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
  • 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
• • 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
  • 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
  • C11D1/02—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
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

• the invention relates to detergents and cleaning agents based on alkyl glycosides and synthetic anionic surfactants.
• alkyl glycosides which are acetals from sugars and fatty alcohols with at least 8 carbon atoms, can be produced entirely from renewable raw materials, namely fat on the one hand and sugars or starches on the other hand.
• alkyl oligoglycoside, alkyl polyglycoside, alkyl oligosaccharide and alkyl polysaccharide refer to those alkylated glycoses in which 1 acetal-like alkyl radical is assigned to more than one glycose radical, that is to say to a poly or oligosaccharide radical. These terms are considered to be synonymous with each other.
• alkyl monoglycoside means the acetal of a monosaccharide. Since the reaction products from the sugars and the alcohols are generally mixtures, the term alkyl glycoside means both alkyl monoglycosides and alkyl poly (oligo) glycosides, unless the structural differences are important.
• the German patent 593 422 discloses the maltosides and lactosides of aliphatic alcohols with more than 8 carbon atoms and their use as emulsifying, cleaning and wetting agents.
• the washing effect of the soap is improved, which is explained by the effect of the cetyl maltoside as a lime soap dispersant.
• Such ternary alkyl glycoside mixtures have already been used in combination with other known anionic or nonionic surfactants.
• European patent application 75 995 describes mixtures of alkyl polysaccharides and other nonionic surfactants.
• European patent application 105 556 discloses cleaning agents which contain alkyl polysaccharides, another nonionic surfactant and an anionic surfactant from the group consisting of glyceryl ether sulfonates, ethoxylated alkylphenol ether sulfates, alkyl sulfates and alkylbenzenesulfonates.
• alkyl glycoside mixtures are combined with anionic surfactants and, if appropriate, other conventional detergent and cleaning agent components.
• Preferred anionic surfactants are saturated or unsaturated soaps, which can be hydroxylated or sulfonated in the a-position, and in particular alkylbenzenesulfonates.
• the alkyl poly (oligo) glycosides used contain about 1.5 to 10 glycose units per molecule. This value is an average value and also takes into account the presence of alkyl monoglycosides in a corresponding proportion. However, alkyl glucosides with a degree of oligomerization of 2 or higher are found to be particularly suitable.
• the economically most important anion surfactant which is also used most frequently in combination with ternary alkyl glycoside mixtures, belongs to the surfactant class of alkyl benzene sulfonates.
• the object of the present invention is to create a washing and cleaning agent which contains a combination of nonionic surfactants and an anionic surfactant from the group of sulfates and sulfonates, which can be obtained entirely from native, ie renewable, fat-chemical raw materials.
• This combination is also intended to substitute those surfactant mixtures in which the anionic surfactants, which are based exclusively on petrochemical, that is to say non-renewable, raw materials, for example surfactants from the class of the alkylbenzenesulfonates.
• Substitution in reduced phosphate detergents and cleaning agents is of particular interest.
• “Reduced phosphate” means in the following those washing and cleaning agents which contain at most 30% by weight, preferably less than 20% by weight, of phosphates, calculated as alkali metal tripolyphosphates, and in particular are free of phosphates.
• washing and cleaning agents according to the invention show a significantly better biodegradability in comparison to agents containing alkylbenzenesulfonate and also a significantly better skin ver indolence.
• phosphate-reduced detergents according to the invention have better washability than commercially available phosphate-reduced detergents based on alkylbenzenesulfonate.
• the products according to the invention remain liquid at a content of 60% washing active substance, whereas products based on alkylbenzenesulfonates already form precipitates at this content and can no longer be pumped.
• Alkyl glycosides suitable for the purposes of this invention are described, for example, in US Pat. Nos. 3,547,828 and 3,839,318.
• Alkyl glycosides used with particular preference are the process products described in German patent applications 37 23 826 and P 38 33 780.0, which have an alkyl monoglycoside content of over 70% by weight (based on the total amount of alkyl mono- and alkyl oligoglycosides) and an average degree of oligomerization x of less than 1.5, preferably 1.1 to 1.4.
• the sugar component comes from the usual aldoses or ketoses, such as. B. glucose, fructose, mannose, galactose, talose, gulose, allose, old rose, idose, arabinose, xylose, lyxose and ribose. Because of the better reactivity, the reducing saccharides, the aldoses, are preferably used. Among the aldoses, glucose is particularly suitable due to its easy accessibility and availability in technical quantities.
• the alkyl glycosides used with particular preference in the invention are therefore the alkyl glucosides.
• alkyl in alkylglycoside broadly encompasses the remainder of an aliphatic alcohol of any chain length, preferably a primary aliphatic alcohol having 8 to 22 carbon atoms and in particular a fatty alcohol having 10 to 18 carbon atoms obtainable from natural fats, so that the The term saturated and unsaturated radicals and their mixture including those with different chain lengths in the mixture.
• Typical alkyl glycosides are those in which alkyl is octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and mixtures thereof.
• Particularly suitable alkyl glycosides contain a coconut fatty alkyl residue, i.e. H. Decyl, dodecyl and tetradecyl residues.
• alkyl glycosides whose alkyl radical is derived from synthetic primary alcohols, in particular the so-called oxo alcohols, which have a certain percentage, usually 20 to 40%, of branched isomers with a 2-methyl radical , derives.
• oxo alcohols which have a certain percentage, usually 20 to 40%, of branched isomers with a 2-methyl radical .
• surfactants are less preferred if the focus is also on the intended use of surfactants with a natural raw material base of the hydrophobic part.
• alkyl glycosides contain more than 70% by weight, in particular 75 to 90% by weight, of alkyl monoglycoside, based on the total amount of alkyl monoglycoside and alkyl oligoglycoside.
• alkyl glycoside mixtures consist of 30 to 90% by weight, preferably 50 to 90% by weight alkyl monoglycoside, 2 to 40% by weight, preferably 3 to 25% by weight alkyl oligoglycoside, 0.5 to 5% by weight. %, preferably 1 to 4% by weight of residual fatty alcohol and 3 to 25% by weight, preferably 5 to 15% by weight of polyglycose.
• the latter are formed in a side reaction in the alkylation reaction by condensation of the glycose molecules with one another.
• the average molecular weight of these polyglycoses is from 2000 to 10,000.
• alkyl sulfates used for the purposes of the invention as anionic surfactants according to formula (11) are preferably derived from fatty alcohols which are obtained from natural fatty acids or fatty acid mixtures. They are in the form of the alkali, alkaline earth or ammonium salts, ammonium salts also being understood to mean the salts of organic ammonium bases.
• Suitable alkyl sulfates have a linear alkyl or alkenyl group R, having 6 to 26, preferably 10 to 22, carbon atoms.
• Alkyl or alkenyl radicals having 16 to 22 carbon atoms that is to say sulfates, whose fatty alkyl groups consist, for example, of coconut, tallow, lauryl, myristyl, palmityl, stearyl and oleyl radicals and mixtures thereof, are particularly preferred.
• Sulfates of fatty alcohol mixtures which are derived from natural, linear fatty alcohols and have a C chain distribution of 0 to 3% by weight of C12, 5 to 14% by weight of C14, 25 to 35% by weight of Ci 6 , 17 are particularly preferred up to 27% by weight of C 18 , 10 to 20% by weight of C 20 and 10 to 20% by weight of C 22 , a hydroxyl number between 210 and 220 and an iodine number of less than 1.0.
• Anionic surfactants according to formula (111) are obtained by reacting saturated fatty acids and fatty acid esters, which are in turn predominantly based on natural raw materials, by reacting with S0 3 and then converting them to the alkali metal, alkaline earth metal or ammonium salts.
• Suitable a-sulfoesters and sulfo-acid disalts are derived from fatty acids with 8 to 22, preferably 12 to 18, carbon atoms.
• R 3 consists of linear or branched alkyl chains with 1 to 6, preferably 1 to 4, carbon atoms.
• Particularly preferred embodiments are the methyl esters, e.g. B.
• the a-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids can take place at the same time.
• the disalt can have a proportion of 10% to 50%. Its presence does not adversely affect the wash-active properties of the a-sulfoesters.
• the secondary sulfohydroxy esters contained as anionic surfactant components according to formula (IV) in at least one of the surfactant combinations according to the invention are derived from unsaturated fatty acids in which y is 0 or a number from 1 to 17, z is a number from 1 to 18 and the sum (y + z ) can be a number from 4 to 18, from.
• Preferred secondary sulfohydroxy esters are obtained if unsaturated fatty acids are used for the sulfonation, in which the sum (y + z) is a number from 8 to 18, preferably 8 to 14 and R 4 is a linear or branched alkyl radical having 1 to 6, preferably 1 represents up to 4 carbon atoms.
• Suitable fatty acids are therefore, for example, lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid, gadoleic acid and erucic acid, as well as mixtures of these and various oleate cuts obtainable from tallow fats.
• a particularly preferred embodiment is an ester according to the invention with y and z equal to 7, where R 4 is a branched alkyl radical with 4 carbon atoms, for example a secondary sulfohydroxy ester based on oleic acid isobutyl ester.
• the process for the preparation of the secondary sulfohydroxy esters is described in detail using the example of oleic acid lower alkyl ester sulfonates in the earlier application P 38 28 892.3.
• the sulfonation of the oleate cuts used can be carried out with gaseous sulfur trioxide in conventional sulfonation reactors, in particular of the falling film type, at temperatures in the preferred range from 15 to 30 ° C.
• Secondary dialkyl ether sulfates of the formula (V) can be obtained by reacting secondary hydroxydialkyl ethers of the general formula (VI) with gaseous sulfur trioxide and subsequent neutralization with aqueous alkali, alkaline earth or ammonium hydroxide.
• R ⁇ here means an aliphatic linear or branched, saturated alkyl radical having 1 to 18, preferably 1 to 8, in particular 4 to 8C atoms
• Rs is an aliphatic linear, saturated alkyl radical having 6 to 16, preferably 6 to 14 and in particular 10 to 12 C atoms means, the sum (Rs + R ⁇ ) being at least 7 and a maximum of 28 and preferably being between 14 and 18 C atoms.
• p can be a number from 1 to 30, preferably from 1 to 10
• n can be an integer from 2 to 4.
• N is preferably the number 2.
• Suitable further components of liquid or solid detergents and cleaning agents are, for the purposes of this invention, for.
• Suitable organic and inorganic builder substances are weakly acidic, neutral or alkaline salts, in particular alkali salts, which are able to precipitate or complex calcium ions to tie.
• alkali salts which are able to precipitate or complex calcium ions to tie.
• the water-soluble alkali metal or alkali polyphosphates in particular pentasodium triphosphate, are of particular importance in addition to the alkali ortho- and alkali pyrophosphates. All or part of these phosphates can be replaced by organic complexing agents for calcium ions.
• Suitable phosphorus-containing organic complexing agents are the water-soluble salts of alkanephosphonic acids, amino and hydroxyalkanephosphonic acids and phosphonopolycarboxylic acids such as.
• the nitrogen-free and phosphorus-free polycarboxylic acids which form complex salts with calcium ions which also include polymers containing carboxyl groups, are of particular importance.
• Polycarboxylic acids containing ether groups are also suitable, such as 2,2'-oxydisuccinic acid and polyhydric alcohols or hydroxycarboxylic acids partially or completely etherified with glycolic acid, e.g. B. biscarboxymethylethylene glycol, carboxymethyloxy succinic acid, carboxymethyl tartronic acid and carboxymethylated or oxidized polysaccharides.
• Polymeric carboxylic acids with a molecular weight of at least 350 in the form of water-soluble salts are also suitable.
• Particularly preferred polymeric polycarboxylates have a molecular weight in the range from 500 to 175,000 and in particular in the range from 10,000 to 100,000.
• These compounds include, for example, polyacrylic acid, polyhydroxyacrylic acid, polymaleic acid and the copolymers of the corresponding monomeric carboxylic acids with one another or with ethylenically unsaturated compounds such as vinyl methyl ether .
• the water-soluble salts of polyglyoxylic acid are also suitable.
• water-insoluble inorganic builders are, for. B. the finely divided, synthetic bound water containing sodium aluminosilicates of the zeolite A type described in DE-OS 24 12 837 as phosphate substitutes for detergents and cleaning agents.
• the cation-exchanging sodium aluminosilicates are used in the usual hydrated, finely crystalline form. They have practically no particles larger than 30 ⁇ m and preferably consist of at least 80% particles smaller than 10 ⁇ m.
• Your calcium binding capacity which is determined according to the details of DE-OS 24 12 837, is in the range of 100 to 200 mg CaO / g.
• Zeolite NaA is particularly suitable, as is zeolite NaX and mixtures of NaA and NaX.
• Suitable inorganic, non-complexing salts are the alkali salts of bicarbonates, carbonates, borates, sulfates and silicates, which are also referred to as "washing alkalis".
• alkali silicates especially the sodium silicates with a ratio of Na 2 0: Si0 2 such as 1: 1 to 1: 3.5 can be used.
• the detergents according to the invention can additionally contain bleaching agents and bleach activators.
• bleaching agents and bleach activators include sodium perborate tetrahydrate (NaB0 2 .H 2 0 2 .3H 2 0) and monohydrate (NaB0 2 .H 2 0 2 ) are of particular importance.
• other borates which supply H 2 0 2 can also be used, e.g. B. the Perborax Na 2 B 4 .0 7 . 4H 2 0 2 .
• These compounds can be partially or completely by other active oxygen carriers, in particular by peroxypyrophosphates, citrate perhydrates, urea / H 2 0 2 - or melamine / H 2 0 2 compounds as well as by H 2 0 2 delivering peracid salts such as.
• active oxygen carriers in particular by peroxypyrophosphates, citrate perhydrates, urea / H 2 0 2 - or melamine / H 2 0 2 compounds as well as by H 2 0 2 delivering peracid salts such as.
• KHSOs caroates
• perbenzoates or peroxyphthalates can be replaced.
• the detergents and cleaning agents can contain dirt carriers which keep the dirt detached from the fibers suspended in the liquor and thus prevent graying.
• water-soluble colloids usually of an organic nature, are suitable, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
• Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
• surfactants can also be added to the mixtures, provided that they do not interfere with the positive effect of the washing and cleaning agents according to the invention.
• the mixtures in experiment (b) contain the surfactant mixtures to be tested, consisting of anionic surfactant according to the formulas (II) to (V) and alkyl glycoside (I).
• a coconut alkyl glucoside (C 12 / C 14 ) was used as the alkyl glycoside.
• Composition (GC analysis): 62.8% by weight monoglucoside, 15.4% by weight diglucoside, 5.8% by weight triglucoside, 3% by weight residual fatty alcohol, 8% by weight polyglucose; Degree of oligomerization x 1.3.
• standard soiling was used.
• the reflectance values were determined photometrically (Zeiss reflectometer, for lipstick and make-up with a Y filter). Remission differences of 2% and more are significant.
• Surfactant mixture (a) from 12.5% by weight of dodecylbenzenesulfonate and 2.5% by weight of fatty alcohol ethoxylate
• surfactant mixture (b) from 12.5% by weight of saturated a-sulfoesters (III), consisting of a mixture of the sodium salts of a-Sulfotalgfett Textremethylestern, and 2.5 wt .-% (I).
• Example 6 was repeated with a mixing ratio in (a) and (b) of 7.5% by weight to 7.5% by weight.
• Example 7 was repeated with a mixing ratio in (a) and (b) of 12.5% by weight nonionic surfactant to 2.5% by weight anionic surfactant.
• saucers were coated with 2 g of mixed water, protein, fat and carbohydrates mixed with water. Then 8 liters of tap water (16 d) and 8 liters of softened water (3 d), each at 45 ° C., were placed in a bowl. To clean the soiled plates, 1.2 g of a cleaning agent consisting of an anionic surfactant according to formula (V) (DAES) and / or a C 12 / C 14 -alkyl glucoside (APG) used according to formula (I) were added and the plates washed until the foam of the solution disappears. The mixing ratio was varied as indicated in Table 9.
• DAES anionic surfactant according to formula (DAES)
• APG C 12 / C 14 -alkyl glucoside

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Citations (7)

• 1988
  • 1988-11-17 DE DE3838808A patent/DE3838808A1/de not_active Withdrawn
• 1989
  • 1989-11-08 EP EP89912904A patent/EP0445152A1/fr active Pending
  • 1989-11-08 EP EP19890120716 patent/EP0370312A3/fr not_active Withdrawn
  • 1989-11-08 KR KR1019900701530A patent/KR900701984A/ko not_active Application Discontinuation
  • 1989-11-08 WO PCT/EP1989/001334 patent/WO1990005772A2/fr not_active Application Discontinuation
  • 1989-11-08 JP JP2500158A patent/JPH04501734A/ja not_active Withdrawn
• 1991
  • 1991-05-16 DK DK91933A patent/DK93391D0/da not_active Application Discontinuation

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