WO1994000543A1 - Wasch- und reinigungsmittel in flüssiger bis pastöser form - Google Patents
Wasch- und reinigungsmittel in flüssiger bis pastöser form Download PDFInfo
- Publication number
- WO1994000543A1 WO1994000543A1 PCT/EP1993/001509 EP9301509W WO9400543A1 WO 1994000543 A1 WO1994000543 A1 WO 1994000543A1 EP 9301509 W EP9301509 W EP 9301509W WO 9400543 A1 WO9400543 A1 WO 9400543A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fatty acid
- weight
- fatty
- composition according
- glycerol esters
- Prior art date
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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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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6501999A JPH07508054A (ja) | 1992-06-22 | 1993-06-15 | 液状ないしペースト状洗剤 |
EP93912976A EP0647260B1 (de) | 1992-06-22 | 1993-06-15 | Wasch- und reinigungsmittel in flüssiger bis pastöser form |
DE59303205T DE59303205D1 (de) | 1992-06-22 | 1993-06-15 | Wasch- und reinigungsmittel in flüssiger bis pastöser form |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4220423.2 | 1992-06-22 | ||
DE4220423A DE4220423A1 (de) | 1992-06-22 | 1992-06-22 | Wasch- und Reinigungsmittel in flüssiger bis pastöser Form |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994000543A1 true WO1994000543A1 (de) | 1994-01-06 |
Family
ID=6461563
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1993/001509 WO1994000543A1 (de) | 1992-06-22 | 1993-06-15 | Wasch- und reinigungsmittel in flüssiger bis pastöser form |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0647260B1 (de) |
JP (1) | JPH07508054A (de) |
AT (1) | ATE140258T1 (de) |
DE (2) | DE4220423A1 (de) |
ES (1) | ES2089825T3 (de) |
WO (1) | WO1994000543A1 (de) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998010047A1 (de) * | 1996-09-02 | 1998-03-12 | Henkel Kommanditgesellschaft Auf Aktien | Wässrige handgeschirrspülmittel |
WO2003038029A1 (en) * | 2001-11-01 | 2003-05-08 | Unilever N.V. | Liquid detergent compositions |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2197974A1 (de) * | 1972-09-02 | 1974-03-29 | Henkel & Cie Gmbh | |
WO1991009009A1 (de) * | 1989-12-15 | 1991-06-27 | Henkel Kommanditgesellschaft Auf Aktien | Verfahren zur herstellung von salzen sulfierter fettsäureglycerinester |
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1992
- 1992-06-22 DE DE4220423A patent/DE4220423A1/de not_active Withdrawn
-
1993
- 1993-06-15 WO PCT/EP1993/001509 patent/WO1994000543A1/de active IP Right Grant
- 1993-06-15 EP EP93912976A patent/EP0647260B1/de not_active Expired - Lifetime
- 1993-06-15 DE DE59303205T patent/DE59303205D1/de not_active Expired - Fee Related
- 1993-06-15 AT AT93912976T patent/ATE140258T1/de not_active IP Right Cessation
- 1993-06-15 JP JP6501999A patent/JPH07508054A/ja active Pending
- 1993-06-15 ES ES93912976T patent/ES2089825T3/es not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2197974A1 (de) * | 1972-09-02 | 1974-03-29 | Henkel & Cie Gmbh | |
WO1991009009A1 (de) * | 1989-12-15 | 1991-06-27 | Henkel Kommanditgesellschaft Auf Aktien | Verfahren zur herstellung von salzen sulfierter fettsäureglycerinester |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1998010047A1 (de) * | 1996-09-02 | 1998-03-12 | Henkel Kommanditgesellschaft Auf Aktien | Wässrige handgeschirrspülmittel |
US6187733B1 (en) | 1996-09-02 | 2001-02-13 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous manual dishwashing composition containing a monoglyceride sulfate and at least two other surfactants |
WO2003038029A1 (en) * | 2001-11-01 | 2003-05-08 | Unilever N.V. | Liquid detergent compositions |
US6894017B2 (en) | 2001-11-01 | 2005-05-17 | Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. | Liquid detergent compositions |
Also Published As
Publication number | Publication date |
---|---|
DE4220423A1 (de) | 1993-12-23 |
ES2089825T3 (es) | 1996-10-01 |
JPH07508054A (ja) | 1995-09-07 |
ATE140258T1 (de) | 1996-07-15 |
EP0647260B1 (de) | 1996-07-10 |
EP0647260A1 (de) | 1995-04-12 |
DE59303205D1 (de) | 1996-08-14 |
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