
Family Cites Families (2)
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 |
-
1992
- 1992-06-22 DE DE4220423A patent/DE4220423A1/en not_active Withdrawn
-
1993
- 1993-06-15 WO PCT/EP1993/001509 patent/WO1994000543A1/en active IP Right Grant
- 1993-06-15 AT AT93912976T patent/ATE140258T1/en not_active IP Right Cessation
- 1993-06-15 JP JP6501999A patent/JPH07508054A/en active Pending
- 1993-06-15 ES ES93912976T patent/ES2089825T3/en not_active Expired - Lifetime
- 1993-06-15 DE DE59303205T patent/DE59303205D1/en not_active Expired - Fee Related
- 1993-06-15 EP EP93912976A patent/EP0647260B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH07508054A (en) | 1995-09-07 |
DE4220423A1 (en) | 1993-12-23 |
EP0647260A1 (en) | 1995-04-12 |
DE59303205D1 (en) | 1996-08-14 |
ES2089825T3 (en) | 1996-10-01 |
WO1994000543A1 (en) | 1994-01-06 |
ATE140258T1 (en) | 1996-07-15 |
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