EP1249489A1 - Detergent tablets with improved disintegration properties - Google Patents
Detergent tablets with improved disintegration properties Download PDFInfo
- Publication number
- EP1249489A1 EP1249489A1 EP02007552A EP02007552A EP1249489A1 EP 1249489 A1 EP1249489 A1 EP 1249489A1 EP 02007552 A EP02007552 A EP 02007552A EP 02007552 A EP02007552 A EP 02007552A EP 1249489 A1 EP1249489 A1 EP 1249489A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- alkyl
- alcohol
- detergent
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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- 239000003599 detergent Substances 0.000 title claims abstract description 59
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 41
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 28
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 239000013543 active substance Substances 0.000 claims abstract description 13
- -1 alkenyl sulfates Chemical class 0.000 claims description 137
- 125000004432 carbon atom Chemical group C* 0.000 claims description 59
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 47
- 239000000194 fatty acid Substances 0.000 claims description 47
- 229930195729 fatty acid Natural products 0.000 claims description 47
- 150000004665 fatty acids Chemical class 0.000 claims description 38
- 229920002678 cellulose Polymers 0.000 claims description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 30
- 239000001913 cellulose Substances 0.000 claims description 24
- 102000004190 Enzymes Human genes 0.000 claims description 21
- 108090000790 Enzymes Proteins 0.000 claims description 21
- 239000007884 disintegrant Substances 0.000 claims description 18
- 150000002170 ethers Chemical class 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 13
- 239000003205 fragrance Substances 0.000 claims description 12
- 102000004169 proteins and genes Human genes 0.000 claims description 12
- 108090000623 proteins and genes Proteins 0.000 claims description 12
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 11
- 239000003945 anionic surfactant Substances 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 239000004615 ingredient Substances 0.000 claims description 9
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 239000012459 cleaning agent Substances 0.000 claims description 7
- 239000000344 soap Substances 0.000 claims description 7
- 125000005907 alkyl ester group Chemical group 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
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- 125000002091 cationic group Chemical group 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
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- 150000001875 compounds Chemical class 0.000 description 20
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- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 18
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
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- ZFNVDHOSLNRHNN-UHFFFAOYSA-N xi-3-(4-Isopropylphenyl)-2-methylpropanal Chemical compound O=CC(C)CC1=CC=C(C(C)C)C=C1 ZFNVDHOSLNRHNN-UHFFFAOYSA-N 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- 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
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0086—Laundry tablets
-
- 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
-
- 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
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
Definitions
- the present invention is in the field of compact molded articles that are active in washing and cleaning Have properties.
- the invention relates to detergent tablets, used for washing textiles in a household washing machine and briefly as Detergent tablets are called.
- Detergent tablets are widely described in the prior art and enjoy popular with consumers because of the simple dosage. Tableted washing and Detergents have a number of advantages over powdered ones: they are easier to dose and to handle and have advantages in terms of storage and due to their compact structure while transporting. Detergent tablets are consequently also comprehensive in the patent literature described. A problem that occurs when using washing and cleaning active moldings occurs again and again, the decay and dissolving speed of the molded bodies is too low Conditions of use. Since sufficiently stable, i.e.
- shape and break resistant molded articles only can be produced by relatively high pressure, there is a strong compression of the molded parts and to a consequent delayed disintegration of the Shaped body in the aqueous liquor and thus to a slow release of the active substances in the washing or cleaning process.
- the delayed disintegration of the molded body continues to have Disadvantage that conventional detergent tablets do not pass through the induction chamber of Have household washing machines rinsed in as the tablets will not wash in quickly enough Secondary particles disintegrate that are small enough to be washed into the washing drum from the dispensing chamber to become.
- EP 0 522 766 A discloses moldings made from a compact, particulate detergent composition containing surfactants, builders and disintegration aids (for example based on cellulose), at least some of the particles being coated with the disintegration agent, which has both binder and disintegration action shows when dissolving the moldings in water.
- This document also indicates the general difficulty of producing moldings with adequate stability and good solubility at the same time.
- the particle size in the mixture to be pressed should be above 200 ⁇ m, the upper and lower limits of the individual particle sizes should not differ from one another by more than 700 ⁇ m.
- binders which may have an explosive effect (in particular polyethylene glycol) is disclosed in EP 0 711 828 A (Unilever), which describes detergent tablets which are produced by pressing a particulate detergent composition at temperatures between 28 ° C. and the melting point of the binder material , always pressing below the melting temperature. From the examples in this document it can be seen that the moldings produced in accordance with their teaching have higher breaking strengths if compression is carried out at elevated temperature.
- alkyl polyglycosides in detergent tablets has already been disclosed in DE 19754289 (Henkel). It is generally described here that the addition of alkylpolyglycosides improves the solubility of tablets, especially if they have high breaking strength. There is no restriction on the use of certain surfactants, nor are there specific quantitative ratios of the surfactants to one another.
- the present invention has for its object to provide detergent tablets, which have the desired properties of high hardness and mechanical stability and yet combine more favorable decay speeds.
- the invention accordingly relates to detergent tablets made of compressed particulate detergent and detergent, comprising surfactants and, if appropriate, further detergent components, characterized in that the tablets are surfactants from the group of fatty alcohol alkoxylates and alkyl polyglycosides in a ratio of 10: 1 to 1:10 , preferably 5: 1 to 1: 5, in particular 2: 1 to 1: 2 - based on the active substance content.
- Typical examples are fatty alcohol polyethylene glycol / polypropylene glycol ether of the formula (I) or fatty alcohol polypropylene glycol / polyethylene glycol ether of the formula (II) .
- Fatty alcohol polyethylene glycol / polypropylene glycol ethers of the formula (I) are preferred, R 1 O (CH 2 CH 2 O) n [CH 2 (CH 3 ) CHO] m H used, in which R 1 is an alkyl and / or alkylene radical having 8 to 22 carbon atoms, n is a number from 1 to 40, preferably 1 to 30, in particular 1 to 15, and m is 0 or a number of 1 to 10.
- Fatty alcohol polypropylene glycol / polyethylene glycol ether of the formula (II) can also preferably be used, R 2 O [CH 2 (CH 3 ) CHO] q (CH 2 CH 2 O) r H in which R 2 is an alkyl and / or alkylene radical having 8 to 22 carbon atoms, q is a number from 1 to 5 and r is a number from 0 to 15.
- the moldings contain fatty alcohol polyethylene glycol / polypropylene glycol ether of the formula (I) in which R 1 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, n is a number from 1 to 10, and m is 0 stands. These are addition products of 1 to 10 moles of ethylene oxide with monofunctional fatty alcohols.
- Fatty alcohol alkoxylates of the formula (1) are also preferably used, in which R 1 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, n is a number from 2 to 7 and m is a number from 3 to 7 stands. These are addition products of monofunctional alcohols alkoxylated first with 2 to 7 mol of ethylene oxide and then with 3 to 7 mol of propylene oxide.
- the detergent tablets according to the invention contain alkyl and alkenyl oligoglycosides, hereinafter referred to briefly as APG. These usually follow the formula (II), R 3 O [G] p in which R 3 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP 0301298 A1 and WO 90/03977.
- the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
- the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
- the index number p in the general formula (III) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10.
- Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.
- the alkyl or alkenyl radical R 3 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
- the alkyl or alkenyl radical R 3 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms.
- Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above.
- Alkyl oligoglucosides based on hardened C12 / 14 coconut alcohol with a DP of 1 to 3 are preferred.
- the detergent tablets contain 0.5 to 25% by weight, preferably 1 to 15% by weight, in particular 1 to 10% by weight, of alkyl polyglycosides - calculated as an active substance based on the shaped body.
- the detergent tablets form further nonionic surfactants contain, which are selected from the group that is formed by hydroxy mixed ethers, fatty acid lower alkyl esters and amine oxides.
- nonionic surfactants are, in addition to the alkylphenol polyglycol ethers already described, Fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated Triglycerides, mixed ethers or mixed formals, fatty acid N-alkylglucamides, protein hydrolyzates (especially vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, and polysorbates. If the nonionic surfactants contain polyglycol ether chains, these can be a conventional, but preferably have a narrow homolog distribution (narrow range).
- Preferred further nonionic surfactants are hydroxy mixed ethers of the formula (IV) R 4 O [CH 2 CHR 5 O] b [CH 2 CHR 6 O] y CR 7 HCH (OH) R 8 in which R 4 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, R 5 is hydrogen or a methyl or ethyl radical, R 6 is hydrogen or a methyl or ethyl radical, R 7 is hydrogen or an alkyl radical having 2 to 18 Carbon atoms and R 8 represents an alkyl radical having 2 to 22 carbon atoms.
- B stands for 0 or numbers from 1 to 40, y for 0 or numbers from 1 to 40, whereby the sum of x and y should be greater than / equal to 1.
- Hydroxy mixed ethers can be ring opening products of both internal olefins (R 7 is not hydrogen) or internal olefins (R 7 is hydrogen), the latter being preferred.
- R 8 CHOCHR 7 1,2-epoxyalkanes
- R 7 is hydrogen
- R 8 is an aliphatic saturated, straight-chain or branched alkyl radical having 2 to 22, in particular 6 to 16 carbon atoms, with alkoxylated alcohols ,
- Preferred hydroxy mixed ethers for the purposes of the invention are those derived from alkoxylates of monohydric alcohols of the formula R 4 -OH having 4 to 18 carbon atoms, where R 4 is an aliphatic, saturated, straight-chain or branched alkyl radical, in particular having 6 to 16 carbon atoms, and R 7 represents hydrogen.
- Suitable straight-chain alcohols are butanol-1, capron, ⁇ nanth, capryl, pelargon, caprinal alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, palmity alcohol, heptadecanol-1, stearyl alcohol, nonadecanol 1, arachidyl alcohol, heneicosanol-1, behenyl alcohol and their technical mixtures, as are obtained in the high-pressure hydrogenation of technical methyl esters based on fats and oils.
- branched alcohols examples include so-called oxo alcohols, which usually carry 2 to 4 methyl groups as branches and are produced by the oxo process, and so-called Guerbet alcohols, which are branched in the 2-position with an alkyl group.
- Suitable Guerbet alcohols are 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol and / or 2-octyldodecanol.
- the alcohols are used in the form of their alkoxylates, which are prepared in a known manner by reacting the alcohols in any order with ethylene oxide, propylene oxide and / or butylene oxide.
- Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (V) R 12 CO (OCH 2 CHR 9 ) s OR 10 in which R 12 CO stands for a linear or branched, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms, R 9 for hydrogen or methyl, R 10 for linear or branched alkyl radicals with 1 to 4 carbon atoms and s for numbers from 1 to 20 stands.
- Typical examples are the formal insert products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide in the methyl, ethyl, propyl, isopropyl, butyl and tert-butyl esters of caproic acid, caprylic acid, 2 -Ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linoienic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and technical and erucic mixtures.
- the products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite. Conversion products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.
- amine oxides Compounds of the formula (VI) and / or (VII) can be used as amine oxides .
- the preparation of the amine oxides of the formula (VI) starts from tertiary fatty amines which have at least one long alkyl radical and is oxidized in the presence of hydrogen peroxide.
- R 13 represents a linear or branched alkyl radical having 6 to 22, preferably 12 to 18 carbon atoms
- R 14 and R 15 independently of one another are R 13 or, if appropriate hydroxy-substituted alkyl radical having 1 to 4 carbon atoms.
- Amine oxides of the formula (VI) are preferably used, in which R 13 and R 14 are C 12/14 and C 12/18 cocoalkyl radicals and R 15 is a methyl or a hydroxyethyl radical. Also preferred are amine oxides of the formula (VI) in which R 13 represents a C 12/14 or C 12/18 cocoalkyl radical and R 14 and R 15 have the meaning of a methyl or hydroxyethyl radical.
- alkylamido -amine oxides of the formula (VII)
- the alkylamido radical R 17 CONH being obtained by the reaction of linear or branched carboxylic acids, preferably having 6 to 22, preferably having 12 to 18, carbon atoms, in particular from C 12/14 or C 12/18 - fatty acids with amines.
- R 18 represents a linear or branched alkylene group having 2 to 6, preferably 2 to 4 carbon atoms and R 14 and R 15 have the meaning given in formula (VI) .
- the detergent tablets can contain anionic surfactants.
- anionic surfactants are soaps, alkylbenzenesulfonates, secondary alkanesulfonates, Olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, Alkyl and / or alkenyl sulfates, alkyl ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, fatty alcohol (ether) phosphates, Monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, Mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their
- Anionic surfactants are preferably selected from the group consisting of alkyl and / or Alkenyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, soaps, monoglyceride (ether) sulfates and alkane sulfonates, in particular fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkane sulfonates and linear Alkylbenzenesulfonates.
- Alkyl and / or alkenyl sulfates which are also often referred to as fatty alcohol sulfates, are to be understood as meaning the sulfation products of primary alcohols which follow the formula (VIII) R 19 O-SO 3 X
- R 19 represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
- alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, aryl selenyl alcohol, elaidyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained from high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis.
- the sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts.
- Alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred.
- ether sulfates are known anionic surfactants which are produced on an industrial scale by SO 3 - or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
- SO 3 - or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
- ether sulfates are suitable which follow the formula (IX) R 20 O- (CH 2 CH 2 O) a SO 3 X in which R 20 represents a linear or branched alkyl and / or alkenyl radical with 6 to 22 carbon atoms, a for numbers from 1 to 10 and X for an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
- Typical examples are the sulfates of addition products with an average of 1 to 10 and in particular 2 to 5 mol ethylene oxide onto capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, oleyl alcohol, o
- the ether sulfates can have both a conventional and a narrow homolog distribution. It is particularly preferred to use ether sulfates based on adducts of an average of 2 to 3 mol ethylene oxide with technical C 12/14 or C 12/18 coconut fatty alcohol fractions in the form of their sodium and / or magnesium salts.
- Alkylbenzenesulfonates preferably follow the formula (X) R 21 -Ph-SO 3 X in which R 21 is a branched but preferably linear alkyl radical having 10 to 18 carbon atoms, Ph is a phenyl radical and X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
- R 21 is a branched but preferably linear alkyl radical having 10 to 18 carbon atoms
- Ph is a phenyl radical
- X is an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
- Dodecylbenzenesulfonates, tetradecylbenzenesulfonates, hexadecylbenzenesulfonates and their technical mixtures in the form of the sodium salts are preferably
- soaps are to be understood as meaning fatty acid salts of the formula (XI) R 22 CO-OX in which R 22 CO represents a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and again X stands for alkali and / or alkaline earth metal, ammonium, alkylammonium or alkanolammonium.
- Typical examples are the sodium, potassium, magnesium, ammonium and triethanolammonium salts of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaoleic acid, petoleic acid, linoleic acid, petoleic acid, linoleic acid, linoleic acid, petol acid Linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures.
- coconut or palm kernel fatty acid is preferably used in the form of its sodium or potassium salts.
- Monoglyceride sulfates and monoglyceride ether sulfates are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry.
- the usual starting point for their preparation is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized. It is also possible to react the partial glycerides with suitable sulfating agents, preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. EP 0561825 B1, EP 0561999 B1 (Henkel)].
- the neutralized substances can be subjected to ultrafiltration in order to reduce the electrolyte content to a desired level [DE 4204700 A1 (Henkel)].
- Overviews of the chemistry of the monoglyceride sulfates are, for example, by AK Biswas et al. in J.Am.Oil.Chem.Soc. 37 , 171 (1960) and FU Ahmed J.Am.Oil.Chem.Soc. 67 , 8 (1990).
- the monoglyceride (ether) sulfates to be used in accordance with the invention follow the formula (XII), in which R 23 C0 represents a linear or branched acyl radical having 6 to 22 carbon atoms, c, d and e in total 0 or numbers 1 to 30, preferably 2 to 10, and X represents an alkali or alkaline earth metal.
- Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride as well as their ethylene oxide adducts or their formulated with sulfuric acid trioxide.
- Monoglyceride sulfates of the formula (XII) are preferably used, in which R 23 CO represents a linear acyl radical having 8 to 18 carbon atoms.
- Alkane sulfonates can be divided into primary and secondary alkane sulfonates. This means compounds of the formula (XIII) where in primary alkanesulfonates R 24 is hydrogen and R 25 is an alkyl radical with no more than 50 carbons. The secondary alkanesulfonates are preferred.
- R 24 and R 25 represent alkyl radicals, where R 24 and R 25 together should not have more than 50 carbon atoms.
- the detergent tablets according to the invention contain cationic and / or amphoteric or zwitterionic surfactants selected from the Group formed by esterquats, alkyl betaines, alkyl amido betaines, imidazolinium betaines.
- cationic surfactants are tetraalkylammonium compounds, for example Dimethyldistearylammonium chloride or Hydroxyethyl Hydroxycetyl Dimmonium Chloride (Dehyquart® E).
- ester quats is particularly preferred.
- R 27 CO is an acyl radical having 6 to 22 carbon atoms
- R 28 and R 29 independently of one another are hydrogen or R 27 CO
- R 30 is an alkyl radical having 1 to 4 carbon atoms or a (CH 2 CH 2 O) x4 H- Group, x1, x2 and x3 in total for 0 or numbers from 1 to 12, x4 for numbers from 1 to 12 and Y for halide, alkyl sulfate or alkyl phosphate.
- ester quats that can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, in the pressure splitting of natural fats and oils.
- Technical C12 / 18 coconut fatty acids and in particular partially hardened C16 / 18 tallow or palm fatty acids as well as high elaidic acid C16 / 18 fatty acid cuts are preferably used.
- the fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters.
- an application ratio of 1.2 1 to 2.2 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous.
- the preferred ester quats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C16 / 18-tallow or palm fatty acid (iodine number 0 to 40).
- quaternized fatty acid triethanolamine ester salts of the formula (XIV) have proven to be particularly advantageous in which R 27 CO for an acyl radical having 16 to 18 carbon atoms, R 28 for R 27 CO, R 29 for hydrogen, R 30 for a methyl group, ( x1 + x2 + x3) is 0 and Y is methyl sulfate.
- quaternized ester salts of fatty acids with diethanolalkylamines of the formula (XV) are also suitable as esterquats.
- R 31 CO for an acyl radical with 6 to 22 carbon atoms
- R 32 for hydrogen or R 31 CO
- R 33 and R 34 independently of one another for alkyl radicals with 1 to 4 carbon atoms
- x5 and x6 in total for 0 or numbers from 1 to 12
- Y represents halide, alkyl sulfate or alkyl phosphate.
- ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (XVI) should be mentioned as a further group of suitable ester quats, in which R 35 CO for an acyl radical with 6 to 22 carbon atoms, R 36 for hydrogen or R 35 CO, R 37 , R 38 and R 39 independently of one another for alkyl radicals with 1 to 4 carbon atoms, x7 and x8 in total for 0 or numbers from 1 to 12 and Y represents halide, alkyl sulfate or alkyl phosphate.
- suitable ester quats are substances in which the ester bond is replaced by an amide bond and which preferably follow the formula (XVII) based on diethylenetriamine, in which R 40 CO represents an acyl radical with 6 to 22 carbon atoms, R 41 for hydrogen or R 40 CO, R 42 and R 43 independently of one another for alkyl radicals with 1 to 4 carbon atoms and Y for halide, alkyl sulfate or alkyl phosphate.
- Such amide ester quats are available on the market, for example, under the name Incroquat® (Croda).
- the detergent tablets can be alkylbetaines, Alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and / or sulfobetaines contain.
- alkyl betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XVIII) in which R 44 for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R 45 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 46 for alkyl radicals with 1 to 4 carbon atoms, y1 for numbers from 1 to 6 and Z for a Alkali and / or alkaline earth metal or ammonium.
- R 44 for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms
- R 45 for hydrogen or alkyl radicals with 1 to 4 carbon atoms
- R 46 for alkyl radicals with 1 to 4 carbon atoms
- y1 for numbers from 1 to 6 and Z for a Alkali and / or alkaline earth metal or ammonium.
- Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine, C12 / 14-cocoalkyldimethylamine, myristyldimethylamine, cetyldimethylethylethylstimethylmethylamine, stearyldimethylamine, stearyldimethylamine, stearyldimethylamine, stearyldimethylamine, stearyldimethylamine, stearyldimethylamine, stearyldimethylamine, stearyldimethylamine, stamyldimethylamine, stamethyldimethylamine, stamethyldimethylamine, stamethyldimethylamine, stamethyldimethylamine, stamethyldimethylamine, stamethyldimethylamine, stamethyldimethylamine, stamethyld
- Carboxyalkylation products of amidoamines which follow the formula (XIX) are also suitable, in the R 47 CO for an aliphatic acyl radical with 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R 48 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 49 for alkyl radicals with 1 to 4 carbon atoms, y2 and y3 independently of one another represents numbers from 1 to 6 and Z represents an alkali and / or alkaline earth metal or ammonium.
- Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and arachic acid, arachic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C8 / 18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.
- Imidazolinium betaines are also suitable. These substances are also involved known substances, for example by cyclizing condensation of 1 or 2 moles of fatty acid obtained with polyvalent amines such as aminoethyl ethanolamine (AEEA) or diethylene triamine can be. The corresponding carboxyalkylation products make mixtures different open-chain betaines. Typical examples are condensation products of the above Fatty acids with AEEA, preferably imidazolines based on lauric acid or again C12 / 14 coconut fatty acid, which are then betainized with sodium chloroacetate.
- AEEA aminoethyl ethanolamine
- diethylene triamine diethylene triamine
- the surfactant granules according to the invention can contain disintegrants.
- disintegrant is to be understood as meaning substances which are contained in the surfactant granules in order to accelerate their disintegration when brought into contact with water. Overviews can be found, for example, in J.Pharm.Sci. 61 (1972) or Römpp Chemielexikon, 9th edition, volume 6, p. 4440.
- the disintegrants can be present in the granules homogeneously distributed macroscopically, but from a microscopic point of view they can form zones of increased concentration due to the manufacturing process.
- the preferred disintegrants include polysaccharides, such as, for example, natural starch and its derivatives (carboxymethyl starch, starch glycolates in the form of their alkali salts, agar agar, guar gum, pectins etc.), celluloses and their derivatives (carboxymethyl cellulose, microcrystalline cellulose), polyvinylpyrrolidone, collidone, alginic acid and their alkali salts (alginates), amorphous or also partially crystalline layered silicates (bentonites), polyurethanes, polyethylene glycols and gas-generating systems.
- polysaccharides such as, for example, natural starch and its derivatives (carboxymethyl starch, starch glycolates in the form of their alkali salts, agar agar, guar gum, pectins etc.), celluloses and their derivatives (carboxymethyl cellulose, microcrystalline cellulose), polyvinylpyrrolidone, collidon
- the detergent tablets contain 0.5 to 10% by weight, preferably 1 to 7% by weight and in particular 2 to 6% by weight of a disintegration aid, each based on the weight of the molded body.
- Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 1 to 7% by weight and in particular 2 contain up to 6 wt .-%.
- Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a ⁇ -1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
- Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
- Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
- Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
- celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
- the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
- the cellulose derivatives mentioned are preferably not used alone as cellulose-based disintegrants used, but used in a mixture with cellulose.
- the content of these mixtures Cellulose derivatives is preferably below 50% by weight, particularly preferably below 20 wt .-%, based on the disintegrant based on cellulose. Is particularly preferred as Cellulose-based disintegrant used pure cellulose that is free of cellulose derivatives.
- microcrystalline cellulose As a further disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used.
- This microcrystalline cellulose is made by partial hydrolysis obtained from celluloses under conditions that only the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses attack and completely dissolve the crystalline areas (approx. 70%) but leave it undamaged.
- a subsequent disaggregation by hydrolysis The resulting micro-fine celluloses provide the microcrystalline celluloses, the primary particle sizes 5 ⁇ m and, for example, to granules with an average particle size of 200 ⁇ m are compactible.
- the detergent tablets may preferably have one or more further auxiliaries and Additives, from the group of builders, optical brighteners, enzymes, enzyme stabilizers, defoamers, Co-disintegrants, proteins and protein derivatives, small amounts of neutral filling salts as well as dyes and fragrances.
- Zeolites for example, can be used as builders .
- the fine crystalline, synthetic and bound water-containing zeolite which is frequently used as a detergent builder is preferably zeolite A and / or P.
- zeolite P for example, zeolite MAP (R) (commercial product from Crosfield) is particularly preferred.
- zeolite X and mixtures of A, X and / or P and Y are also suitable.
- zeolite X and mixtures of A, X and / or P and Y are also suitable.
- zeolite X and mixtures of A, X and / or P and Y are also suitable.
- VEGOBOND AX® commercial product from Condea Augusta SpA
- the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
- the zeolite can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties.
- the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
- the term “amorphous” is also understood to mean “X-ray amorphous”.
- silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
- it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
- Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 4400024 A1.
- Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
- phosphates as builders, unless such use should be avoided for ecological reasons.
- Suitable are in particular the sodium salts of orthophosphates, pyrophosphates and in particular Tripolyphosphate.
- Their content is generally not more than 25% by weight, preferably not more than 20 wt .-%, each based on the finished agent.
- tripolyphosphates even in small amounts up to a maximum of 10% by weight, based on the finished agents, in combination with other builder substances to a synergistic improvement of the Secondary washing power.
- the builders are in the detergent tablets from 0 to 70, preferably in amounts from 10 to 60% by weight, in particular 20 to 40% by weight, based on the shaped body.
- Usable organic builders are, for example, those that can be used in the form of their sodium salts
- Polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, Sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use from ecological Reasons is not objectionable, as well as mixtures of these.
- Preferred salts are the Salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, Sugar acids and mixtures of these. The acids themselves can also be used.
- acids typically also have the property of an acidifying component and thus also serve to set a lower and milder one pH value of detergents or cleaning agents.
- citric acid succinic acid
- glutaric acid glutaric acid
- adipic acid glutaric acid
- gluconic acid any mixtures of these.
- Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
- the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000.
- DE dextrose equivalent
- Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2,000 to 30,000 are common.
- a preferred dextrin is in British patent application GB 9419091 A1 described.
- the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
- Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0232202 A1, EP 0427349 A1, EP 0472042 A1 and EP 0542496 A1 as well as from international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94 / 28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known.
- An oxidized oligosaccharide according to German patent application DE 19600018 A1 is also suitable.
- a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
- Suitable cobuilders are oxidisuccinates and other derivatives of disuccinates, preferably Ethylenediamine. Glycerol disuccinates are also particularly preferred in this context and glycerol trisuccinates, as described, for example, in the US patents US 4,524,009, US 4,639,325, in European patent application EP 0150930 A1 and the Japanese patent application JP 93/339896. Suitable amounts are in Formulations containing zeolite and / or silicate at 3 to 15% by weight.
- organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which at least Contain 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups, Such cobuilders are described, for example, in international patent application WO 95/20029.
- Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or Polymethacrylic acid, for example those with a molecular weight of 800 to 150,000 (on Acid sourced and measured against polystyrene sulfonic acid).
- Suitable copolymeric polycarboxylates are especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable proven to contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid.
- Your relative Molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (measured in each case against polystyrene sulfonic acid).
- the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution are, with 20 to 55 wt .-% aqueous solutions are preferred.
- Granular polymers are usually mixed into one or more basic granules.
- biodegradable polymers from more than two different monomer units, for example those which according to DE 4300772 A1 as monomers salts of acrylic acid and Maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers according to DE 4221381 C2 Contain salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
- Further preferred copolymers are those described in German patent applications DE 4303320 A1 and DE 4417734 A1 and as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
- Builder substances include polymeric aminodicarboxylic acids, their salts or their precursors call. Polyaspartic acids or their salts and derivatives are particularly preferred.
- polyacetals which are reacted with dialdehydes
- dialdehydes Polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example can be obtained as described in European patent application EP 0280223 A1.
- Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde as well as their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid receive.
- the moldings can also contain components that allow oil and fat to be washed out made of textiles.
- the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and also from polymers of phthalic acid and / or terephthalic acid or of known from the prior art their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these.
- the sulfonated derivatives of phthalic acid and terephthalic acid polymers are especially preferred among these.
- Suitable ingredients are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses, which have no outstanding builder properties, or mixtures of these; in particular, alkali carbonate and / or amorphous alkali silicate, especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
- the content of sodium carbonate in the final preparations is preferably up to 40% by weight, advantageously between 2 and 35% by weight.
- the content of sodium silicate in the agents (without special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.
- bleaching agents which serve as bleaching agents and supply H 2 O 2 in water
- sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
- the bleaching agent content is preferably 0 to 35% by weight and in particular up to 30% by weight, advantageously using perborate monohydrate or percarbonate.
- Compounds which are aliphatic peroxocarboxylic acids under perhydrolysis conditions can be used as bleach activators with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally result in substituted perbenzoic acid can be used.
- Substances that are suitable O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups wear.
- Multi-acylated alkylenediamines are preferred (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and from the German patent applications DE 19616693
- bleach activators or in their place can also be those from the European patent specifications EP 0446982 B1 and EP 0453 003 B1 known sulfonimines and / or bleach-enhancing Transition metal salts or transition metal complexes as so-called bleaching catalysts be included.
- the transition metal compounds in question include in particular the manganese, iron, cobalt, ruthenium known from German patent application DE 19529905 A1 or molybdenum-salt complexes and their from German patent application DE 19620267 A1 known N-analog connections, which are known from German patent application DE 19536082 A1
- Manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes which in the German Patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, Titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, derived from the German Patent application DE 19620411 A1 known cobalt, iron, copper and ruthenium amine complexes, the manganese, copper and cobalt complexes described in German patent application DE 4416438 A1, the cobalt complexes described in European patent application EP 0272030 A1, the manganese complexes known from the European patent application EP 0693550
- bleach-boosting Transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are in usual amounts, preferably in an amount up to 1 wt .-%, especially of 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the molded body used.
- Particularly suitable enzymes are those from the class of hydrolases, such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can help maintain color and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.
- hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and micro
- Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable.
- Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
- Enzyme mixtures for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
- Known cutinases are examples of such lipolytically active enzymes.
- Peroxidases or oxidases have also proven to be suitable in some cases.
- Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
- Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
- the enzymes can be adsorbed on carriers and / or embedded in coating substances around them protect against premature decomposition.
- the percentage of enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
- 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.
- calcium salts magnesium salts also serve as stabilizers.
- 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.
- Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
- Water-soluble colloids of mostly organic nature are suitable for this, 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, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
- cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the shaped body, are preferably used .
- the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
- Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brighteners can also be used.
- Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also in small amounts, for example Contain 10 -6 to 10 -3 wt .-%, preferably by 10 -5 wt .-%, of a blue dye.
- a particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).
- soil release polymers are those which are suitable are, preferably ethylene terephthalate and / or polyethylene glycol terephthalate contained, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate in the range of 50: 50 to 90: may be 10 degrees.
- the molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100.
- the polymers are characterized by an average molecular weight of about 5000 to 200,000 and can have a block, but preferably a random structure.
- Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Also preferred are those polymers which have linking polyethylene glycol units with a molecular weight of 750 to 5000, preferably of 1000 to about 3000 and a molecular weight of the polymer from about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).
- Wax-like compounds can be used as defoamers .
- Compounds which have a melting point at atmospheric pressure above 25 ° C. (room temperature), preferably above 50 ° C. and in particular above 70 ° C., are understood to be “waxy”.
- the waxy defoamer substances are practically insoluble in water, ie at 20 ° C. they have a solubility of less than 0.1% by weight in 100 g of water.
- all wax-like defoamer substances known from the prior art can be contained.
- Suitable waxy compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohols, and paraffin waxes or mixtures thereof.
- the silicone compounds known for this purpose can of course also be used.
- Suitable paraffin waxes generally represent a complex mixture of substances without a sharp melting point. For characterization, one usually determines its melting range by differential thermal analysis (DTA), as described in "The Analyst” 87 (1962), 420, and / or its solidification point This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., cannot be used according to the invention. For example, the paraffin wax mixtures known from EP 0309931 A1 of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point of 62 ° C.
- paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and is preferably absent entirely.
- Particularly preferred paraffin wax mixtures at 30 ° C have a liquid fraction of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid fraction of less than 30% by weight, preferably of 5 % By weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular 40% by weight % to 55% by weight, at 80 ° C a liquid content of 80% by weight to 100% by weight, and at 90 ° C a liquid content of 100% by weight.
- the temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C. in particularly preferred paraffin wax mixtures, in particular at 75 ° C. to 82 ° C.
- the paraffin waxes can be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.
- Suitable bisamides as defoamers are those which differ from saturated fatty acids with 12 to 22, preferably derived from 14 to 18 carbon atoms and from alkylenediamines with 2 to 7 carbon atoms.
- suitable Fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof as they are from natural fats or hardened oils, such as tallow or hydrogenated palm oil are.
- Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, Pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
- Preferred diamines are ethylenediamine and hexamethylenediamine.
- Bismyristoylethylenediamine, particularly preferred bisamides are Bispalmitoylethylenediamine, bisstearoylethylenediamine and their mixtures and the corresponding derivatives of hexamethylenediamine.
- Suitable carboxylic acid esters as defoamers are derived from carboxylic acids with 12 to 28 carbon atoms.
- these are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid.
- the alcohol part of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain.
- suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol as well as ethylene glycol, glycerin, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol.
- Preferred esters are those of ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid.
- Eligible esters of polyhydric alcohols are, for example, xylitol monopalmitate, pentarythritol monostearate, glycerol monostearate, ethylene glycol monostearate and sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan dilaurate, sorbitan dististearate, sorbitan dandghenoate and mixed sorbitan dibehenate, and sorbitan dandebehenate, and sorbitan dandebehenate as well as mixed sorbitan dandebehenate and sorbitan dandebiolate.
- Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred. Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this.
- esters as defoamers are beeswax, which mainly consists of the esters CH 3 (CH 2 ) 24 COO (CH 2 ) 27 CH 3 and CH 3 (CH 2 ) 26 COO (CH 2 ) 25 CH 3 , and carnauba wax , which is a mixture of carnauba acid alkyl esters, often in combination with small amounts of free carnauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.
- beeswax which mainly consists of the esters CH 3 (CH 2 ) 24 COO (CH 2 ) 27 CH 3 and CH 3 (CH 2 ) 26 COO (CH 2 ) 25 CH 3
- carnauba wax which is a mixture of carnauba acid alkyl esters, often in combination with small amounts of free carnauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.
- Suitable carboxylic acids as a further defoamer compound are in particular behenic acid, stearic acid, Oleic acid, palmitic acid, myristic acid and lauric acid and their mixtures, as made up natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil are. Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred.
- Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of those described Fatty acids.
- Dialkyl ethers may also be present as defoamers.
- the ethers can be asymmetric or be constructed symmetrically, i.e. two identical or different alkyl chains, preferably containing 8 to 18 carbon atoms.
- Typical examples are di-n-octyl ether, Di-i-octyl ether and di-n-stearyl ether, particularly suitable are dialkyl ethers which have a melting point have above 25 ° C, in particular above 40 ° C.
- Suitable defoamer compounds are fatty ketones, which are based on the relevant methods of preparative organic chemistry can be obtained.
- carboxylic acid magnesium salts which at temperatures above 300 ° C below Elimination of carbon dioxide and water are pyrolyzed, for example according to the German Offenlegungsschrift 2553900.
- Suitable fatty ketones are those obtained by pyrolysis of the magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, Petroselinic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid can be produced.
- Suitable defoamers are fatty acid polyethylene glycol esters, which are preferably basic homogeneously catalyzed addition of ethylene oxide to fatty acids can be obtained. Especially done the addition of ethylene oxide to the fatty acids in the presence of alkanolamines as catalysts.
- alkanolamines especially triethanolamine, leads to an extremely selective ethoxylation fatty acids, especially when it comes to producing low-ethoxylated compounds.
- those which have one Have melting point above 25 ° C, especially above 40 ° C.
- the paraffin waxes described are particularly preferably used alone as wax-like defoamers or in a mixture with one of the other wax-like defoamers, the proportion of paraffin waxes in the mixture preferably making up more than 50% by weight, based on the waxy defoamer mixture.
- the paraffin waxes can be applied to carriers if necessary. All known inorganic and / or organic carrier materials are suitable as carrier materials. Examples of typical inorganic carrier materials are alkali carbonates, aluminosilicates, water-soluble sheet silicates, alkali silicates, alkali sulfates, for example sodium sulfate, and alkali phosphates.
- the alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO 2 of 1: 1.5 to 1: 3.5.
- the use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water.
- the aluminosilicates referred to as carrier material include, in particular, the zeolites, for example zeolite NaA and NaX.
- the compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass. Silicates which are commercially available under the name Aerosil® or Sipernat® can also be used.
- suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch.
- Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof.
- Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit.
- the mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50.
- native starch which is composed of amylose and amylopectin. Starch is referred to as native starch as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat.
- Carrier materials which can be used individually or more than one of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch.
- alkali carbonates in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate and zeolites are particularly suitable.
- Suitable silicones are conventional organopolysiloxanes, which contain finely divided silica in turn can also be silanized.
- organopolysiloxanes are, for example described in European patent application EP 0496510 A1.
- Polydiorganosiloxanes are particularly preferred, which are known from the prior art. But it can also use siloxane crosslinked compounds are used, as they are known to those skilled in the art under the name silicone resins are known.
- the polydiorganosiloxanes contain finely divided silica, which also silanes can be.
- Silica-containing dimethylpolysiloxanes are particularly suitable.
- the polydiorganosiloxanes have a Brookfield viscosity at 25 ° C in the range from 5,000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas.
- the silicones are preferably on carrier materials applied. Suitable carrier materials are already in connection with the paraffins have been described.
- the carrier materials are generally in amounts of 40 to 90% by weight, preferably in amounts of 45 to 75% by weight, based on defoamers.
- Shaped bodies can also contain co-disintegrants , such as polyvinylpyrrolidone, collidone, alginic acid and their alkali metal salts, amorphous or also partially crystalline layered silicates (bentonites), polyurethanes, polyethylene glycols and gas-generating systems.
- co-disintegrants such as polyvinylpyrrolidone, collidone, alginic acid and their alkali metal salts, amorphous or also partially crystalline layered silicates (bentonites), polyurethanes, polyethylene glycols and gas-generating systems.
- Proteins and protein derivatives may also be present, which have the resolving power of the invention Improve surfactant mixtures significantly.
- Expressly here is the unpublished Application DE 19956802 referenced, the disclosure of which is also part of the disclosure of the present Invention is made.
- Protein hydrolyzates and their condensation products with fatty acids are preferred as protein components, and subordinate protein hydrolyzate esters and quaternized protein fatty acid condensates are also suitable.
- Protein hydrolysates are degradation products of animal or vegetable proteins, for example collagen, elastin or keratin and preferably almond and potato protein, and in particular wheat, rice and soy protein, which are cleaved by acidic, alkaline and / or enzymatic hydrolysis and then have an average molecular weight in Have range from 600 to 4000, preferably 2000 to 3500.
- protein hydrolyzates do not represent a surfactant in the classic sense due to the lack of a hydrophobic residue, they are widely used for the formulation of surface-active agents because of their dispersing properties.
- Anionic surfactants so-called protein fatty acid condensates, which have properties comparable to soaps, can be produced from the protein hydrolyzates by condensation with C 6 -C 22 , preferably C 12 -C 18 fatty acids.
- fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances .
- Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexylpropylatepylatepylatepylatepionate, stally.
- the ethers include, for example, benzyl ethyl ether
- the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal
- the ketones include, for example, the jonones, ⁇ -isomethylionone and methylcedryl ketone the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol
- the hydrocarbons mainly include the terpenes such as limonene and pinene, but preference is given to using mixtures of different fragrances which together produce an appealing fragrance.
- Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
- the fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release.
- Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
- the final preparations can also contain inorganic salts as fillers or fillers , for example sodium sulfate, which is preferably present in amounts of 0 to 20, in particular 1 to 12,% by weight, based on the shaped body.
- inorganic salts for example sodium sulfate, which is preferably present in amounts of 0 to 20, in particular 1 to 12,% by weight, based on the shaped body.
- Shaped bodies preferably tablets, are generally produced by Tableting or press agglomeration.
- the particulate press agglomerates obtained can either used directly as a detergent or previously treated by customary methods and / or processed.
- the usual post-treatments include powdering with finely divided ingredients of detergents or cleaning agents, which means the bulk density in general is further increased.
- the procedure is also a preferred aftertreatment according to German patent applications 19524287 A1 and 19547457 A1, being dust-like or at least finely divided ingredients (the so-called fine fractions) of those produced according to the invention
- Particulate process end products, which serve as the core, are glued and thus Means are created which have these so-called fines as an outer shell. advantageously, this in turn occurs through melting agglomeration.
- the solid detergents are in tablet form, these tablets in particular from storage and transport technology Reasons preferably have rounded corners and edges.
- the base of these tablets can be circular or rectangular, for example.
- the Colors blue, green, white, pink and their color combinations are particularly preferred.
- the Tablets can also contain pressed and unpressed parts.
- Molded body with special advantageous dissolution rates are obtained if the granular components before pressing a proportion of particles having a diameter outside the range of 0.02 to 6 mm have less than 20, preferably less than 10 wt .-%.
- a particle size distribution is preferred in the range from 0.05 to 2.0 and particularly preferably from 0.2 to 1.0 mm.
- Shaped bodies can be produced in a predetermined size and shape by predetermined spatial shapes. Practically all expediently manageable configurations come into consideration as the spatial shape, for example So the training as a board, the rod or bar shape, cubes, cuboids and the like Room elements with flat side surfaces and, in particular, cylindrical configurations circular or oval cross section. This last embodiment covers the form of presentation from tablets to compact cylinder pieces with a ratio of height to diameter above 1.
- the portioned compacts can each be designed as separate individual elements be, which corresponds to the predetermined dosage of detergents and / or cleaning agents. Likewise but it is possible to form compacts that have a plurality of such mass units in one compact connect, the portionability being easy to separate, in particular by predetermined predetermined breaking points smaller units is provided.
- the usual type with horizontally arranged mechanics can be the portioned Moldings as tablets, in cylindrical or cuboid form, are expedient, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.
- Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, especially for manufacturing such compacts.
- the spatial shape of another embodiment of the shaped bodies is the induction chamber adapted from commercially available household washing machines, so that the moldings without metering aid can be dosed directly into the induction chamber, where they are during the induction process dissolves.
- the detergent tablets via a metering aid easily possible and preferred in the context of the present invention.
- Another preferred shaped body that can be produced has a plate-like or sheet-like shape Structure with alternating thick long and thin short segments, so that individual segments broken off from this "bolt" at the predetermined breaking points, which represent the short, thin segments and can be entered into the machine.
- This principle of the "bar-shaped" shaped body detergent can also be in other geometric shapes, for example vertical triangles, which are connected to each other only on one of their sides, can be realized.
- Table 1 shows test formulations for detergent tablets and their solubilities.
- the data relate to% by weight, based on the shaped body, and the wash-active substances (coconut alcohol sulfate sodium salt, LAS, fatty alcohol alkoxylate FAAO, C12 / 14-alkyl polyglucopside APG) were calculated on active substance (*).
- the active substance describes the absolute content of wash-active substances.
- Recipes are balanced to 100% using sodium sulfate (ad 100).
- the moldings can contain up to 15% by weight of free or bound water, which is introduced, for example, by using builders or disintegrants.
- the hardness of the tablets was measured by deforming the tablet to fracture, the force acting on the side surfaces of the tablet and the maximum force that the tablet was able to withstand.
- composition 1 2 3 4 5 6 V1 V2 V3 V4
- Coconut alcohol sulfate sodium salt 1 3.2 (3 *) 3.2 (3 *) 6.3 (6 *) 6.3 (6 *) 3.2 (3 *) 6.3 (6 *) 3.2 (3 *) 3.2 (3 *) 3.2 (3 *) LAS 2) 8.6 (6 *) 8.6 (6 *) 8.6 (6 *) 4.3 (3 *) 4.3 (3 *) 8.6 (6 *) 4.3 (3 *) 8.6 (6 *) 8.6 (6 *) Fatty alcohol alkoxylate FAAO 3) 2 (2 *) 4 (4 *) 5 (5 *) 2 (2 *) 4 (4 *) 5 (5 *) 6 (6 *) 6 (6 *) 5.6 (5.6 *) 0.4 (0.4 *) C12 / 14-alkyl polyglucopside APG 4) 8 (4 *) 4 (2 *) 2 (1 * ) 8 (4 *) 4 (2 *) 2 (1 *) - - 0.8 (0.4 *) 11.2 (5.6 *) FAAO / APG ratio - based on active substance
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Abstract
Description
Die vorliegende Erfindung liegt auf dem Gebiet der kompakten Formkörper, die wasch- und reinigungsaktive Eigenschaften aufweisen. Insbesondere betrifft die Erfindung Wasch- und Reinigungsmittelformkörper, die zum Waschen von Textilien in einer Haushaltswaschmaschine eingesetzt und kurz als Waschmitteltabletten bezeichnet werden.The present invention is in the field of compact molded articles that are active in washing and cleaning Have properties. In particular, the invention relates to detergent tablets, used for washing textiles in a household washing machine and briefly as Detergent tablets are called.
Wasch- und Reinigungsmittelformkörper sind im Stand der Technik breit beschrieben und erfreuen sich beim Verbraucher wegen der einfachen Dosierung zunehmender Beliebtheit. Tablettierte Wasch- und Reinigungsmittel haben gegenüber pulverförmigen eine Reihe von Vorteilen: Sie sind einfacher zu dosieren und zu handhaben und haben aufgrund ihrer kompakten Struktur Vorteile bei der Lagerung und beim Transport. Auch in der Patentliteratur sind Wasch- und Reinigungsmittelformkörper folglich umfassend beschrieben. Ein Problem, das bei der Anwendung von wasch- und reinigungsaktiven Formkörpern immer wieder auftritt, ist die zu geringe Zerfalls- und Lösegeschwindigkeit der Formkörper unter Anwendungsbedingungen. Da hinreichend stabile, d.h. form- und bruchbeständige Formkörper nur durch verhältnismäßig hohe Preßdrucke hergestellt werden können, kommt es zu einer starken Verdichtung der Formkörperbestandteile und zu einer daraus folgenden verzögerten Desintegration des Formkörpers in der wäßrigen Flotte und damit zu einer zu langsamen Freisetzung der Aktivsubstanzen im Wasch- bzw. Reinigungsvorgang. Die verzögerte Desintegration der Formkörper hat weiterhin den Nachteil, dass sich übliche Wasch- und Reinigungsmittelformkörper nicht über die Einspülkammer von Haushaltswaschmaschinen einspülen lassen, da die Tabletten nicht in hinreichend schneller Zeit in Sekundärpartikel zerfallen, die klein genug sind, um aus Einspülkammer in die Waschtrommel eingespült zu werden.Detergent tablets are widely described in the prior art and enjoy popular with consumers because of the simple dosage. Tableted washing and Detergents have a number of advantages over powdered ones: they are easier to dose and to handle and have advantages in terms of storage and due to their compact structure while transporting. Detergent tablets are consequently also comprehensive in the patent literature described. A problem that occurs when using washing and cleaning active moldings occurs again and again, the decay and dissolving speed of the molded bodies is too low Conditions of use. Since sufficiently stable, i.e. shape and break resistant molded articles only can be produced by relatively high pressure, there is a strong compression of the molded parts and to a consequent delayed disintegration of the Shaped body in the aqueous liquor and thus to a slow release of the active substances in the washing or cleaning process. The delayed disintegration of the molded body continues to have Disadvantage that conventional detergent tablets do not pass through the induction chamber of Have household washing machines rinsed in as the tablets will not wash in quickly enough Secondary particles disintegrate that are small enough to be washed into the washing drum from the dispensing chamber to become.
Zur Überwindung der Dichotomie zwischen Härte, d.h. Transport- und Handhabungsstabilität, und leichtem Zerfall der Formkörper sind im Stand der Technik viele Lösungsansätze entwickelt worden. Ein insbesondere aus der Pharmazie bekannter und auf das Gebiet der Wasch- und Reinigungsmittelformkörper ausgedehnter Ansatz ist die Inkorporation bestimmter Desintegrationshilfsmittel, die den Zutritt von Wasser erleichtern oder bei Zutritt von Wasser quellen bzw. gasentwickelnd oder in anderer Form desintegrierend wirken. Andere Lösungsvorschläge aus der Patentliteratur beschreiben die Verpressung von Vorgemischen bestimmter Teilchengrößen, die Trennung einzelner Inhaltsstoffe von bestimmten anderen Inhaltsstoffen sowie die Beschichtung einzelner Inhaltsstoffe oder des gesamten Formkörpers mit Bindemitteln. To overcome the dichotomy between hardness, i.e. Transport and handling stability, and easy disintegration of the shaped bodies, many solutions have been developed in the prior art. On especially known from pharmacy and in the field of detergent tablets extended approach is the incorporation of certain disintegration aids that provide access facilitate water or swell when water enters or develops gas or in some other form act disintegrating. Other proposed solutions from the patent literature describe compression of premixes of certain particle sizes, the separation of individual ingredients from certain other ingredients as well as the coating of individual ingredients or the whole Shaped body with binders.
So offenbart die EP 0 522 766 A (Unilever) Formkörper aus einer kompaktierten, teilchenförmigen Waschmittelzusammensetzung, enthaltend Tenside, Builder und Desintegrationshilfsmittel (beispielsweise auf Cellulosebasis), wobei zumindest ein Teil der Partikel mit dem Desintegrationsmittel beschichtet ist, das sowohl Binder- als auch Desintegrationswirkung beim Auflösen der Formkörper in Wasser zeigt. Diese Schrift weist auch auf die generelle Schwierigkeit hin, Formkörper mit adäquater Stabilität bei gleichzeitig guter Löslichkeit herzustellen. Die Teilchengröße im zu verpressenden Gemisch soll dabei oberhalb von 200 µm liegen, wobei Ober- und Untergrenze der einzelnen Teilchengrößen um nicht mehr als 700 µm voneinander abweichen sollen.For example, EP 0 522 766 A (Unilever) discloses moldings made from a compact, particulate detergent composition containing surfactants, builders and disintegration aids (for example based on cellulose), at least some of the particles being coated with the disintegration agent, which has both binder and disintegration action shows when dissolving the moldings in water. This document also indicates the general difficulty of producing moldings with adequate stability and good solubility at the same time. The particle size in the mixture to be pressed should be above 200 µm, the upper and lower limits of the individual particle sizes should not differ from one another by more than 700 µm.
Weitere Schriften, die sich mit der Herstellung vom Waschmittelformkörpern befassen, sind die EP 0 716 144 A (Unilever), die Formkörper mit einer externen Hülle aus wasserlöslichem Material beschreibt, sowie die EP 0 711 827 A (Unilever), die als Inhaltsstoff ein Citrat mit einer definierten Löslichkeit enthalten.Other documents that deal with the production of detergent tablets are EP 0 716 144 A (Unilever), which describes tablets with an external shell made of water-soluble material, and EP 0 711 827 A (Unilever), which contains a citrate as an ingredient contain with a defined solubility.
Der Einsatz von Bindemitteln, die gegebenenfalls Sprengwirkung entfalten (insbesondere Polyethylenglycol), wird in der EP 0 711 828 A (Unilever) offenbart, die Waschmittelformkörper beschreibt, welche durch Verpressen einer teilchenförmigen Waschmittelzusammensetzung bei Temperaturen zwischen 28°C und dem Schmelzpunkt des Bindematerials hergestellt werden, wobei stets unterhalb der Schmelztemperatur verpreßt wird. Aus den Beispielen dieser Schrift ist zu entnehmen, dass die gemäß ihrer Lehre hergestellten Formkörper höhere Bruchfestigkeiten aufweisen, wenn bei erhöhter Temperatur verpreßt wird.The use of binders which may have an explosive effect (in particular polyethylene glycol) is disclosed in EP 0 711 828 A (Unilever), which describes detergent tablets which are produced by pressing a particulate detergent composition at temperatures between 28 ° C. and the melting point of the binder material , always pressing below the melting temperature. From the examples in this document it can be seen that the moldings produced in accordance with their teaching have higher breaking strengths if compression is carried out at elevated temperature.
Waschmitteltabletten, in denen einzelne Inhaltsstoffe getrennt von anderen vorliegen, werden auch in der EP 0 481 793 A (Unilever) beschrieben. Die in dieser Schrift offenbarten Waschmitteltabletten enthaltend Natriumpercarbonat, das von allen anderen Komponenten, die seine Stabilität beeinflussen könnten, räumlich getrennt vorliegt.Detergent tablets in which individual ingredients are present separately from others are also described in EP 0 481 793 A (Unilever). The detergent tablets disclosed in this document contain sodium percarbonate, which is spatially separated from all other components that could influence its stability.
Der Einsatz von Alkylpolyglycosiden in Waschmitteltabletten wird bereits in der DE 19754289 (Henkel) offenbart. Hier wird allgemein beschrieben, dass ein Zusatz von Alkylpolyglycosiden die Löslichkeit von Tabletten, besonders bei hoher Bruchfestigkeit, verbessert. Es erfolgt weder eine Einschränkung zum Einsatz bestimmter Tenside, noch werden bestimmte Mengenverhältnisse der Tenside zueinander angegeben. The use of alkyl polyglycosides in detergent tablets has already been disclosed in DE 19754289 (Henkel). It is generally described here that the addition of alkylpolyglycosides improves the solubility of tablets, especially if they have high breaking strength. There is no restriction on the use of certain surfactants, nor are there specific quantitative ratios of the surfactants to one another.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, Wasch- und Reinigungsmitteltabletten bereitzustellen, die die gewünschten Eigenschaften hoher Härte und mechanischer Stabilität und dennoch günstiger Zerfallsgeschwindigkeiten miteinander vereinen.The present invention has for its object to provide detergent tablets, which have the desired properties of high hardness and mechanical stability and yet combine more favorable decay speeds.
Es wurde nun gefunden, dass Waschmitteltabletten mit hoher Härte und dennoch äußerst hoher Zerfallsgeschwindigkeit hergestellt werden können, wenn man bei der Herstellung der Wasch- und Reinigungsmittelrezeptur Fettalkoholalkoxylaten und Alkylpolyglycoside im erfindungsgemäßen Verhältnis einsetzt.It has now been found that detergent tablets with high hardness and yet extremely high disintegration speed can be produced if one in the manufacture of the detergent and cleaning agent formulation Fatty alcohol alkoxylates and alkyl polyglycosides in the ratio according to the invention starts.
Gegenstand der Erfindung sind demnach Wasch- und Reinigungsmittelformkörper aus verdichtetem teilchenförmigen Wasch- und Reinigungsmittel, enthaltend Tenside sowie gegebenenfalls weitere Wasch- und Reinigungsmittelbestandteile, dadurch gekennzeichnet, dass die Formkörper Tenside aus der Gruppe der Fettalkoholalkoxylate und Alkylpolyglycoside im Verhältnis 10:1 bis 1:10, vorzugsweise 5:1 bis 1:5, insbesondere 2:1 bis 1:2 - bezogen auf den Aktivsubstanzgehalt - enthalten.The invention accordingly relates to detergent tablets made of compressed particulate detergent and detergent, comprising surfactants and, if appropriate, further detergent components, characterized in that the tablets are surfactants from the group of fatty alcohol alkoxylates and alkyl polyglycosides in a ratio of 10: 1 to 1:10 , preferably 5: 1 to 1: 5, in particular 2: 1 to 1: 2 - based on the active substance content.
Typische Beispiele hierfür sind Fettalkoholpolyethylenglykol/polypropylenglykolether der Formel (I) bzw. Fettalkoholpolypropylenglykol/polyethylenglykolether der Formel (II).Typical examples are fatty alcohol polyethylene glycol / polypropylene glycol ether of the formula (I) or fatty alcohol polypropylene glycol / polyethylene glycol ether of the formula (II) .
Es werden bevorzugt Fettalkoholpolyethylenglykol/polypropylenglykolether der Formel (I),
Vorzugsweise können auch Fettalkoholpolypropylenglykol/polyethylenglykolether der Formel (II) eingesetzt
werden,
Einer bevorzugten Ausführungsform entsprechend enthalten die Formkörper Fettalkoholpolyethylenglykol/polypropylenglykolether der Formel (I) in der R1 für einen aliphatischen, gesättigten, geradkettigen oder verzweigten Alkylrest mit 8 bis 16 C-Atomen, n für eine Zahl von 1 bis 10, und m für 0 steht. Es handelt sich hierbei um Anlagerungsprodukte von 1 bis 10 Mol Ethylenoxid an monofunktionelle Fettalkohole.According to a preferred embodiment, the moldings contain fatty alcohol polyethylene glycol / polypropylene glycol ether of the formula (I) in which R 1 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, n is a number from 1 to 10, and m is 0 stands. These are addition products of 1 to 10 moles of ethylene oxide with monofunctional fatty alcohols.
Weiterhin bevorzugt werden Fettalkoholalkoxylate der Formel (1) eingesetzt, in der R1 für einen aliphatischen, gesättigten, geradkettigen oder verzweigten Alkylrest mit 8 bis 16 C-Atomen, n für eine Zahl von 2 bis 7 und m für eine Zahl von 3 bis 7 steht. Es handelt sich hierbei um Anlagerungsprodukte von zunächst mit 2 bis 7 Mol Ethylenoxid und dann mit 3 bis 7 Mol Propylenoxid alkoxylierten monofunktionellen Alkohole.Fatty alcohol alkoxylates of the formula (1) are also preferably used, in which R 1 is an aliphatic, saturated, straight-chain or branched alkyl radical having 8 to 16 carbon atoms, n is a number from 2 to 7 and m is a number from 3 to 7 stands. These are addition products of monofunctional alcohols alkoxylated first with 2 to 7 mol of ethylene oxide and then with 3 to 7 mol of propylene oxide.
Die erfindungsgemäßen Wasch- und Reinigungsmittelformkörper enthalten Alkyl- und Alkenyloligoglykoside,
nachfolgend kurz als APG bezeichnet. Diese folgen üblicherweise der Formel (II),
Sie können nach den einschlägigen Verfahren der präparativen organischen Chemie erhalten werden.
Stellvertretend für das umfangreiche Schrifttum sei hier auf die Schriften EP 0301298 A1 und
WO 90/03977 verwiesen. Die Alkyl- und/oder Alkenyloligoglykoside können sich von Aldosen bzw. Ketosen
mit 5 oder 6 Kohlenstoffatomen, vorzugsweise der Glucose ableiten. Die bevorzugten Alkylund/oder
Alkenyloligoglykoside sind somit Alkyl- und/oder Alkenyloligoglucoside. Die Indexzahl p in der
allgemeinen Formel (III) gibt den Oligomerisierungsgrad (DP), d. h. die Verteilung von Mono- und
Oligoglykosiden an und steht für eine Zahl zwischen 1 und 10. Während p in einer gegebenen Verbindung
stets ganzzahlig sein muss und hier vor allem die Werte p = 1 bis 6 annehmen kann, ist der Wert
p für ein bestimmtes Alkyloligoglykosid eine analytisch ermittelte rechnerische Größe, die meistens eine
gebrochene Zahl darstellt. Vorzugsweise werden Alkyl- und/oder Alkenyloligoglykoside mit einem mittleren
Oligomerisierungsgrad p von 1,1 bis 3,0 eingesetzt. Aus anwendungstechnischer Sicht sind solche
Alkyl- und/oder Alkenyloligoglykoside bevorzugt, deren Oligomerisierungsgrad kleiner als 1,7 ist und
insbesondere zwischen 1,2 und 1,4 liegt.
Der Alkyl- bzw. Alkenylrest R3 kann sich von primären Alkoholen mit 4 bis 11, vorzugsweise 8 bis
10 Kohlenstoffatomen ableiten. Typische Beispiele sind Butanol, Capronalkohol, Caprylalkohol, Caprinalkohol
und Undecylalkohol sowie deren technische Mischungen, wie sie beispielsweise bei der Hydrierung
von technischen Fettsäuremethylestern oder im Verlauf der Hydrierung von Aldehyden aus der
Roelen'schen Oxosynthese erhalten werden. Bevorzugt sind Alkyloligoglucoside der Kettenlänge
C8-C10 (DP = 1 bis 3), die als Vorlauf bei der destillativen Auftrennung von technischem
C8-C18-Kokosfettalkohol anfallen und mit einem Anteil von weniger als 6 Gew.-% C12-Alkohol verunreinigt
sein können sowie Alkyloligoglucoside auf Basis technischer C9/11-Oxoalkohole (DP = 1 bis 3).
Der Alkyl- bzw. Alkenylrest R3 kann sich ferner auch von primären Alkoholen mit 12 bis 22, vorzugsweise
12 bis 14 Kohlenstoffatomen ableiten. Typische Beispiele sind Laurylalkohol, Myristylalkohol,
Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol, Elaidylalkohol, Petroselinylalkohol,
Arachylalkohol, Gadoleylalkohol, Behenylalkohol, Erucylalkohol, Brassidylalkohol sowie
deren technische Gemische, die wie oben beschrieben erhalten werden können. Bevorzugt sind Alkyloligoglucoside
auf Basis von gehärtetem C12/14-Kokosalkohol mit einem DP von 1 bis 3.The detergent tablets according to the invention contain alkyl and alkenyl oligoglycosides, hereinafter referred to briefly as APG. These usually follow the formula (II),
They can be obtained according to the relevant procedures in preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP 0301298 A1 and WO 90/03977. The alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (III) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p in a given compound must always be an integer, and especially here can assume the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.
The alkyl or alkenyl radical R 3 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of chain length C8-C10 (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical C8-C18 coconut fatty alcohol by distillation and can be contaminated with a proportion of less than 6% by weight of C12 alcohol and Alkyl oligoglucosides based on technical C9 / 11 oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R 3 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C12 / 14 coconut alcohol with a DP of 1 to 3 are preferred.
In einer weiteren Ausführungsform enthalten die Wasch- und Reinigungsmittelformkörper 0,5 bis 25 Gew.%, vorzugsweise 1 bis 15 Gew.%, insbesonder 1 bis 10 Gew. % Alkylpolyglycoside - berechnet als Aktivsubstanz bezogen auf den Formkörper.In a further embodiment, the detergent tablets contain 0.5 to 25% by weight, preferably 1 to 15% by weight, in particular 1 to 10% by weight, of alkyl polyglycosides - calculated as an active substance based on the shaped body.
Weiterhin bevorzugt ist, dass die Wasch- und Reinigungsmittelformkörper weitere nichtionische Tenside enthalten, die ausgewählt sind aus der Gruppe, die gebildete wird von Hydroxymischethern, Fettsäureniedrigalkylestern und Aminoxiden.It is further preferred that the detergent tablets form further nonionic surfactants contain, which are selected from the group that is formed by hydroxy mixed ethers, fatty acid lower alkyl esters and amine oxides.
Typische Beispiele für nichtionische Tenside sind, neben den bereits beschriebenen, Alkylphenolpolyglycolether, Fettsäurepolyglycolester, Fettsäureamidpolyglycolether, Fettaminpolyglycolether, alkoxylierte Triglyceride, Mischether bzw. Mischformale, Fettsäure-N-alkylglucamide, Proteinhydrolysate (insbesondere pflanzliche Produkte auf Weizenbasis), Polyolfettsäureester, Zuckerester, Sorbitanester, und Polysorbate. Sofern die nichtionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung (narrow range) aufweisen.Typical examples of nonionic surfactants are, in addition to the alkylphenol polyglycol ethers already described, Fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated Triglycerides, mixed ethers or mixed formals, fatty acid N-alkylglucamides, protein hydrolyzates (especially vegetable products based on wheat), polyol fatty acid esters, sugar esters, sorbitan esters, and polysorbates. If the nonionic surfactants contain polyglycol ether chains, these can be a conventional, but preferably have a narrow homolog distribution (narrow range).
Bevorzugt werden als weitere nichtionische Tenside sind Hydroxymischether der Formel (IV)
Hydroxymischether können Ringöffnungsprodukte von sowohl innenständigen Olefinen (R7 ungleich Wasserstoff) oder entständigen Olefinen (R7 gleich Wasserstoff) sein, wobei letztere bevorzugt sind.Hydroxy mixed ethers can be ring opening products of both internal olefins (R 7 is not hydrogen) or internal olefins (R 7 is hydrogen), the latter being preferred.
Diese werden hergestellt durch Umsetzung von 1,2-Epoxyalkanen (R8CHOCHR7), wobei R7 für Wasserstoff, R8 für einen aliphatischen gesättigten, geradkettigen oder verzweigten Alkylrest mit 2 bis 22, insbesondere 6 bis 16 Kohlenstoffatomen steht, mit alkoxyliert Alkoholen.These are prepared by reacting 1,2-epoxyalkanes (R 8 CHOCHR 7 ), where R 7 is hydrogen, R 8 is an aliphatic saturated, straight-chain or branched alkyl radical having 2 to 22, in particular 6 to 16 carbon atoms, with alkoxylated alcohols ,
Bevorzugt im Sinne der Erfindung werden solche Hydroxymischether, die sich von Alkoxylaten von einwertigen
Alkoholen der Formel R4-OH mit 4 bis 18 Kohlenstoffatomen ableiten, wobei R4 für einen
aliphatischen, gesättigten, geradkettigen oder verzweigten Alkylrest, insbesondere mit 6 bis
16 Kohlenstoffatomen, und R7 für Wasserstoff steht.
Beispiele für geeignete geradkettige Alkohole sind Butanol-1, Capron-, Önanth-, Capryl-, Pelargon-,
Caprinalkohol, Undecanol-1, Laurylalkohol, Tridecanol-1, Myristylalkohol, Pentadecanol-1, Palmitylakohol,
Heptadecanol-1, Stearylalkohol, Nonadecanol-1, Arachidylalkohol, Heneicosanol-1, Behenylalkohol
sowie deren technische Mischungen, wie sie bei der Hochdruckhydrierung von technischen
Methylestern auf Basis von Fetten und Ölen anfallen. Beispiele für derartige verzweigte Alkohole sind
so genannte Oxoalkohole, die meist 2 bis 4 Methylgruppen als Verzweigungen tragen und nach dem
Oxoprozess hergestellt werden und so genannte Guerbetalkohole, die in 2-Stellung mit einer
Alkylgruppe verzweigt sind. Geeignete Guerbetalkohole sind 2-Ethylhexanol, 2-Butyloctanol,
2-Hexyldecanol und/oder 2-Octyldodecanol.Preferred hydroxy mixed ethers for the purposes of the invention are those derived from alkoxylates of monohydric alcohols of the formula R 4 -OH having 4 to 18 carbon atoms, where R 4 is an aliphatic, saturated, straight-chain or branched alkyl radical, in particular having 6 to 16 carbon atoms, and R 7 represents hydrogen.
Examples of suitable straight-chain alcohols are butanol-1, capron, Önanth, capryl, pelargon, caprinal alcohol, undecanol-1, lauryl alcohol, tridecanol-1, myristyl alcohol, pentadecanol-1, palmity alcohol, heptadecanol-1, stearyl alcohol, nonadecanol 1, arachidyl alcohol, heneicosanol-1, behenyl alcohol and their technical mixtures, as are obtained in the high-pressure hydrogenation of technical methyl esters based on fats and oils. Examples of such branched alcohols are so-called oxo alcohols, which usually carry 2 to 4 methyl groups as branches and are produced by the oxo process, and so-called Guerbet alcohols, which are branched in the 2-position with an alkyl group. Suitable Guerbet alcohols are 2-ethylhexanol, 2-butyloctanol, 2-hexyldecanol and / or 2-octyldodecanol.
Die Alkohole werden in Form ihrer Alkoxylate eingesetzt, die durch Umsetzung der Alkohole in beliebiger
Reihenfolge mit Ethylenoxid, Propylenoxid und/oder Butylenoxid auf bekannte Weise hergestellt
werden.
In einer bevorzugten Ausführungsform werden Alkoxylate von Alkoholen, die durch Umsetzung mit
10 bis 80 Mol Ethylenoxid entstehen eingesetzt, wobei R5, R6 und R7 für Wasserstoff steht und
b+y=1-80 ist.
Eine weitere Ausführungsform beschreibt sowohl Alkoxylate, die durch Umsetzung von Alkohol mit 1 bis
10 Mol Propylenoxid (R5= Methyl, b=1-10) und 10 bis 40 Mol Ethylenoxid (R6=Wasserstoff, y=10-40)
entstehen, und auch durch Umsetzung mit 10 bis 40 Mol Ethylenoxid (R5= Wasserstoff, b=10-40) und
1 bis 10 Mol Propylenoxid (R6= Methyl, y=1-10) entstehen, wobei R7 jeweils für Wasserstoff steht.
Besonders geeignet sind Hydroxymischether der Formel (IV), wobei R7 für Wasserstoff, R5 für einen
Methylrest, und R6 für Wasserstoff stehen, die vorteilhafterweise durch Umsetzung von Alkohol mit 1 bis
3 Mol Propylenoxid (b=1-3) und anschließend mit 10 bis 25 Mol Ethylenoxid (y=10-25) hergestellt worden
sind.The alcohols are used in the form of their alkoxylates, which are prepared in a known manner by reacting the alcohols in any order with ethylene oxide, propylene oxide and / or butylene oxide.
In a preferred embodiment, alkoxylates of alcohols which are formed by reaction with 10 to 80 mol of ethylene oxide are used, where R 5 , R 6 and R 7 are hydrogen and b + y = 1-80.
Another embodiment describes both alkoxylates which are formed by reacting alcohol with 1 to 10 mol of propylene oxide (R 5 = methyl, b = 1-10) and 10 to 40 mol of ethylene oxide (R 6 = hydrogen, y = 10-40), and also by reaction with 10 to 40 moles of ethylene oxide (R 5 = hydrogen, b = 10-40) and 1 to 10 moles of propylene oxide (R 6 = methyl, y = 1-10), R 7 each representing hydrogen.
Hydroxy mixed ethers of the formula (IV) are particularly suitable, where R 7 is hydrogen, R 5 is a methyl radical and R 6 is hydrogen, which is advantageously carried out by reacting alcohol with 1 to 3 mol of propylene oxide (b = 1-3) and then with 10 to 25 moles of ethylene oxide (y = 10-25) have been prepared.
Als alkoxylierte Fettsäureniedrigalkylester kommen Tenside der Formel (V) in Betracht,
Üblicherweise erfolgt die Herstellung der Produkte durch Insertion der Alkylenoxide in die Carbonylesterbindung
in Gegenwart spezieller Katalysatoren, wie z.B. calcinierter Hydrotalcit.
Besonders bevorzugt sind Umsetzungsprodukte von durchschnittlich 5 bis 10 Mol Ethylenoxid in die
Esterbindung von technischen Kokosfettsäuremethylestern.Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (V)
The products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, such as, for example, calcined hydrotalcite.
Conversion products of an average of 5 to 10 moles of ethylene oxide into the ester linkage of technical coconut fatty acid methyl esters are particularly preferred.
Als Aminoxide können Verbindungen der Formel (VI) und/oder (VII) eingesetzt werden.
Bei der Herstellung der Aminoxide der Formel (VI) geht man von tertiären Fettaminen aus, die mindestens
einen langen Alkylrest aufweisen, und oxidiert sie in Gegenwart von Wasserstoffperoxid. Bei
den im Sinne der Erfindung in Betracht kommenden Aminoxiden der Formel (VI), steht R13 für einen
linearen oder verzweigten Alkylrest mit 6 bis 22, vorzugsweise 12 bis 18 Kohlenstoffatomen, sowie R14
und R15 unabhängig voneinander für R13 oder einen gegebenenfalls hydroxysubstituierten Alkylrest mit
1 bis 4 Kohlenstoffatomen. Vorzugsweise werden Aminoxide der Formel (VI) eingesetzt, in der R13 und
R14 für C12/14- bzw. C12/18-Kokosalkylreste stehen und R15 einen Methyl- oder einen Hydroxyethylrest
bedeutet. Ebenfalls bevorzugt sind Aminoxide der Formel (VI), in denen R13 für einen C12/14- bzw.
C12/18- Kokosalkylrest steht und R14 und R15 die Bedeutung eines Methyl- oder Hydroxyethylrestes haben.
Weitere geeignete Aminoxide sind Alkylamido-aminoxide der Formel (VII), wobei der Alkylamido-Rest
R17CONH durch die Reaktion von linearen oder verzweigten Carbonsäuren, vorzugsweise mit 6 bis 22,
bevorzugt mit 12 bis 18 Kohlenstoffatomen, insbesondere aus C12/14- bzw. C12/18- Fettsäuren mit Aminen
entsteht. Dabei stellt R18 eine linerare oder verzweigte Alkylengruppe dar mit 2 bis 6, vorzugsweise
2 bis 4 Kohlenstoffatomen und R14 und R15 haben die in Formel (VI) angegebene Bedeutung.Compounds of the formula (VI) and / or (VII) can be used as amine oxides . The preparation of the amine oxides of the formula (VI) starts from tertiary fatty amines which have at least one long alkyl radical and is oxidized in the presence of hydrogen peroxide. In the case of the amine oxides of the formula (VI) which are suitable for the purposes of the invention, R 13 represents a linear or branched alkyl radical having 6 to 22, preferably 12 to 18 carbon atoms, and R 14 and R 15 independently of one another are R 13 or, if appropriate hydroxy-substituted alkyl radical having 1 to 4 carbon atoms. Amine oxides of the formula (VI) are preferably used, in which R 13 and R 14 are C 12/14 and C 12/18 cocoalkyl radicals and R 15 is a methyl or a hydroxyethyl radical. Also preferred are amine oxides of the formula (VI) in which R 13 represents a C 12/14 or C 12/18 cocoalkyl radical and R 14 and R 15 have the meaning of a methyl or hydroxyethyl radical.
Further suitable amine oxides are alkylamido -amine oxides of the formula (VII) , the alkylamido radical R 17 CONH being obtained by the reaction of linear or branched carboxylic acids, preferably having 6 to 22, preferably having 12 to 18, carbon atoms, in particular from C 12/14 or C 12/18 - fatty acids with amines. R 18 represents a linear or branched alkylene group having 2 to 6, preferably 2 to 4 carbon atoms and R 14 and R 15 have the meaning given in formula (VI) .
Weiterhin können die Wasch- und Reinigungsmittelformkörper anionische Tenside enthalten. Typische Beispiele für anionische Tenside sind Seifen, Alkylbenzolsulfonate, sekundäre Alkansulfonate, Olefinsulfonate, Alkylethersulfonate, Glycerinethersulfonate, α-Methylestersulfonate, Sulfofettsäuren, Alkyl- und/oder Alkenylsulfate, Alkylethersulfate, Glycerinethersulfate, Hydroxymischethersulfate, Fettalkohol(ether)phosphate, Monoglycerid(ether)sulfate, Fettsäureamid(ether)sulfate, Mono- und Dialkylsulfosuccinate, Mono- und Dialkylsulfosuccinamate, Sulfotriglyceride, Amidseifen, Ethercarbonsäuren und deren Salze, Fettsäureisethionate, Fettsäuresarcosinate, Fettsäuretauride, N-Acylaminosäuren wie beispielsweise Acyllactylate, Acyltartrate, Acylglutamate und Acylaspartate, Alkyloligoglucosidsulfate, Proteinfettsäurekondensate (insbesondere pflanzliche Produkte auf Weizenbasis) und Alkyl(ether)phosphate. Sofern die anionischen Tenside Polyglycoletherketten enthalten, können diese eine konventionelle, vorzugsweise jedoch eine eingeengte Homologenverteilung aufweisen.Furthermore, the detergent tablets can contain anionic surfactants. Typical examples of anionic surfactants are soaps, alkylbenzenesulfonates, secondary alkanesulfonates, Olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, α-methyl ester sulfonates, sulfo fatty acids, Alkyl and / or alkenyl sulfates, alkyl ether sulfates, glycerol ether sulfates, hydroxy mixed ether sulfates, fatty alcohol (ether) phosphates, Monoglyceride (ether) sulfates, fatty acid amide (ether) sulfates, mono- and dialkyl sulfosuccinates, Mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates, fatty acid taurides, N-acylamino acids such as for example acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, Protein fatty acid condensates (especially vegetable products based on wheat) and alkyl (ether) phosphates. If the anionic surfactants contain polyglycol ether chains, they can be a conventional, but preferably have a narrow homolog distribution.
Bevorzugt sind anionische Tenside ausgewählt aus der Gruppe, die gebildet wird von Alkyl- und/oder Alkenylsulfate, Alkylethersulfate, Alkylbenzolsulfonate, Seifen, Monoglycerid(ether)sulfate und Alkansulfonate, insbesondere Fettalkoholsulfate, Fettalkoholethersulfate, sekundäre Alkansulfonate und lineare Alkylbenzolsulfonate.Anionic surfactants are preferably selected from the group consisting of alkyl and / or Alkenyl sulfates, alkyl ether sulfates, alkyl benzene sulfonates, soaps, monoglyceride (ether) sulfates and alkane sulfonates, in particular fatty alcohol sulfates, fatty alcohol ether sulfates, secondary alkane sulfonates and linear Alkylbenzenesulfonates.
Unter Alkyl- und/oder Alkenylsulfaten, die auch häufig als Fettalkoholsulfate bezeichnet werden, sind
die Sulfatierungsprodukte primärer Alkohole zu verstehen, die der Formel (VIII) folgen,
in der R19 für einen linearen oder verzweigten, aliphatischen Alkyl- und/oder Alkenylrest mit 6 bis 22,
vorzugsweise 12 bis 18 Kohlenstoffatomen und X für ein Alkali- und/oder Erdalkalimetall, Ammonium,
Alkylammonium, Alkanolammonium oder Glucammonium steht.
Typische Beispiele für Alkylsulfate, die im Sinne der Erfindung Anwendung finden können, sind die
Sulfatierungsprodukte von Capronalkohol, Caprylalkohol, Caprinalkohol, 2-Ethylhexylalkohol, Laurylalkohol,
Myristylalkohol, Cetylalkohol, Palmoleylalkohol, Stearylalkohol, Isostearylalkohol, Oleylalkohol,
Elaidylalkohol, Petroselinylalkohol, Arachylalkohol, Gadoleylalkohol, Behenylalkohol und Erucylalkohol
sowie deren technischen Gemischen, die durch Hochdruckhydrierung technischer Methylesterfraktionen
oder Aldehyden aus der Roelenschen Oxosynthese erhalten werden. Die Sulfatierungsprodukte können
vorzugsweise in Form ihrer Alkalisalze und insbesondere ihrer Natriumsalze eingesetzt werden. Besonders
bevorzugt sind Alkylsulfate auf Basis von C16/18-Talgfettalkoholen bzw. pflanzliche Fettalkohole vergleichbarer
C-Kettenverteilung in Form ihrer Natriumsalze. in which R 19 represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
Typical examples of alkyl sulfates which can be used in the context of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, aryl selenyl alcohol, elaidyl alcohol, Behenyl alcohol and erucyl alcohol and their technical mixtures, which are obtained from high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis. The sulfation products can preferably be used in the form of their alkali metal salts and in particular their sodium salts. Alkyl sulfates based on C 16/18 tallow fatty alcohols or vegetable fatty alcohols of comparable C chain distribution in the form of their sodium salts are particularly preferred.
Alkylethersulfate ("Ethersulfate") stellen bekannte anionische Tenside dar, die großtechnisch durch
SO3- oder Chlorsulfonsäure (CSA)-Sulfatierung von Fettalkohol- oder Oxoalkoholpolyglycolethern und
nachfolgende Neutralisation hergestellt werden. Im Sinne der Erfindung kommen Ethersulfate in Betracht,
die der Formel (IX) folgen,
Alkylbenzolsulfonate folgen vorzugsweise der Formel (X)
Unter Seifen sind schließlich Fettsäuresalze der Formel (XI) zu verstehen,
Monoglyceridsulfate und Monoglyceridethersulfate stellen bekannte anionische Tenside dar, die nach den einschlägigen Methoden der präparativen organischen Chemie erhalten werden können. Üblicherweise geht man zu ihrer Herstellung von Triglyceriden aus, die gegebenenfalls nach Ethoxylierung zu den Monoglyceriden umgeestert und nachfolgend sulfatiert und neutralisiert werden. Gleichfalls ist es möglich, die Partialglyceride mit geeigneten Sulfatierungsmitteln, vorzugsweise gasförmiges Schwefeltrioxid oder Chlorsulfonsäure umzusetzen [vgl. EP 0561825 B1, EP 0561999 B1 (Henkel)]. Die neutralisierten Stoffe können - falls gewünscht - einer Ultrafiltration unterworfen werden, um den Elektrolytgehalt auf ein gewünschtes Maß zu vermindern [DE 4204700 A1 (Henkel)]. Übersichten zur Chemie der Monoglyceridsulfate sind beispielsweise von A. K. Biswas et al. in J.Am.Oil.Chem.Soc. 37, 171 (1960) und F. U. Ahmed J.Am.Oil.Chem.Soc. 67, 8 (1990) erschienen. Die im Sinne der Erfindung einzusetzenden Monoglycerid(ether)sulfate folgen der Formel (XII), in der R23C0 für einen linearen oder verzweigten Acylrest mit 6 bis 22 Kohlenstoffatomen, c, d und e in Summe für 0 oder für Zahlen von 1 bis 30, vorzugsweise 2 bis 10, und X für ein Alkali- oder Erdalkalimetall steht. Typische Beispiele für im Sinne der Erfindung geeignete Monoglycerid(ether)sulfate sind die Umsetzungsprodukte von Laurinsäuremonoglycerid, Kokosfettsäuremonoglycerid, Palmitinsäuremonoglycerid, Stearinsäuremonoglycerid, Ölsäuremonoglycerid und Talgfettsäuremonoglycerid sowie deren Ethylenoxidaddukte mit Schwefeltrioxid oder Chlorsulfonsäure in Form ihrer Natriumsalze. Vorzugsweise werden Monoglyceridsulfate der Formel (XII) eingesetzt, in der R23CO für einen linearen Acylrest mit 8 bis 18 Kohlenstoffatomen steht.Monoglyceride sulfates and monoglyceride ether sulfates are known anionic surfactants which can be obtained by the relevant methods of preparative organic chemistry. The usual starting point for their preparation is triglycerides, which, if appropriate, are transesterified to the monoglycerides after ethoxylation and subsequently sulfated and neutralized. It is also possible to react the partial glycerides with suitable sulfating agents, preferably gaseous sulfur trioxide or chlorosulfonic acid [cf. EP 0561825 B1, EP 0561999 B1 (Henkel)]. If desired, the neutralized substances can be subjected to ultrafiltration in order to reduce the electrolyte content to a desired level [DE 4204700 A1 (Henkel)]. Overviews of the chemistry of the monoglyceride sulfates are, for example, by AK Biswas et al. in J.Am.Oil.Chem.Soc. 37 , 171 (1960) and FU Ahmed J.Am.Oil.Chem.Soc. 67 , 8 (1990). The monoglyceride (ether) sulfates to be used in accordance with the invention follow the formula (XII), in which R 23 C0 represents a linear or branched acyl radical having 6 to 22 carbon atoms, c, d and e in total 0 or numbers 1 to 30, preferably 2 to 10, and X represents an alkali or alkaline earth metal. Typical examples of monoglyceride (ether) sulfates suitable for the purposes of the invention are the reaction products of lauric acid monoglyceride, coconut fatty acid monoglyceride, palmitic acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride and tallow fatty acid monoglyceride as well as their ethylene oxide adducts or their formulated with sulfuric acid trioxide. Monoglyceride sulfates of the formula (XII) are preferably used, in which R 23 CO represents a linear acyl radical having 8 to 18 carbon atoms.
Alkansulfonate lassen sich in primäre und sekundäre Alkansulfonate einteilen. Darunter versteht man Verbindungen der Formel (XIII), wobei bei primären Alkansulfonaten R24 für Wasserstoff und R25 für einen Alkylrest mit nicht mehr als 50 Kohlenstoffen steht. Bevorzugt sind die sekundären Alkansulfonate.Alkane sulfonates can be divided into primary and secondary alkane sulfonates. This means compounds of the formula (XIII) where in primary alkanesulfonates R 24 is hydrogen and R 25 is an alkyl radical with no more than 50 carbons. The secondary alkanesulfonates are preferred.
R24 und R25 stehen für Alkylreste, wobei R24 und R25 zusammen nicht mehr als 50 Kohlenstoffatome haben sollen.R 24 and R 25 represent alkyl radicals, where R 24 and R 25 together should not have more than 50 carbon atoms.
In einer bevorzugten Ausführungsform enthalten die erfindungsgemäßen Wasch- und Reinigungsmittelformkörper kationischen und/oder amphoteren bzw. zwitterionische Tenside, ausgewählt aus der Gruppe, die gebildet wird von Esterquats, Alkylbetainen, Alkylamidobetainen, Imidazoliniumbetainen. In a preferred embodiment, the detergent tablets according to the invention contain cationic and / or amphoteric or zwitterionic surfactants selected from the Group formed by esterquats, alkyl betaines, alkyl amido betaines, imidazolinium betaines.
Typische Beispiele für kationische Tenside sind Tetraalkylammoniumverbindungen, wie beispielsweise Dimethyldistearylammoniumchlorid oder Hydroxyethyl Hydroxycetyl Dimmonium Chloride (Dehyquart® E). Besonders bevorzugt ist der Einsatz von Esterquats.Typical examples of cationic surfactants are tetraalkylammonium compounds, for example Dimethyldistearylammonium chloride or Hydroxyethyl Hydroxycetyl Dimmonium Chloride (Dehyquart® E). The use of ester quats is particularly preferred.
Hierbei handelt es sich z.B. um quaternierte Fettsäuretriethanolaminestersalze der Formel (XIV), in der R27CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R28 und R29 unabhängig voneinander für Wasserstoff oder R27CO, R30 für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH2CH2O)x4H-Gruppe, x1, x2 und x3 in Summe für 0 oder Zahlen von 1 bis 12, x4 für Zahlen von 1 bis 12 und Y für Halogenid, Alkylsulfat oder Alkylphosphat steht. Typische Beispiele für Esterquats, die im Sinne der Erfindung Verwendung finden können, sind Produkte auf Basis von Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Isostearinsäure, Stearinsäure, Ölsäure, Elaidinsäure, Arachinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, wie sie beispielsweise bei der Druckspaltung natürlicher Fette und Öle anfallen. Vorzugsweise werden technische C12/18-Kokosfettsäuren und insbesondere teilgehärtete C16/18-Talg- bzw. Palmfettsäuren sowie elaidinsäurereiche C16/18-Fettsäureschnitte eingesetzt. Zur Herstellung der quaternierten Ester können die Fettsäuren und das Triethanolamin im molaren Verhältnis von 1,1:1 bis 3 :1 eingesetzt werden. Im Hinblick auf die anwendungstechnischen Eigenschaften der Esterquats hat sich ein Einsatzverhältnis von 1,2 1 bis 2,2 1, vorzugsweise 1,5 : 1 bis 1,9 : 1 als besonders vorteilhaft erwiesen. Die bevorzugten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar und leiten sich von technischer C16/18- Talg- bzw. Palmfettsäure (lodzahl 0 bis 40) ab. Aus anwendungstechnischer Sicht haben sich quaternierte Fettsäuretriethanolaminestersalze der Formel (XIV) als besonders vorteilhaft erwiesen, in der R27CO für einen Acylrest mit 16 bis 18 Kohlenstoffatomen, R28 für R27CO, R29 für Wasserstoff, R30 für eine Methylgruppe, (x1+x2+x3) für 0 und Y für Methylsulfat steht. These are, for example, quaternized fatty acid triethanolamine ester salts of the formula (XIV), in which R 27 CO is an acyl radical having 6 to 22 carbon atoms, R 28 and R 29 independently of one another are hydrogen or R 27 CO, R 30 is an alkyl radical having 1 to 4 carbon atoms or a (CH 2 CH 2 O) x4 H- Group, x1, x2 and x3 in total for 0 or numbers from 1 to 12, x4 for numbers from 1 to 12 and Y for halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats that can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, in the pressure splitting of natural fats and oils. Technical C12 / 18 coconut fatty acids and in particular partially hardened C16 / 18 tallow or palm fatty acids as well as high elaidic acid C16 / 18 fatty acid cuts are preferably used. The fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters. With regard to the application properties of the ester quats, an application ratio of 1.2 1 to 2.2 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The preferred ester quats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C16 / 18-tallow or palm fatty acid (iodine number 0 to 40). From an application point of view, quaternized fatty acid triethanolamine ester salts of the formula (XIV) have proven to be particularly advantageous in which R 27 CO for an acyl radical having 16 to 18 carbon atoms, R 28 for R 27 CO, R 29 for hydrogen, R 30 for a methyl group, ( x1 + x2 + x3) is 0 and Y is methyl sulfate.
Neben den quaternierten Fettsäuretriethanolaminestersalzen kommen als Esterquats ferner auch quaternierte Estersalze von Fettsäuren mit Diethanolalkylaminen der Formel (XV) in Betracht, in der R31CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R32 für Wasserstoff oder R31CO, R33 und R34 unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, x5 und x6 in Summe für 0 oder Zahlen von 1 bis 12 und Y für Halogenid, Alkylsulfat oder Alkylphosphat steht.In addition to the quaternized fatty acid triethanolamine ester salts, quaternized ester salts of fatty acids with diethanolalkylamines of the formula (XV) are also suitable as esterquats. in which R 31 CO for an acyl radical with 6 to 22 carbon atoms, R 32 for hydrogen or R 31 CO, R 33 and R 34 independently of one another for alkyl radicals with 1 to 4 carbon atoms, x5 and x6 in total for 0 or numbers from 1 to 12 and Y represents halide, alkyl sulfate or alkyl phosphate.
Als weitere Gruppe geeigneter Esterquats sind schließlich die quaternierten Estersalze von Fettsäuren mit 1,2-Dihydroxypropyldialkylaminen der Formel (XVI) zu nennen, in der R35CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R36 für Wasserstoff oder R35CO, R37, R38 und R39 unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, x7 und x8 in Summe für 0 oder Zahlen von 1 bis 12 und Y für Halogenid, Alkylsulfat oder Alkylphosphat steht.Finally, the quaternized ester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines of the formula (XVI) should be mentioned as a further group of suitable ester quats, in which R 35 CO for an acyl radical with 6 to 22 carbon atoms, R 36 for hydrogen or R 35 CO, R 37 , R 38 and R 39 independently of one another for alkyl radicals with 1 to 4 carbon atoms, x7 and x8 in total for 0 or numbers from 1 to 12 and Y represents halide, alkyl sulfate or alkyl phosphate.
Schließlich kommen als Esterquats noch Stoffe in Frage, bei denen die Ester- durch eine Amidbindung ersetzt ist und die vorzugsweise basierend auf Diethylentriamin der Formel (XVII) folgen, in der R40CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R41 für Wasserstoff oder R40CO, R42 und R43 unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen und Y für Halogenid, Alkylsulfat oder Alkylphosphat steht. Derartige Amidesterquats sind beispielsweise unter der Bezeichnung Incroquat® (Croda) im Markt erhältlich. Finally, suitable ester quats are substances in which the ester bond is replaced by an amide bond and which preferably follow the formula (XVII) based on diethylenetriamine, in which R 40 CO represents an acyl radical with 6 to 22 carbon atoms, R 41 for hydrogen or R 40 CO, R 42 and R 43 independently of one another for alkyl radicals with 1 to 4 carbon atoms and Y for halide, alkyl sulfate or alkyl phosphate. Such amide ester quats are available on the market, for example, under the name Incroquat® (Croda).
Als amphotere bzw. zwitterionische Tenside können die Wasch- und Reinigungsmittelformkörper Alkylbetaine, Alkylamidobetaine, Aminopropionate, Aminoglycinate, Imidazoliniumbetaine und/oder Sulfobetaine enthalten.As amphoteric or zwitterionic surfactants, the detergent tablets can be alkylbetaines, Alkyl amido betaines, aminopropionates, aminoglycinates, imidazolinium betaines and / or sulfobetaines contain.
Beispiele für geeignete Alkylbetaine stellen die Carboxyalkylierungsprodukte von sekundären und insbesondere tertiären Aminen dar, die der Formel (XVIII) folgen, in der R44 für Alkyl- und/oder Alkenylreste mit 6 bis 22 Kohlenstoffatomen, R45 für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R46 für Alkylreste mit 1 bis 4 Kohlenstoffatomen, y1 für Zahlen von 1 bis 6 und Z für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind die Carboxymethylierungsprodukte von Hexylmethylamin, Hexyldimethylamin, Octyldimethylamin, Decyldimethylamin, Dodecylmethylamin, Dodecyldimethylamin, Dodecylethylmethylamin, C12/14-Kokosalkyldimethylamin, Myristyldimethylamin, Cetyldimethylamin, Stearyldimethylamin, Stearylethylmethylamin, Oleyldimethylamin, C16/18-Talgalkyldimethylamin sowie deren technische Gemische.Examples of suitable alkyl betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XVIII) in which R 44 for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R 45 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 46 for alkyl radicals with 1 to 4 carbon atoms, y1 for numbers from 1 to 6 and Z for a Alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine, C12 / 14-cocoalkyldimethylamine, myristyldimethylamine, cetyldimethylethylethylstimethylmethylamine, stearyldimethylamine, stearyldimethylamine, stearyldimethylamine, stearyldimethylamine, stearyldimethylamine, stearyldimethylamine, stearyldimethylamine, stamyldimethylamine, stamethyldimethylamine, stamethyldimethylamine, stamethyldimethylamine,
Weiterhin kommen auch Carboxyalkylierungsprodukte von Amidoaminen in Betracht, die der Formel (XIX) folgen, in der R47CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen und 0 oder 1 bis 3 Doppelbindungen, R48 für Wasserstoff oder Alkylreste mit 1 bis 4 Kohlenstoffatomen, R49 für Alkylreste mit 1 bis 4 Kohlenstoffatomen, y2 und y3 unabhängig von einander für Zahlen von 1 bis 6 und Z für ein Alkali- und/oder Erdalkalimetall oder Ammonium steht. Typische Beispiele sind Umsetzungsprodukte von Fettsäuren mit 6 bis 22 Kohlenstoffatomen, namentlich Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Gemische, mit N,N-Dimethylaminoethylamin, N,N-Dimethylaminopropylamin, N,N-Diethylaminoethylamin und N,N-Diethylaminopropylamin, die mit Natriumchloracetat kondensiert werden. Bevorzugt ist der Einsatz eines Kondensationsproduktes von C8/18-Kokosfettsäure-N,N-dimethylaminopropylamid mit Natriumchloracetat.Carboxyalkylation products of amidoamines which follow the formula (XIX) are also suitable, in the R 47 CO for an aliphatic acyl radical with 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, R 48 for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R 49 for alkyl radicals with 1 to 4 carbon atoms, y2 and y3 independently of one another represents numbers from 1 to 6 and Z represents an alkali and / or alkaline earth metal or ammonium. Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, gadoleic acid and arachic acid, arachic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C8 / 18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.
Weiterhin kommen auch Imidazoliniumbetaine in Betracht. Auch bei diesen Substanzen handelt es sich um bekannte Stoffe, die beispielsweise durch cyclisierende Kondensation von 1 oder 2 Mol Fettsäure mit mehrwertigen Aminen wie beispielsweise Aminoethylethanolamin (AEEA) oder Diethylentriamin erhalten werden können. Die entsprechenden Carboxyalkylierungsprodukte stellen Gemische unterschiedlicher offenkettiger Betaine dar. Typische Beispiele sind Kondensationsprodukte der oben genannten Fettsäuren mit AEEA, vorzugsweise Imidazoline auf Basis von Laurinsäure oder wiederum C12/14-Kokosfettsäure, die anschließend mit Natriumchloracetat betainisiert werden.Imidazolinium betaines are also suitable. These substances are also involved known substances, for example by cyclizing condensation of 1 or 2 moles of fatty acid obtained with polyvalent amines such as aminoethyl ethanolamine (AEEA) or diethylene triamine can be. The corresponding carboxyalkylation products make mixtures different open-chain betaines. Typical examples are condensation products of the above Fatty acids with AEEA, preferably imidazolines based on lauric acid or again C12 / 14 coconut fatty acid, which are then betainized with sodium chloroacetate.
Die erfindungsgemäßen Tensidgranulate können Sprengmittel enthalten. Unter dem Begriff Sprengmittel
sind Stoffe zu verstehen, die in den Tensidgranulaten enthalten sind, um deren Zerfall beim Inkontaktbringen
mit Wasser zu beschleunigen. Übersichten hierzu finden sich z.B. in J.Pharm.Sci. 61 (1972)
oder Römpp Chemielexikon, 9. Auflage, Band 6, S. 4440. Die Sprengmittel können im Granulat
makroskopisch betrachtet homogen verteilt vorliegen, können mikroskopisch gesehen jedoch herstellungsbedingt
Zonen erhöhter Konzentration bilden.
Zu den bevorzugten Sprengmitteln gehören Polysaccharide, wie z.B. natürliche Stärke und deren Derivate
(Carboxymethylstärke, Stärkeglycolate in Form ihrer Alkalisalze, Agar Agar, Guar Gum, Pektine
usw.), Cellulosen und deren Derivate (Carboxymethylcellulose, mikrokristalline Cellulose), Polyvinylpyrrolidon,
Kollidon, Alginsäure und deren Alkalisalze (Alginate), amorphe oder auch teilweise kristalline
Schichtsilicate (Bentonite), Polyurethane, Polyethylenglycole sowie gaserzeugende Systeme. Weitere
Sprengmittel, die im Sinne der Erfindung zugegen sein können, sind beispielsweise den Druckschriften
WO 98/40462 (Rettenmeyer), WO 98/55583 und WO 98/55590 (Unilever) und WO 98/40463,
DE 19709991 und DE 19710254 (Henkel) zu entnehmen. Auf die Lehre dieser Schriften wird ausdrücklich
Bezug genommen. The surfactant granules according to the invention can contain disintegrants. The term disintegrant is to be understood as meaning substances which are contained in the surfactant granules in order to accelerate their disintegration when brought into contact with water. Overviews can be found, for example, in J.Pharm.Sci. 61 (1972) or Römpp Chemielexikon, 9th edition, volume 6, p. 4440. The disintegrants can be present in the granules homogeneously distributed macroscopically, but from a microscopic point of view they can form zones of increased concentration due to the manufacturing process.
The preferred disintegrants include polysaccharides, such as, for example, natural starch and its derivatives (carboxymethyl starch, starch glycolates in the form of their alkali salts, agar agar, guar gum, pectins etc.), celluloses and their derivatives (carboxymethyl cellulose, microcrystalline cellulose), polyvinylpyrrolidone, collidone, alginic acid and their alkali salts (alginates), amorphous or also partially crystalline layered silicates (bentonites), polyurethanes, polyethylene glycols and gas-generating systems. Further disintegrants which may be present in the sense of the invention are, for example, the publications WO 98/40462 (Rettenmeyer), WO 98/55583 and WO 98/55590 (Unilever) and WO 98/40463, DE 19709991 and DE 19710254 (Henkel) refer to. Reference is expressly made to the teaching of these writings.
In einer bevorzugten Ausführungsform enthalten die Wasch- und Reinigungsmittelformkörper 0,5 bis 10 Gew.-%, vorzugsweise 1 bis 7 Gew.-% und insbesondere 2 bis 6 Gew.-% eines Desintegrationshilfsmittels, jeweils bezogen auf das Formkörpergewicht.In a preferred embodiment, the detergent tablets contain 0.5 to 10% by weight, preferably 1 to 7% by weight and in particular 2 to 6% by weight of a disintegration aid, each based on the weight of the molded body.
Als bevorzugte Desintegrationsmittel werden im Rahmen der vorliegenden Erfindung Desintegrationsmittel auf Cellulosebasis eingesetzt, so dass bevorzugte Wasch- und Reinigungsmittelformkörper ein solches Desintegrationsmittel auf Cellulosebasis in Mengen von 0,5 bis 10 Gew.-%, vorzugsweise 1 bis 7 Gew.-% und insbesondere 2 bis 6 Gew.-% enthalten. Reine Cellulose weist die formale Bruttozusammensetzung (C6H10O5)n auf und stellt formal betrachtet ein β-1,4-Polyacetal von Cellobiose dar, die ihrerseits aus zwei Molekülen Glucose aufgebaut ist. Geeignete Cellulosen bestehen dabei aus ca. 500 bis 5000 Glucose-Einheiten und haben demzufolge durchschnittliche Molmassen von 50.000 bis 500.000. Als Desintegrationsmittel auf Cellulosebasis verwendbar sind im Rahmen der vorliegenden Erfindung auch Cellulose-Derivate, die durch polymeranaloge Reaktionen aus Cellulose erhältlich sind. Solche chemisch modifizierten Cellulosen umfassen dabei beispielsweise Produkte aus Veresterungen bzw. Veretherungen, in denen Hydroxy-Wasserstoffatome substituiert wurden. Aber auch Cellulosen, in denen die Hydroxy-Gruppen gegen funktionelle Gruppen, die nicht über ein Sauerstoffatom gebunden sind, ersetzt wurden, lassen sich als Cellulose-Derivate einsetzen. In die Gruppe der Cellulose-Derivate fallen beispielsweise Alkalicellulosen, Carboxymethylcellulose (CMC), Celluloseester und -ether sowie Aminocellulosen.Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 1 to 7% by weight and in particular 2 contain up to 6 wt .-%. Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
Die genannten Cellulosederivate werden vorzugsweise nicht allein als Desintegrationsmittel auf Cellulosebasis eingesetzt, sondern in Mischung mit Cellulose verwendet. Der Gehalt dieser Mischungen an Cellulosederivaten beträgt vorzugsweise unterhalb 50 Gew.-%, besonders bevorzugt unterhalb 20 Gew.-%, bezogen auf das Desintegrationsmittel auf Cellulosebasis. Besonders bevorzugt wird als Desintegrationsmittel auf Cellulosebasis reine Cellulose eingesetzt, die frei von Cellulosederivaten ist.The cellulose derivatives mentioned are preferably not used alone as cellulose-based disintegrants used, but used in a mixture with cellulose. The content of these mixtures Cellulose derivatives is preferably below 50% by weight, particularly preferably below 20 wt .-%, based on the disintegrant based on cellulose. Is particularly preferred as Cellulose-based disintegrant used pure cellulose that is free of cellulose derivatives.
Als weiteres Desintegrationsmittel auf Cellulosebasis oder als Bestandteil dieser Komponente kann mikrokristalline Cellulose verwendet werden. Diese mikrokristalline Cellulose wird durch partielle Hydrolyse von Cellulosen unter solchen Bedingungen erhalten, die nur die amorphen Bereiche (ca. 30% der Gesamt-Cellulosemasse) der Cellulosen angreifen und vollständig auflösen, die kristallinen Bereiche (ca. 70%) aber unbeschadet lassen. Eine nachfolgende Desaggregation der durch die Hydrolyse entstehenden mikrofeinen Cellulosen liefert die mikrokristallinen Cellulosen, die Primärteilchengrößen von ca. 5 µm aufweisen und beispielsweise zu Granulaten mit einer mittleren Teilchengröße von 200 µm kompaktierbar sind. As a further disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is made by partial hydrolysis obtained from celluloses under conditions that only the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses attack and completely dissolve the crystalline areas (approx. 70%) but leave it undamaged. A subsequent disaggregation by hydrolysis The resulting micro-fine celluloses provide the microcrystalline celluloses, the primary particle sizes 5 µm and, for example, to granules with an average particle size of 200 µm are compactible.
Bevorzugt können die Wasch- und Reinigungsmittelformkörper einen oder mehrere weitere Hilfs- und Zusatzstoffen, aus der Gruppe der Builder, optischen Aufheller, Enzyme, Enzymstabilisatoren, Entschäumer, Co-Sprengmittel, Proteine und Proteinderivate, geringe Mengen an neutralen Füllsalzen sowie Farb- und Duftstoffe enthalten.The detergent tablets may preferably have one or more further auxiliaries and Additives, from the group of builders, optical brighteners, enzymes, enzyme stabilizers, defoamers, Co-disintegrants, proteins and protein derivatives, small amounts of neutral filling salts as well as dyes and fragrances.
Als Builder können beispielsweise Zeolithe eingesetzt werden. Der als Waschmittelbuilder häufig eingesetzte feinkristalline, synthetische und gebundenes Wasser enthaltende Zeolith ist vorzugsweise Zeolith A und/oder P. Als Zeolith P wird beispielsweise Zeolith MAP(R) (Handelsprodukt der Firma Crosfield) besonders bevorzugt. Geeignet sind jedoch auch Zeolith X sowie Mischungen aus A, X und/oder P wie auch Y. Von besonderem Interesse ist auch ein cokristallisiertes Natrium/Kalium-Aluminiumsilicat aus Zeolith A und Zeolith X, welches als VEGOBOND AX® (Handelsprodukt der Firma Condea Augusta S.p.A.) im Handel erhältlich ist. Der Zeolith kann als sprühgetrocknetes Pulver oder auch als ungetrocknete, von ihrer Herstellung noch feuchte, stabilisierte Suspension zum Einsatz kommen. Für den Fall, dass der Zeolith als Suspension eingesetzt wird, kann diese geringe Zusätze an nichtionischen Tensiden als Stabilisatoren enthalten, beispielsweise 1 bis 3 Gew.-%, bezogen auf Zeolith, an ethoxylierten C12-C18-Fettalkoholen mit 2 bis 5 Ethylenoxidgruppen, C12-C14-Fettalkoholen mit 4 bis 5 Ethylenoxidgruppen oder ethoxylierten Isotridecanolen. Geeignete Zeolithe weisen eine mittlere Teilchengröße von weniger als 10 µm (Volumenverteilung; Messmethode: Coulter Counter) auf und enthalten vorzugsweise 18 bis 22 Gew.-%, insbesondere 20 bis 22 Gew.-% an gebundenem Wasser.Zeolites, for example, can be used as builders . The fine crystalline, synthetic and bound water-containing zeolite which is frequently used as a detergent builder is preferably zeolite A and / or P. As zeolite P, for example, zeolite MAP (R) (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P and Y are also suitable. Of particular interest is also a cocrystallized sodium / potassium aluminum silicate made of zeolite A and zeolite X, which as VEGOBOND AX® (commercial product from Condea Augusta SpA) is commercially available. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
Geeignete Substitute bzw. Teilsubstitute für Phosphate und Zeolithe sind kristalline, schichtförmige
Natriumsilicate ("Schichtsilicate") der allgemeinen Formel NaMSixO2x+1·yH2O, wobei M Natrium oder
Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte
für x 2, 3 oder 4 sind. Derartige kristalline Schichtsilicate werden beispielsweise in der europäischen Patentanmeldung
EP 0164514 A1 beschrieben. Bevorzugte kristalline Schichtsilicate der angegebenen
Formel sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind
sowohl β- als auch δ-Natriumdisilicate Na2Si2O5·yH2O bevorzugt, wobei β-Natriumdisilicat beispielsweise
nach dem Verfahren erhalten werden kann, das in der internationalen Patentanmeldung
WO 91/08171 beschrieben ist. Weitere geeignete Schichtsilicate sind beispielsweise aus den Patentanmeldungen
DE 2334899 A1, EP 0026529 A1 und DE 3526405 A1 bekannt. Ihre Verwendbarkeit ist
nicht auf eine spezielle Zusammensetzung bzw. Strukturformel beschränkt. Bevorzugt sind hier jedoch
Smectite, insbesondere Bentonite. Geeignete Schichtsilicate, die zur Gruppe der mit Wasser quellfähigen
Smectite zählen, sind z.B. solche der allgemeinen Formeln
Zu den bevorzugten Buildersubstanzen gehören auch amorphe Natriumsilicate mit einem Modul Na2O : SiO2 von 1 : 2 bis 1 : 3,3, vorzugsweise von 1 : 2 bis 1: 2,8 und insbesondere von 1 : 2 bis 1 : 2,6, welche löseverzögert sind und Sekundärwascheigenschaften aufweisen. Die Löseverzögerung gegenüber herkömmlichen amorphen Natriumsilicaten kann dabei auf verschiedene Weise, beispielsweise durch Oberflächenbehandlung, Compoundierung, Kompaktierung/Verdichtung oder durch Übertrocknung hervorgerufen worden sein. Im Rahmen dieser Erfindung wird unter dem Begriff "amorph" auch "röntgenamorph" verstanden. Dies heißt, dass die Silicate bei Röntgenbeugungsexperimenten keine scharfen Röntgenreflexe liefern, wie sie für kristalline Substanzen typisch sind, sondern allenfalls ein oder mehrere Maxima der gestreuten Röntgenstrahlung, die eine Breite von mehreren Gradeinheiten des Beugungswinkels aufweisen. Es kann jedoch sehr wohl sogar zu besonders guten Buildereigenschaften führen, wenn die Silicatpartikel bei Elektronenbeugungsexperimenten verwaschene oder sogar scharfe Beugungsmaxima liefern. Dies ist so zu interpretieren, dass die Produkte mikrokristalline Bereiche der Größe 10 bis einige Hundert nm aufweisen, wobei Werte bis max. 50 nm und insbesondere bis max. 20 nm bevorzugt sind. Derartige sogenannte röntgenamorphe Silicate, welche ebenfalls eine Löseverzögerung gegenüber den herkömmlichen Wassergläsern aufweisen, werden beispielsweise in der deutschen Patentanmeldung DE 4400024 A1 beschrieben. Insbesondere bevorzugt sind verdichtete/kompaktierte amorphe Silicate, compoundierte amorphe Silicate und übertrocknete röntgenamorphe Silicate.The preferred builder substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 4400024 A1. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
Selbstverständlich ist auch ein Einsatz der allgemein bekannten Phosphate als Buildersubstanzen möglich, sofern ein derartiger Einsatz nicht aus ökologischen Gründen vermieden werden sollte. Geeignet sind insbesondere die Natriumsalze der Orthophosphate, der Pyrophosphate und insbesondere der Tripolyphosphate. Ihr Gehalt beträgt im Allgemeinen nicht mehr als 25 Gew.-%, vorzugsweise nicht mehr als 20 Gew.-%, jeweils bezogen auf das fertige Mittel. In einigen Fällen hat es sich gezeigt, dass insbesondere Tripolyphosphate schon in geringen Mengen bis maximal 10 Gew.-%, bezogen auf das fertige Mittel, in Kombination mit anderen Buildersubstanzen zu einer synergistischen Verbesserung des Sekundärwaschvermögens führen. Of course, it is also possible to use the generally known phosphates as builders, unless such use should be avoided for ecological reasons. Suitable are in particular the sodium salts of orthophosphates, pyrophosphates and in particular Tripolyphosphate. Their content is generally not more than 25% by weight, preferably not more than 20 wt .-%, each based on the finished agent. In some cases it has been shown that in particular tripolyphosphates even in small amounts up to a maximum of 10% by weight, based on the finished agents, in combination with other builder substances to a synergistic improvement of the Secondary washing power.
Die Builder sind in den Wasch- und Reinigungsmittelformkörper von 0 bis 70, vorzugsweise in Mengen von 10 bis 60, insbesondere 20 bis 40 Gew.-% - bezogen auf den Formkörper - enthalten.The builders are in the detergent tablets from 0 to 70, preferably in amounts from 10 to 60% by weight, in particular 20 to 40% by weight, based on the shaped body.
Brauchbare organische Gerüstsubstanzen sind beispielsweise die in Form ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren und Mischungen aus diesen. Auch die Säuren an sich können eingesetzt werden. Die Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH-Wertes von Wasch- oder Reinigungsmitteln. Insbesondere sind hierbei Citronensäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Gluconsäure und beliebige Mischungen aus diesen zu nennen.Usable organic builders are, for example, those that can be used in the form of their sodium salts Polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, Sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use from ecological Reasons is not objectionable, as well as mixtures of these. Preferred salts are the Salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, Sugar acids and mixtures of these. The acids themselves can also be used. The In addition to their builder effect, acids typically also have the property of an acidifying component and thus also serve to set a lower and milder one pH value of detergents or cleaning agents. In particular, citric acid, succinic acid, To name glutaric acid, adipic acid, gluconic acid and any mixtures of these.
Weitere geeignete organische Buildersubstanzen sind Dextrine, beispielsweise Oligomere bzw. Polymere von Kohlenhydraten, die durch partielle Hydrolyse von Stärken erhalten werden können. Die Hydrolyse kann nach üblichen, beispielsweise säure- oder enzymkatalysierten Verfahren durchgeführt werden. Vorzugsweise handelt es sich um Hydrolyseprodukte mit mittleren Molmassen im Bereich von 400 bis 500 000. Dabei ist ein Polysaccharid mit einem Dextrose-Äquivalent (DE) im Bereich von 0,5 bis 40, insbesondere von 2 bis 30 bevorzugt, wobei DE ein gebräuchliches Maß für die reduzierende Wirkung eines Polysaccharids im Vergleich zu Dextrose, welche ein DE von 100 besitzt, ist. Brauchbär sind sowohl Maltodextrine mit einem DE zwischen 3 und 20 und Trockenglucosesirupe mit einem DE zwischen 20 und 37 als auch so genannte Gelbdextrine und Weißdextrine mit höheren Molmassen im Bereich von 2 000 bis 30 000. Ein bevorzugtes Dextrin ist in der britischen Patentanmeldung GB 9419091 A1 beschrieben. Bei den oxidierten Derivaten derartiger Dextrine handelt es sich um deren Umsetzungsprodukte mit Oxidationsmitteln, welche in der Lage sind, mindestens eine Alkoholfunktion des Saccharidrings zur Carbonsäurefunktion zu oxidieren. Derartige oxidierte Dextrine und Verfahren ihrer Herstellung sind beispielsweise aus den europäischen Patentanmeldungen EP 0232202 A1, EP 0427349 A1, EP 0472042 A1 und EP 0542496 A1 sowie den internationalen Patentanmeldungen WO 92/18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 und WO 95/20608 bekannt. Ebenfalls geeignet ist ein oxidiertes Oligosaccharid gemäß der deutschen Patentanmeldung DE 19600018 A1. Ein an C6 des Saccharidrings oxidiertes Produkt kann besonders vorteilhaft sein.Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure for the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2,000 to 30,000 are common. A preferred dextrin is in British patent application GB 9419091 A1 described. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0232202 A1, EP 0427349 A1, EP 0472042 A1 and EP 0542496 A1 as well as from international patent applications WO 92/18542, WO 93/08251, WO 93/16110, WO 94 / 28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known. An oxidized oligosaccharide according to German patent application DE 19600018 A1 is also suitable. A product oxidized at C 6 of the saccharide ring can be particularly advantageous.
Weitere geeignete Cobuilder sind Oxidisuccinate und andere Derivate von Disuccinaten, vorzugsweise Ethylendiamindisuccinat. Besonders bevorzugt sind in diesem Zusammenhang auch Glycerindisuccinate und Glycerintrisuccinate, wie sie beispielsweise in den US-amerikanischen Patentschriften US 4,524,009, US 4,639,325, in der europäischen Patentanmeldung EP 0150930 A1 und der japanischen Patentanmeldung JP 93/339896 beschrieben werden. Geeignete Einsatzmengen liegen in zeolithhaltigen und/oder silikathaltigen Formulierungen bei 3 bis 15 Gew.-%.Other suitable cobuilders are oxidisuccinates and other derivatives of disuccinates, preferably Ethylenediamine. Glycerol disuccinates are also particularly preferred in this context and glycerol trisuccinates, as described, for example, in the US patents US 4,524,009, US 4,639,325, in European patent application EP 0150930 A1 and the Japanese patent application JP 93/339896. Suitable amounts are in Formulations containing zeolite and / or silicate at 3 to 15% by weight.
Weitere brauchbare organische Cobuilder sind beispielsweise acetylierte Hydroxycarbonsäuren bzw. deren Salze, welche gegebenenfalls auch in Lactonform vorliegen können und welche mindestens 4 Kohlenstoffatome und mindestens eine Hydroxygruppe sowie maximal zwei Säuregruppen enthalten, Derartige Cobuilder werden beispielsweise in der internationalen Patentanmeldung WO 95/20029 beschrieben.Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which at least Contain 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups, Such cobuilders are described, for example, in international patent application WO 95/20029.
Geeignete polymere Polycarboxylate sind beispielsweise die Natriumsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 800 bis 150 000 (auf Säure bezogen und jeweils gemessen gegen Polystyrolsulfonsäure). Geeignete copolymere Polycarboxylate sind insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im Allgemeinen 5 000 bis 200 000, vorzugsweise 10 000 bis 120 000 und insbesondere 50 000 bis 100 000 (jeweils gemessen gegen Polystyrolsulfonsäure). Die (co-)polymeren Polycarboxylate können entweder als Pulver oder als wässrige Lösung eingesetzt werden, wobei 20 bis 55 Gew.-%ige wässrige Lösungen bevorzugt sind. Granulare Polymere werden zumeist nachträglich zu einem oder mehreren Basisgranulaten zugemischt. Insbesondere bevorzugt sind auch biologisch abbaubare Polymere aus mehr als zwei verschiedenen Monomereinheiten, beispielsweise solche, die gemäß der DE 4300772 A1 als Monomere Salze der Acrylsäure und der Maleinsäure sowie Vinylalkohol bzw. Vinylalkohol-Derivate oder gemäß der DE 4221381 C2 als Monomere Salze der Acrylsäure und der 2-Alkylallylsulfonsäure sowie Zucker-Derivate enthalten. Weitere bevorzugte Copolymere sind solche, die in den deutschen Patentanmeldungen DE 4303320 A1 und DE 4417734 A1 beschrieben werden und als Monomere vorzugsweise Acrolein und Acrylsäure/Acrylsäuresalze bzw. Acrolein und Vinylacetat aufweisen. Ebenso sind als weitere bevorzugte Buildersubstanzen polymere Aminodicarbonsäuren, deren Salze oder deren Vorläufersubstanzen zu nennen. Besonders bevorzugt sind Polyasparaginsäuren bzw. deren Salze und Derivate.Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or Polymethacrylic acid, for example those with a molecular weight of 800 to 150,000 (on Acid sourced and measured against polystyrene sulfonic acid). Suitable copolymeric polycarboxylates are especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable proven to contain 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000 (measured in each case against polystyrene sulfonic acid). The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution are, with 20 to 55 wt .-% aqueous solutions are preferred. Granular polymers are usually mixed into one or more basic granules. Particularly preferred are also biodegradable polymers from more than two different monomer units, for example those which according to DE 4300772 A1 as monomers salts of acrylic acid and Maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers according to DE 4221381 C2 Contain salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives. Further preferred copolymers are those described in German patent applications DE 4303320 A1 and DE 4417734 A1 and as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate. Are also preferred as others Builder substances include polymeric aminodicarboxylic acids, their salts or their precursors call. Polyaspartic acids or their salts and derivatives are particularly preferred.
Weitere geeignete Buildersubstanzen sind Polyacetale, welche durch Umsetzung von Dialdehyden mit Polyolcarbonsäuren, welche 5 bis 7 C-Atome und mindestens 3 Hydroxylgruppen aufweisen, beispielsweise wie in der europäischen Patentanmeldung EP 0280223 A1 beschrieben, erhalten werden können. Bevorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutaraldehyd, Terephthalaldehyd sowie deren Gemischen und aus Polyolcarbonsäuren wie Gluconsäure und/oder Glucoheptonsäure erhalten. Other suitable builder substances are polyacetals, which are reacted with dialdehydes Polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example can be obtained as described in European patent application EP 0280223 A1. Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde as well as their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid receive.
Zusätzlich können die Formkörper auch Komponenten enthalten, welche die Öl- und Fett-Auswaschbarkeit aus Textilien positiv beeinflussen. Zu den bevorzugten öl- und fettlösenden Komponenten zählen beispielsweise nichtionische Celluloseether wie Methylcellulose und Methylhydroxypropylcellulose mit einem Anteil an Methoxyl-Gruppen von 15 bis 30 Gew.-% und an Hydroxypropoxyl-Gruppen von 1 bis 15 Gew.-%, jeweils bezogen auf den nichtionischen Celluloseether, sowie die aus dem Stand der Technik bekannten Polymere der Phthalsäure und/oder der Terephthalsäure bzw. von deren Derivaten, insbesondere Polymere aus Ethylenterephthalaten und/oder Polyethylenglykolterephthalaten oder anionisch und/oder nichtionisch modifizierten Derivaten von diesen. Besonders bevorzugt von diesen sind die sulfonierten Derivate der Phthalsäure- und der Terephthalsäure-Polymere.In addition, the moldings can also contain components that allow oil and fat to be washed out made of textiles. Among the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and also from polymers of phthalic acid and / or terephthalic acid or of known from the prior art their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Especially preferred among these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.
Weitere geeignete Inhaltsstoffe sind wasserlösliche anorganische Salze wie Bicarbonate, Carbonate, amorphe Silikate, normale Wassergläser, welche keine herausragenden Buildereigenschaften aufweisen, oder Mischungen aus diesen; insbesondere werden Alkalicarbonat und/oder amorphes Alkalisilikat, vor allem Natriumsilikat mit einem molaren Verhältnis Na2O : SiO2 von 1 : 1 bis 1 : 4,5, vorzugsweise von 1 : 2 bis 1 : 3,5, eingesetzt. Der Gehalt an Natriumcarbonat in den endzubereitungen beträgt dabei vorzugsweise bis zu 40 Gew.-%, vorteilhafterweise zwischen 2 und 35 Gew.-%. Der Gehalt der Mittel an Natriumsilikat (ohne besondere Buildereigenschaften) beträgt im Allgemeinen bis zu 10 Gew.-% und vorzugsweise zwischen 1 und 8 Gew.-%.Other suitable ingredients are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates, normal water glasses, which have no outstanding builder properties, or mixtures of these; in particular, alkali carbonate and / or amorphous alkali silicate, especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used. The content of sodium carbonate in the final preparations is preferably up to 40% by weight, advantageously between 2 and 35% by weight. The content of sodium silicate in the agents (without special builder properties) is generally up to 10% by weight and preferably between 1 and 8% by weight.
Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumperborattetrahydrat und das Natriumperboratmonohydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Natriumpercarbonat, Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure, Phthaloiminopersäure oder Diperdodecandisäure. Der Gehalt an Bleichmitteln beträgt vorzugsweise 0 bis 35 Gew.-% und insbesondere bis 30 Gew.-%, wobei vorteilhafterweise Perboratmonohydrat oder Percarbonat eingesetzt wird.Among the compounds which serve as bleaching agents and supply H 2 O 2 in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. The bleaching agent content is preferably 0 to 35% by weight and in particular up to 30% by weight, advantageously using perborate monohydrate or percarbonate.
Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Geeignet sind Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso-NOBS), Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat, 2,5-Diacetoxy-2,5-dihydrofuran und die aus den deutschen Patentanmeldungen DE 19616693 A1 und DE 19616767 A1 bekannten Enolester sowie acetyliertes Sorbitol und Mannitol beziehungsweise deren in der europäischen Patentanmeldung EP 0525239 A1 beschriebene Mischungen (SORMAN), acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfruktose, Tetraacetylxylose und Octaacetyllactose sowie acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton, und/oder N-acylierte Lactame, beispielsweise N-Benzoylcaprolactam, die aus den internationalen Patentanmeldungen WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 und WO 95/17498 bekannt sind. Die aus der deutschen Patentanmeldung DE 19616769 A1 bekannten hydrophil substituierten Acylacetale und die in der deutschen Patentanmeldung DE 196 16 770 sowie der internationalen Patentanmeldung WO 95/14075 beschriebenen Acyllactame werden ebenfalls bevorzugt eingesetzt. Auch die aus der deutschen Patentanmeldung DE 4443177 A1 bekannten Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden. Derartige Bleichaktivatoren sind im üblichen Mengenbereich, vorzugsweise in Mengen von 1 Gew.-% bis 10 Gew.-%, insbesondere 2 Gew.-% bis 8 Gew.-%, bezogen auf gesamtes Mittel, enthalten. Zusätzlich zu den oben aufgeführten konventionellen Bleichaktivatoren oder an deren Stelle können auch die aus den europäischen Patentschriften EP 0446982 B1 und EP 0453 003 B1 bekannten Sulfonimine und/oder bleichverstärkende Übergangsmetallsalze beziehungsweise Übergangsmetallkomplexe als so genannte Bleichkatalysatoren enthalten sein. Zu den in Frage kommenden Übergangsmetallverbindungen gehören insbesondere die aus der deutschen Patentanmeldung DE 19529905 A1 bekannten Mangan-, Eisen-, Kobalt-, Ruthenium- oder Molybdän-Salenkomplexe und deren aus der deutschen Patentanmeldung DE 19620267 A1 bekannte N-Analogverbindungen, die aus der deutschen Patentanmeldung DE 19536082 A1 bekannten Mangan-, Eisen-, Kobalt-, Ruthenium- oder Molybdän-Carbonylkomplexe, die in der deutschen Patentanmeldung DE 196 05 688 beschriebenen Mangan-, Eisen-, Kobalt-, Ruthenium-, Molybdän-, Titan-, Vanadium- und Kupfer-Komplexe mit stickstoffhaltigen Tripod-Liganden, die aus der deutschen Patentanmeldung DE 19620411 A1 bekannten Kobalt-, Eisen-, Kupfer- und Ruthenium-Aminkomplexe, die in der deutschen Patentanmeldung DE 4416438 A1 beschriebenen Mangan-, Kupfer- und Kobalt-Komplexe, die in der europäischen Patentanmeldung EP 0272030 A1 beschriebenen Kobalt-Komplexe, die aus der europäischen Patentanmeldung EP 0693550 A1 bekannten Mangan-Komplexe, die aus der europäischen Patentschrift EP 0392592 A1 bekannten Mangan-, Eisen-, Kobalt- und Kupfer-Komplexe und/oder die in der europäischen Patentschrift EP 0443651 B1 oder den europäischen Patentanmeldungen EP 0458397 A1, EP 0458398 A1, EP 0549271 A1, EP 0549272 A1, EP 0544490 A1 und EP 0544519 A1 beschriebenen Mangan-Komplexe. Kombinationen aus Bleichaktivatoren und Übergangsmetall-Bleichkatalysatoren sind beispielsweise aus der deutschen Patentanmeldung DE 19613103 A1 und der internationalen Patentanmeldung WO 95/27775 bekannt. Bleichverstärkende Übergangsmetallkomplexe, insbesondere mit den Zentralatomen Mn, Fe, Co, Cu, Mo, V, Ti und/oder Ru, werden in üblichen Mengen, vorzugsweise in einer Menge bis zu 1 Gew.-%, insbesondere von 0,0025 Gew.-% bis 0,25 Gew.-% und besonders bevorzugt von 0,01 Gew.-% bis 0,1 Gew.-%, jeweils bezogen auf den Formkörper, eingesetzt. Compounds which are aliphatic peroxocarboxylic acids under perhydrolysis conditions can be used as bleach activators with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally result in substituted perbenzoic acid can be used. Substances that are suitable O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups wear. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine, are preferred (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and from the German patent applications DE 19616693 A1 and DE 19616767 A1 known enol esters and acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0525239 A1 (SORMAN), acylated Sugar derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and Octaacetyl lactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which result from the international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498 are known. Those known from German patent application DE 19616769 A1 Hydrophilically substituted acylacetals and those in German patent application DE 196 16 770 and The international patent application WO 95/14075 acyl lactams described are also preferred used. The combinations known from German patent application DE 4443177 A1 conventional bleach activators can be used. Such bleach activators are in the usual range of amounts, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total average. In addition to those listed above conventional bleach activators or in their place can also be those from the European patent specifications EP 0446982 B1 and EP 0453 003 B1 known sulfonimines and / or bleach-enhancing Transition metal salts or transition metal complexes as so-called bleaching catalysts be included. The transition metal compounds in question include in particular the manganese, iron, cobalt, ruthenium known from German patent application DE 19529905 A1 or molybdenum-salt complexes and their from German patent application DE 19620267 A1 known N-analog connections, which are known from German patent application DE 19536082 A1 Manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in the German Patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, molybdenum, Titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, derived from the German Patent application DE 19620411 A1 known cobalt, iron, copper and ruthenium amine complexes, the manganese, copper and cobalt complexes described in German patent application DE 4416438 A1, the cobalt complexes described in European patent application EP 0272030 A1, the manganese complexes known from the European patent application EP 0693550 A1, which from the European patent EP 0392592 A1 known manganese, iron, cobalt and copper complexes and / or those in the European patent EP 0443651 B1 or the European patent applications EP 0458397 A1, EP 0458398 A1, EP 0549271 A1, EP 0549272 A1, EP 0544490 A1 and Manganese complexes described in EP 0544519 A1. Combinations of bleach activators and transition metal bleach catalysts are for example from the German patent application DE 19613103 A1 and the international patent application WO 95/27775 are known. bleach-boosting Transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are in usual amounts, preferably in an amount up to 1 wt .-%, especially of 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the molded body used.
Als Enzyme kommen insbesondere solche aus der Klasse der Hydrolasen, wie der Proteasen, Esterasen, Lipasen bzw. lipolytisch wirkenden Enzyme, Amylasen, Cellulasen bzw. andere Glykosylhydrolasen und Gemische der genannten Enzyme in Frage. Alle diese Hydrolasen tragen in der Wäsche zur Entfernung von Verfleckungen, wie protein-, fett- oder stärkehaltigen Verfleckungen, und Vergrauungen bei. Cellulasen und andere Glykosylhydrolasen können durch das Entfernen von Pilling und Mikrofibrillen zur Farberhaltung und zur Erhöhung der Weichheit des Textils beitragen. Zur Bleiche bzw. zur Hemmung der Farbübertragung können auch Oxidoreduktasen eingesetzt werden. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus und Humicola insolens gewonnene enzymatische Wirkstoffe. Vorzugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Dabei sind Enzymmischungen, beispielsweise aus Protease und Amylase oder Protease und Lipase bzw. lipolytisch wirkenden Enzymen oder Protease und Cellulase oder aus Cellulase und Lipase bzw. lipolytisch wirkenden Enzymen oder aus Protease, Amylase und Lipase bzw. lipolytisch wirkenden Enzymen oder Protease, Lipase bzw. lipolytisch wirkenden Enzymen und Cellulase, insbesondere jedoch Protease- und/oder Lipase-haltige Mischungen bzw. Mischungen mit lipolytisch wirkenden Enzymen von besonderem Interesse. Beispiele für derartige lipolytisch wirkende Enzyme sind die bekannten Cutinasen. Auch Peroxidasen oder Oxidasen haben sich in einigen Fällen als geeignet erwiesen. Zu den geeigneten Amylasen zählen insbesondere α-Amylasen, Iso-Amylasen, Pullulanasen und Pektinasen. Als Cellulasen werden vorzugsweise Cellobiohydrolasen, Endoglucanasen und β-Glucosidasen, die auch Cellobiasen genannt werden, bzw. Mischungen aus diesen eingesetzt. Da sich die verschiedenen Cellulase-Typen durch ihre CMCase- und Avicelase-Aktivitäten unterscheiden, können durch gezielte Mischungen der Cellulasen die gewünschten Aktivitäten eingestellt werden.Particularly suitable enzymes are those from the class of hydrolases, such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains, such as stains containing protein, fat or starch, and graying in the laundry. By removing pilling and microfibrils, cellulases and other glycosyl hydrolases can help maintain color and increase the softness of the textile. Oxidoreductases can also be used for bleaching or for inhibiting color transfer. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen. Der Anteil der Enzyme, Enzymmischungen oder Enzymgranulate kann beispielsweise etwa 0,1 bis 5 Gew.-%, vorzugsweise 0,1 bis etwa 2 Gew.-% betragen.The enzymes can be adsorbed on carriers and / or embedded in coating substances around them protect against premature decomposition. The percentage of enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
Zusätzlich zu den mono- und polyfunktionellen Alkoholen 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. Außer Calciumsalzen dienen auch Magnesiumsalze als Stabilisatoren. 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, 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. In addition to calcium salts, magnesium salts also serve as stabilizers. 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.
Vergrauungsinhibitoren haben die Aufgabe, den von der Faser abgelösten Schmutz in der Flotte suspendiert zu halten und so das Wiederaufziehen des Schmutzes zu verhindern. Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise die wasserlöslichen Salze polymerer Carbonsäuren, Leim, Gelatine, Salze von Ethercarbonsäuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich lösliche Stärkepräparate und andere als die oben genannten Stärkeprodukte verwenden, z.B. abgebaute Stärke, Aldehydstärken usw.. Auch Polyvinylpyrrolidon ist brauchbar. Bevorzugt werden jedoch Celluloseether, wie Carboxymethylcellulose (Na-Salz), Methylcellulose, Hydroxyalkylcellulose und Mischether, wie Methylhydroxyethylcellulose, Methylhydroxypropylcellulose, Methylcarboxymethylcellulose und deren Gemische, sowie Polyvinylpyrrolidon beispielsweise in Mengen von 0,1 bis 5 Gew.-%, bezogen den Formkörper, eingesetzt. Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. Water-soluble colloids of mostly organic nature are suitable for this, 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, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the shaped body, are preferably used ,
Die Mittel können als optische Aufheller Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z.B. Salze der 4,4'-Bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholino-Gruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilinogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ der substituierten Diphenylstyryle anwesend sein, z.B. die Alkalisalze des 4,4'-Bis(2-sulfostyryl)-diphenyls, 4,4'-Bis (4-chlor-3-sulfostyryl)-diphenyls, oder 4-(4-Chlorstyryl)-4'-(2-sulfostyryl)-diphenyls. Auch Gemische der vorgenannten Aufheller können verwendet werden. Einheitlich weiße Granulate werden erhalten, wenn die Mittel außer den üblichen Aufhellern in üblichen Mengen, beispielsweise zwischen 0,1 und 0,5 Gew.-%, vorzugsweise zwischen 0,1 und 0,3 Gew.-%, auch geringe Mengen, beispielsweise 10-6 bis 10-3 Gew.-%, vorzugsweise um 10-5 Gew.-%, eines blauen Farbstoffs enthalten. Ein besonders bevorzugter Farbstoff ist Tinolux® (Handelsprodukt der Ciba-Geigy).As optical brighteners, the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brighteners can also be used. Uniformly white granules are obtained if, in addition to the usual brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5% by weight, preferably between 0.1 and 0.3% by weight, and also in small amounts, for example Contain 10 -6 to 10 -3 wt .-%, preferably by 10 -5 wt .-%, of a blue dye. A particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy).
Als schmutzabweisende Polymere ("soil repellants") kommen solche Stoffe in Frage, die vorzugsweise Ethylenterephthalat- und/oder Polyethylenglycolterephthalatgruppen enthalten, wobei das Molverhältnis Ethylenterephthalat zu Polyethylenglycolterephthalat im Bereich von 50 : 50 bis 90 : 10 liegen kann. Das Molekulargewicht der verknüpfenden Polyethylenglycoleinheiten liegt insbesondere im Bereich von 750 bis 5000, d.h., der Ethoxylierungsgrad der Polyethylenglycolgruppenhaltigen Polymere kann ca. 15 bis 100 betragen. Die Polymeren zeichnen sich durch ein durchschnittliches Molekulargewicht von etwa 5000 bis 200.000 aus und können eine Block-, vorzugsweise aber eine Random-Struktur aufweisen. Bevorzugte Polymere sind solche mit Molverhältnissen Ethylenterephthalat/Polyethylenglycolterephthalat von etwa 65:35 bis etwa 90:10, vorzugsweise von etwa 70: 30 bis 80: 20. Weiterhin bevorzugt sind solche Polymeren, die verknüpfende Polyethylenglycoleinheiten mit einem Molekulargewicht von 750 bis 5000, vorzugsweise von 1000 bis etwa 3000 und ein Molekulargewicht des Polymeren von etwa 10.000 bis etwa 50.000 aufweisen. Beispiele für handelsübliche Polymere sind die Produkte Milease® T (ICI) oder Repelotex® SRP 3 (Rhöne-Poulenc). As soil release polymers ( "soil repellants") are those which are suitable are, preferably ethylene terephthalate and / or polyethylene glycol terephthalate contained, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate in the range of 50: 50 to 90: may be 10 degrees. The molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5000, ie the degree of ethoxylation of the polymers containing polyethylene glycol groups can be approximately 15 to 100. The polymers are characterized by an average molecular weight of about 5000 to 200,000 and can have a block, but preferably a random structure. Preferred polymers are those with molar ratios of ethylene terephthalate / polyethylene glycol terephthalate from about 65:35 to about 90:10, preferably from about 70:30 to 80:20. Also preferred are those polymers which have linking polyethylene glycol units with a molecular weight of 750 to 5000, preferably of 1000 to about 3000 and a molecular weight of the polymer from about 10,000 to about 50,000. Examples of commercially available polymers are the products Milease® T (ICI) or Repelotex® SRP 3 (Rhône-Poulenc).
Als Entschäumer können wachsartige Verbindungen eingesetzt werden. Als "wachsartig" werden solche Verbindungen verstanden, die einen Schmelzpunkt bei Atmosphärendruck über 25 °C (Raumtemperatur), vorzugsweise über 50 °C und insbesondere über 70 °C aufweisen. Die wachsartigen Entschäumersubstanzen sind in Wasser praktisch nicht löslich, d.h. bei 20 °C weisen sie in 100 g Wasser eine Löslichkeit unter 0,1 Gew.-% auf. Prinzipiell können alle aus dem Stand der Technik bekannten wachsartigen Entschäumersubstanzen enthalten sein. Geeignete wachsartige Verbindungen sind beispielsweise Bisamide, Fettalkohole, Fettsäuren, Carbonsäureester von ein- und mehrwertigen Alkoholen sowie Paraffinwachse oder Mischungen derselben. Alternativ können natürlich auch die für diesen Zweck bekannten Silikonverbindungen eingesetzt werden.Wax-like compounds can be used as defoamers . Compounds which have a melting point at atmospheric pressure above 25 ° C. (room temperature), preferably above 50 ° C. and in particular above 70 ° C., are understood to be “waxy”. The waxy defoamer substances are practically insoluble in water, ie at 20 ° C. they have a solubility of less than 0.1% by weight in 100 g of water. In principle, all wax-like defoamer substances known from the prior art can be contained. Suitable waxy compounds are, for example, bisamides, fatty alcohols, fatty acids, carboxylic acid esters of mono- and polyhydric alcohols, and paraffin waxes or mixtures thereof. Alternatively, the silicone compounds known for this purpose can of course also be used.
Geeignete Paraffinwachse stellen im Allgemeinen ein komplexes Stoffgemisch ohne scharfen Schmelzpunkt dar. Zur Charakterisierung bestimmt man üblicherweise seinen Schmelzbereich durch Differential-Thermo-Analyse (DTA), wie in "The Analyst" 87 (1962), 420, beschrieben, und/oder seinen Erstarrungspunkt, Darunter versteht man die Temperatur, bei der das Paraffin durch langsames Abkühlen aus dem flüssigen in den festen Zustand übergeht. Dabei sind bei Raumtemperatur vollständig flüssige Paraffine, das heißt solche mit einem Erstarrungspunkt unter 25 °C, erfindungsgemäß nicht brauchbar. Eingesetzt werden können beispielsweise die aus EP 0309931 A1 bekannten Paraffinwachsgemische aus beispielsweise 26 Gew.-% bis 49 Gew.-% mikrokristallinem Paraffinwachs mit einem Erstarrungspunkt von 62 °C bis 90 °C, 20 Gew.-% bis 49 Gew.-% Hartparaffin mit einem Erstarrungspunkt von 42 °C bis 56 °C und 2 Gew.-% bis 25 Gew.-% Weichparaffin mit einem Erstarrungspunkt von 35 °C bis 40 °C. Vorzugsweise werden Paraffine bzw. Paraffingemische verwendet, die im Bereich von 30 °C bis 90 °C erstarren. Dabei ist zu beachten, dass auch bei Raumtemperatur fest erscheinende Paraffinwachsgemische unterschiedliche Anteile an flüssigem Paraffin enthalten können. Bei den erfindungsgemäß brauchbaren Paraffinwachsen liegt dieser Flüssiganteil so niedrig wie möglich und fehlt vorzugsweise ganz. So weisen besonders bevorzugte Paraffinwachsgemische bei 30 °C einen Flüssiganteil von unter 10 Gew.-%, insbesondere von 2 Gew.-% bis 5 Gew.-%, bei 40 °C einen Flüssiganteil von unter 30 Gew.-%, vorzugsweise von 5 Gew.-% bis 25 Gew.-% und insbesondere von 5 Gew.-% bis 15 Gew.-%, bei 60 °C einen Flüssiganteil von 30 Gew.-% bis 60 Gew.-%, insbesondere von 40 Gew.-% bis 55 Gew.-%, bei 80 °C einen Flüssiganteil von 80 Gew.-% bis 100 Gew.-%, und bei 90 °C einen Flüssiganteil von 100 Gew.-% auf. Die Temperatur, bei der ein Flüssiganteil von 100 Gew.-% des Paraffinwachses erreicht wird, liegt bei besonders bevorzugten Paraffinwachsgemischen noch unter 85 °C, insbesondere bei 75 °C bis 82 °C. Bei den Paraffinwachsen kann es sich um Petrolatum, mikrokristalline Wachse bzw. hydrierte oder partiell hydrierte Paraffinwachse handeln.Suitable paraffin waxes generally represent a complex mixture of substances without a sharp melting point. For characterization, one usually determines its melting range by differential thermal analysis (DTA), as described in "The Analyst" 87 (1962), 420, and / or its solidification point This is the temperature at which the paraffin changes from the liquid to the solid state by slow cooling. Paraffins which are completely liquid at room temperature, that is to say those having a solidification point below 25 ° C., cannot be used according to the invention. For example, the paraffin wax mixtures known from EP 0309931 A1 of, for example, 26% by weight to 49% by weight of microcrystalline paraffin wax with a solidification point of 62 ° C. to 90 ° C., 20% by weight to 49% by weight hard paraffin can be used with a solidification point of 42 ° C to 56 ° C and 2 wt .-% to 25 wt .-% soft paraffin with a solidification point of 35 ° C to 40 ° C. Paraffins or paraffin mixtures which solidify in the range from 30 ° C. to 90 ° C. are preferably used. It should be noted that even paraffin wax mixtures that appear solid at room temperature can contain different proportions of liquid paraffin. In the paraffin waxes which can be used according to the invention, this liquid fraction is as low as possible and is preferably absent entirely. Particularly preferred paraffin wax mixtures at 30 ° C have a liquid fraction of less than 10% by weight, in particular from 2% by weight to 5% by weight, at 40 ° C a liquid fraction of less than 30% by weight, preferably of 5 % By weight to 25% by weight and in particular from 5% by weight to 15% by weight, at 60 ° C. a liquid fraction of 30% by weight to 60% by weight, in particular 40% by weight % to 55% by weight, at 80 ° C a liquid content of 80% by weight to 100% by weight, and at 90 ° C a liquid content of 100% by weight. The temperature at which a liquid content of 100% by weight of the paraffin wax is reached is still below 85 ° C. in particularly preferred paraffin wax mixtures, in particular at 75 ° C. to 82 ° C. The paraffin waxes can be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.
Geeignete Bisamide als Entschäumer sind solche, die sich von gesättigten Fettsäuren mit 12 bis 22, vorzugsweise 14 bis 18 C-Atomen sowie von Alkylendiaminen mit 2 bis 7 C-Atomen ableiten. Geeignete Fettsäuren sind Laurin-, Myristin-, Stearin-, Arachin- und Behensäure sowie deren Gemische, wie sie aus natürlichen Fetten beziehungsweise gehärteten Ölen, wie Talg oder hydriertem Palmöl, erhältlich sind. Geeignete Diamine sind beispielsweise Ethylendiamin, 1,3-Propylendiamin, Tetramethylendiamin, Pentamethylendiamin, Hexamethylendiamin, p-Phenylendiamin und Toluylendiamin. Bevorzugte Diamine sind Ethylendiamin und Hexamethylendiamin. Besonders bevorzugte Bisamide sind Bismyristoylethylendiamin, Bispalmitoylethylendiamin, Bisstearoylethylendiamin und deren Gemische sowie die entsprechenden Derivate des Hexamethylendiamins.Suitable bisamides as defoamers are those which differ from saturated fatty acids with 12 to 22, preferably derived from 14 to 18 carbon atoms and from alkylenediamines with 2 to 7 carbon atoms. suitable Fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof as they are from natural fats or hardened oils, such as tallow or hydrogenated palm oil are. Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, Pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine. Preferred diamines are ethylenediamine and hexamethylenediamine. Bismyristoylethylenediamine, particularly preferred bisamides are Bispalmitoylethylenediamine, bisstearoylethylenediamine and their mixtures and the corresponding derivatives of hexamethylenediamine.
Geeignete Carbonsäureester als Entschäumer leiten sich von Carbonsäuren mit 12 bis 28 Kohlenstoffatomen ab. Insbesondere handelt es sich um Ester von Behensäure, Stearinsäure, Hydroxystearinsäure, Ölsäure, Palmitinsäure, Myristinsäure und/oder Laurinsäure. Der Alkoholteil des Carbonsäureesters enthält einen ein- oder mehrwertigen Alkohol mit 1 bis 28 Kohlenstoffatomen in der Kohlenwasserstoffkette. Beispiele von geeigneten Alkoholen sind Behenylalkohol, Arachidylalkohol, Kokosalkohol, 12-Hydroxystearylalkohol, Oleylalkohol und Laurylalkohol sowie Ethylenglykol, Glycerin, Polyvinylalkohol, Saccharose, Erythrit, Pentaerythrit, Sorbitan und/oder Sorbit. Bevorzugte Ester sind solche von Ethylenglykol, Glycerin und Sorbitan, wobei der Säureteil des Esters insbesondere aus Behensäure, Stearinsäure, Ölsäure, Palmitinsäure oder Myristinsäure ausgewählt wird. In Frage kommende Ester mehrwertiger Alkohole sind beispielsweise Xylitmonopalmitat, Pentarythritmonostearat, Glycerinmonostearat, Ethylenglykolmonostearat und Sorbitanmonostearat, Sorbitanpalmitat, Sorbitanmonolaurat, Sorbitandilaurat, Sorbitandistearat, Sorbitandibehenat, Sorbitandioleat sowie gemischte Talgalkylsorbitanmono- und -diester. Brauchbare Glycerinester sind die Mono-, Di- oder Triester von Glycerin und genannten Carbonsäuren, wobei die Mono- oder Dieester bevorzugt sind. Glycerinmonostearat, Glycerinmonooleat, Glycerinmonopalmitat, Glycerinmonobehenat und Glycerindistearat sind Beispiele hierfür. Beispiele für geeignete natürliche Ester als Entschäumer sind Bienenwachs, das hauptsächlich aus den Estern CH3(CH2)24COO(CH2)27CH3 und CH3(CH2)26COO(CH2)25CH3 besteht, und Carnaubawachs, das ein Gemisch von Carnaubasäurealkylestern, oft in Kombination mit geringen Anteilen freier Carnaubasäure, weiteren langkettigen Säuren, hochmolekularen Alkoholen und Kohlenwasserstoffen, ist.Suitable carboxylic acid esters as defoamers are derived from carboxylic acids with 12 to 28 carbon atoms. In particular, these are esters of behenic acid, stearic acid, hydroxystearic acid, oleic acid, palmitic acid, myristic acid and / or lauric acid. The alcohol part of the carboxylic acid ester contains a mono- or polyhydric alcohol with 1 to 28 carbon atoms in the hydrocarbon chain. Examples of suitable alcohols are behenyl alcohol, arachidyl alcohol, coconut alcohol, 12-hydroxystearyl alcohol, oleyl alcohol and lauryl alcohol as well as ethylene glycol, glycerin, polyvinyl alcohol, sucrose, erythritol, pentaerythritol, sorbitan and / or sorbitol. Preferred esters are those of ethylene glycol, glycerol and sorbitan, the acid part of the ester being selected in particular from behenic acid, stearic acid, oleic acid, palmitic acid or myristic acid. Eligible esters of polyhydric alcohols are, for example, xylitol monopalmitate, pentarythritol monostearate, glycerol monostearate, ethylene glycol monostearate and sorbitan monostearate, sorbitan palmitate, sorbitan monolaurate, sorbitan dilaurate, sorbitan dististearate, sorbitan dandghenoate and mixed sorbitan dibehenate, and sorbitan dandebehenate, and sorbitan dandebehenate as well as mixed sorbitan dandebehenate and sorbitan dandebiolate. Glycerol esters which can be used are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, the mono- or diesters being preferred. Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this. Examples of suitable natural esters as defoamers are beeswax, which mainly consists of the esters CH 3 (CH 2 ) 24 COO (CH 2 ) 27 CH 3 and CH 3 (CH 2 ) 26 COO (CH 2 ) 25 CH 3 , and carnauba wax , which is a mixture of carnauba acid alkyl esters, often in combination with small amounts of free carnauba acid, other long-chain acids, high-molecular alcohols and hydrocarbons.
Geeignete Carbonsäuren als weitere Entschäumerverbindung sind insbesondere Behensäure, Stearinsäure, Ölsäure, Palmitinsäure, Myristinsäure und Laurinsäure sowie deren Gemische, wie sie aus natürlichen Fetten bzw. gegebenenfalls gehärteten Ölen, wie Talg oder hydriertem Palmöl, erhältlich sind. Bevorzugt sind gesättigte Fettsäuren mit 12 bis 22, insbesondere 18 bis 22 C-Atomen.Suitable carboxylic acids as a further defoamer compound are in particular behenic acid, stearic acid, Oleic acid, palmitic acid, myristic acid and lauric acid and their mixtures, as made up natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil are. Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred.
Geeignete Fettalkohole als weitere Entschäumerverbindung sind die hydrierten Produkte der beschriebenen Fettsäuren.Suitable fatty alcohols as a further defoamer compound are the hydrogenated products of those described Fatty acids.
Weiterhin können zusätzlich Dialkylether als Entschäumer enthalten sein. Die Ether können asymmetrisch oder aber symmetrisch aufgebaut sein, d.h. zwei gleiche oder verschiedene Alkylketten, vorzugsweise mit 8 bis 18 Kohlenstoffatomen enthalten. Typische Beispiele sind Di-n-octylether, Di-i-octylether und Di-n-stearylether, insbesondere geeignet sind Dialkylether, die einen Schmelzpunkt über 25 °C, insbesondere über 40 °C aufweisen.Dialkyl ethers may also be present as defoamers. The ethers can be asymmetric or be constructed symmetrically, i.e. two identical or different alkyl chains, preferably containing 8 to 18 carbon atoms. Typical examples are di-n-octyl ether, Di-i-octyl ether and di-n-stearyl ether, particularly suitable are dialkyl ethers which have a melting point have above 25 ° C, in particular above 40 ° C.
Weitere geeignete Entschäumerverbindungen sind Fettketone, die nach den einschlägigen Methoden der präparativen organischen Chemie erhalten werden können. Zu ihrer Herstellung geht man beispielsweise von Carbonsäuremagnesiumsalzen aus, die bei Temperaturen oberhalb von 300 °C unter Abspaltung von Kohlendioxid und Wasser pyrolysiert werden, beispielsweise gemäß der deutschen Offenlegungsschrift 2553900. Geeignete Fettketone sind solche, die durch Pyrolyse der Magnesiumsalze von Laurinsäure, Myristinsäure, Palmitinsäure, Palmitoleinsäure, Stearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Arachinsäure, Gadoleinsäure, Behensäure oder Erucasäure hergestellt werden.Other suitable defoamer compounds are fatty ketones, which are based on the relevant methods of preparative organic chemistry can be obtained. One goes to their manufacture, for example of carboxylic acid magnesium salts, which at temperatures above 300 ° C below Elimination of carbon dioxide and water are pyrolyzed, for example according to the German Offenlegungsschrift 2553900. Suitable fatty ketones are those obtained by pyrolysis of the magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, Petroselinic acid, arachidic acid, gadoleic acid, behenic acid or erucic acid can be produced.
Weitere geeignete Entschäumer sind Fettsäurepolyethylenglykolester, die vorzugsweise durch basisch homogen katalysierte Anlagerung von Ethylenoxid an Fettsäuren erhalten werden. Insbesondere erfolgt die Anlagerung von Ethylenoxid an die Fettsäuren in Gegenwart von Alkanolaminen als Katalysatoren. Der Einsatz von Alkanolaminen, speziell Triethanolamin, führt zu einer äußerst selektiven Ethoxylierung der Fettsäuren, insbesondere dann, wenn es darum geht, niedrig ethoxylierte Verbindungen herzustellen. Innerhalb der Gruppe der Fettsäurepolyethylenglykolester werden solche bevorzugt, die einen Schmelzpunkt über 25 °C, insbesondere über 40 °C aufweisen .Other suitable defoamers are fatty acid polyethylene glycol esters, which are preferably basic homogeneously catalyzed addition of ethylene oxide to fatty acids can be obtained. Especially done the addition of ethylene oxide to the fatty acids in the presence of alkanolamines as catalysts. The use of alkanolamines, especially triethanolamine, leads to an extremely selective ethoxylation fatty acids, especially when it comes to producing low-ethoxylated compounds. Within the group of fatty acid polyethylene glycol esters, those which have one are preferred Have melting point above 25 ° C, especially above 40 ° C.
Innerhalb der Gruppe der wachsartigen Entschäumer werden besonders bevorzugt die beschriebenen Paraffinwachse alleine als wachsartige Entschäumer eingesetzt oder in Mischung mit einem der anderen wachsartigen Entschäumer, wobei der Anteil der Paraffinwachse in der Mischung vorzugsweise über 50 Gew.-% - bezogen auf wachsartige Entschäumermischung - ausmacht. Die Paraffinwachse können bei Bedarf auf Träger aufgebracht sein. Als Trägermaterial sind alle bekannten anorganischen und/oder organischen Trägermaterialien geeignet. Beispiele für typische anorganische Trägermaterialien sind Alkalicarbonate, Alumosilikate, wasserlösliche Schichtsilikate, Alkalisilikate, Alkalisulfate, beispielsweise Natriumsulfat, und Alkaliphosphate. Bei den Alkalisilikaten handelt es sich vorzugsweise um eine Verbindung mit einem Molverhältnis Alkalioxid zu SiO2 von 1 : 1,5 bis 1 : 3,5. Die Verwendung derartiger Silikate resultiert in besonders guten Korneigenschaften, insbesondere hoher Abriebsstabilität und dennoch hoher Auflösungsgeschwindigkeit in Wasser. Zu den als Trägermaterial bezeichneten Alumosilikaten gehören insbesondere die Zeolithe, beispielsweise Zeolith NaA und NaX. Zu den als wasserlöslichen Schichtsilikaten bezeichneten Verbindungen gehören beispielsweise amorphes oder kristallines Wasserglas. Weiterhin können Silikate Verwendung finden, welche unter der Bezeichnung Aerosil® oder Sipernat® im Handel sind. Als organische Trägermaterialien kommen zum Beispiel filmbildende Polymere, beispielsweise Polyvinylalkohole, Polyvinylpyrrolidone, Poly-(meth)acrylate, Polycarboxylate, Cellulosederivate und Stärke in Frage. Brauchbare Celluloseether sind insbesondere Alkalicarboxymethylcellulose, Methylcellulose, Ethylcellulose, Hydroxyethylcellulose und so genannte Cellulosemischether, wie zum Beispiel Methylhydroxyethylcellulose und Methylhydroxypropylcellulose, sowie deren Mischungen. Besonders geeignete Mischungen sind aus Natrium-Carboxymethylcellulose und Methylcellulose zusammengesetzt, wobei die Carboxymethylcellulose üblicherweise einen Substitutionsgrad von 0,5 bis 0,8 Carboxymethylgruppen pro Anhydroglukoseeinheit und die Methylcellulose einen Substitutionsgrad von 1,2 bis 2 Methylgruppen pro Anhydroglukoseeinheit aufweist. Die Gemische enthalten vorzugsweise Alkalicarboxymethylcellulose und nichtionischen Celluloseether in Gewichtsverhältnissen von 80 : 20 bis 40 : 60, insbesondere von 75 : 25 bis 50 : 50. Als Träger ist auch native Stärke geeignet, die aus Amylose und Amylopectin aufgebaut ist. Als native Stärke wird Stärke bezeichnet, wie sie als Extrakt aus natürlichen Quellen zugänglich ist, beispielsweise aus Reis, Kartoffeln, Mais und Weizen. Native Stärke ist ein handelsübliches Produkt und damit leicht zugänglich. Als Trägermaterialien können einzeln oder mehrere der vorstehend genannten Verbindungen eingesetzt werden, insbesondere ausgewählt aus der Gruppe der Alkalicarbonate, Alkalisulfate, Alkaliphosphate, Zeolithe, wasserlösliche Schichtsilikate, Alkalisilikate, Polycarboxylate, Celluloseether, Polyacrylat/Polymethacrylat und Stärke. Besonders geeignet sind Mischungen von Alkalicarbonaten, insbesondere Natriumcarbonat, Alkalisilikaten, insbesondere Natriumsilikat, Alkalisulfaten, insbesondere Natriumsulfat und Zeolithen.Within the group of wax-like defoamers, the paraffin waxes described are particularly preferably used alone as wax-like defoamers or in a mixture with one of the other wax-like defoamers, the proportion of paraffin waxes in the mixture preferably making up more than 50% by weight, based on the waxy defoamer mixture. The paraffin waxes can be applied to carriers if necessary. All known inorganic and / or organic carrier materials are suitable as carrier materials. Examples of typical inorganic carrier materials are alkali carbonates, aluminosilicates, water-soluble sheet silicates, alkali silicates, alkali sulfates, for example sodium sulfate, and alkali phosphates. The alkali silicates are preferably a compound with a molar ratio of alkali oxide to SiO 2 of 1: 1.5 to 1: 3.5. The use of such silicates results in particularly good grain properties, in particular high abrasion stability and nevertheless high dissolution rate in water. The aluminosilicates referred to as carrier material include, in particular, the zeolites, for example zeolite NaA and NaX. The compounds referred to as water-soluble layered silicates include, for example, amorphous or crystalline water glass. Silicates which are commercially available under the name Aerosil® or Sipernat® can also be used. Examples of suitable organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose derivatives and starch. Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof. Particularly suitable mixtures are composed of sodium carboxymethyl cellulose and methyl cellulose, the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit. The mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50. Also suitable as a carrier is native starch, which is composed of amylose and amylopectin. Starch is referred to as native starch as it is available as an extract from natural sources, for example from rice, potatoes, corn and wheat. Native starch is a commercially available product and is therefore easily accessible. Carrier materials which can be used individually or more than one of the abovementioned compounds, in particular selected from the group of alkali metal carbonates, alkali metal sulfates, alkali metal phosphates, zeolites, water-soluble sheet silicates, alkali metal silicates, polycarboxylates, cellulose ethers, polyacrylate / polymethacrylate and starch. Mixtures of alkali carbonates, in particular sodium carbonate, alkali silicates, in particular sodium silicate, alkali sulfates, in particular sodium sulfate and zeolites are particularly suitable.
Geeignete Silikone sind übliche Organopolysiloxane, die einen Gehalt an feinteiliger Kieselsäure, die wiederum auch silaniert sein kann, aufweisen können. Derartige Organopolysiloxane sind beispielsweise in der europäischen Patentanmeldung EP 0496510 A1 beschrieben. Besonders bevorzugt sind Polydiorganosiloxane, die aus dem Stand der Technik bekannt sind. Es können aber auch über Siloxan vernetzte Verbindungen eingesetzt werden, wie sie dem Fachmann unter der Bezeichnung Silikonharze bekannt sind. In der Regel enthalten die Polydiorganosiloxane feinteilige Kieselsäure, die auch silaniert sein kann. Insbesondere geeignet sind kieselsäurehaltige Dimethylpolysiloxane. Vorteilhafterweise haben die Polydiorganosiloxane eine Viskosität nach Brookfield bei 25 °C im Bereich von 5 000 mPas bis 30 000 mPas, insbesondere von 15 000 bis 25 000 mPas. Die Silikone sind vorzugsweise auf Trägermaterialien aufgebracht. Geeignete Trägermaterialien sind bereits im Zusammenhang mit den Paraffinen beschrieben worden. Die Trägermaterialien sind in der Regel in Mengen von 40 bis 90 Gew.-%, vorzugsweise in Mengen von 45 bis 75 Gew.-% - bezogen auf Entschäumer - enthalten.Suitable silicones are conventional organopolysiloxanes, which contain finely divided silica in turn can also be silanized. Such organopolysiloxanes are, for example described in European patent application EP 0496510 A1. Polydiorganosiloxanes are particularly preferred, which are known from the prior art. But it can also use siloxane crosslinked compounds are used, as they are known to those skilled in the art under the name silicone resins are known. As a rule, the polydiorganosiloxanes contain finely divided silica, which also silanes can be. Silica-containing dimethylpolysiloxanes are particularly suitable. Advantageously have the polydiorganosiloxanes have a Brookfield viscosity at 25 ° C in the range from 5,000 mPas to 30,000 mPas, in particular from 15,000 to 25,000 mPas. The silicones are preferably on carrier materials applied. Suitable carrier materials are already in connection with the paraffins have been described. The carrier materials are generally in amounts of 40 to 90% by weight, preferably in amounts of 45 to 75% by weight, based on defoamers.
Formkörper können desweiteren Co-Sprengmittel, wie Polyvinylpyrrolidon, Kollidon, Alginsäure und deren Alkalisalze, amorphe oder auch teilweise kristalline Schichtsilicate (Bentonite), Polyurethane, Polyethylenglycole sowie gaserzeugende Systeme enthalten.Shaped bodies can also contain co-disintegrants , such as polyvinylpyrrolidone, collidone, alginic acid and their alkali metal salts, amorphous or also partially crystalline layered silicates (bentonites), polyurethanes, polyethylene glycols and gas-generating systems.
Weiterhin können Proteine und Proteinderivate enthalten sein, die das Auflösungsvermögen der erfindungsgemäßen Tensidmischungen erheblich verbessern. Ausdrücklich wird hier auf die unveröffentlichte Anmeldung DE 19956802 verwiesen, deren Offenbarung auch zum Teil der Offenbarung der vorliegenden Erfindung gemacht wird. Proteins and protein derivatives may also be present, which have the resolving power of the invention Improve surfactant mixtures significantly. Expressly here is the unpublished Application DE 19956802 referenced, the disclosure of which is also part of the disclosure of the present Invention is made.
Als Proteinkomponente kommen vorzugsweise Proteinhydrolysate sowie deren Kondensationsprodukte mit Fettsäuren, untergeordnet auch Proteinhydrolysatester und quaternierte Proteinfettsäurekondensate in Frage. Proteinhydrolysate stellen Abbauprodukte von tierischen oder pflanzlichen Proteinen, beispielsweise Collagen, Elastin oder Keratin und vorzugsweise Mandel- und Kartoffelprotein sowie insbesondere Weizen-, Reis- und Sojaprotein dar, die durch saure, alkalische und/oder enzymatische Hydrolyse gespalten werden und danach ein durchschnittliches Molekulargewicht im Bereich von 600 bis 4000, vorzugsweise 2000 bis 3500 aufweisen. Obschon Proteinhydrolysate in Ermangelung eines hydrophoben Restes keine Tenside im klassischen Sinne darstellen, finden sie wegen ihrer dispergierenden Eigenschaften vielfach Verwendung zur Formulierung oberflächenaktiver Mittel. Übersichten zu Herstellung und Verwendung von Proteinhydrolysaten sind beispielsweise von G. Schuster und A. Domsch in Seifen Öle Fette Wachse 108, 177 (1982) bzw. Cosm.Toil. 99, 63 (1984), von H. W. Steisslinger in Parf.Kosm 72, 556 (1991) und F. Aurich et al. in Tens.Surf.Det. 29, 389 (1992) erschienen. Vorzugsweise werden pflanzliche Proteinhydrolysate auf Basis von Weizengluten oder Reisprotein eingesetzt, deren Herstellung in den beiden Deutschen Patentschriften DE 19502167 C1 und DE 19502168 C1 (Henkel) beschrieben wird. Aus der Proteinhydrolysaten lassen sich durch Kondensation mit C6-C22-, vorzugsweise C12-C18-Fettsäuren anionische Tenside, so genannte Proteinfettsäurekondensate herstellen, die mit Seifen vergleichbare Eigenschaften aufweisen. Vorzugsweise werden Kondensate der genannten Hydrolysate mit Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Linolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure eingesetzt.Protein hydrolyzates and their condensation products with fatty acids are preferred as protein components, and subordinate protein hydrolyzate esters and quaternized protein fatty acid condensates are also suitable. Protein hydrolysates are degradation products of animal or vegetable proteins, for example collagen, elastin or keratin and preferably almond and potato protein, and in particular wheat, rice and soy protein, which are cleaved by acidic, alkaline and / or enzymatic hydrolysis and then have an average molecular weight in Have range from 600 to 4000, preferably 2000 to 3500. Although protein hydrolyzates do not represent a surfactant in the classic sense due to the lack of a hydrophobic residue, they are widely used for the formulation of surface-active agents because of their dispersing properties. Overviews of the production and use of protein hydrolyzates are, for example, by G. Schuster and A. Domsch in Seifen Öle Fette Wachsen 108 , 177 (1982) and Cosm.Toil. 99 , 63 (1984), by HW Steisslinger in Parf.Kosm 72 , 556 (1991) and F. Aurich et al. in Tens.Surf.Det. 29 , 389 (1992). Vegetable protein hydrolyzates based on wheat gluten or rice protein are preferably used, the production of which is described in the two German patents DE 19502167 C1 and DE 19502168 C1 (Henkel). Anionic surfactants, so-called protein fatty acid condensates, which have properties comparable to soaps, can be produced from the protein hydrolyzates by condensation with C 6 -C 22 , preferably C 12 -C 18 fatty acids. Preference is given to condensates of the hydrolysates mentioned with caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, aracholeic acid, araoleic acid, elasoleic acid, araoleic acid used.
Als Parfümöle bzw. Duftstoffe können einzelne Riechstoffverbindungen, z.B. die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden. Riechstoffverbindungen vom Typ der Ester sind z.B. Benzylacetat, Phenoxyethylisobutyrat, p-tert.-Butylcyclohexylacetat, Linalylacetat, Dimethylbenzylcarbinylacetat, Phenylethylacetat, Linalylbenzoat, Benzylformiat, Ethylmethylphenylglycinat, Allylcyclohexylpropionat, Styrallylpropionat und Benzylsalicylat. Zu den Ethern zählen beispielsweise Benzylethylether, zu den Aldehyden z.B. die linearen Alkanale mit 8-18 C-Atomen, Citral, Citronellal, Citronellyloxyacetaldehyd, Cyclamenaldehyd, Hydroxycitronellal, Lilial und Bourgeonal, zu den Ketonen z.B. die Jonone, α-Isomethylionon und Methylcedrylketon, zu den Alkoholen Anethol, Citronellol, Eugenol, Geraniol, Linalool, Phenylethylalkohol und Terpineol, zu den Kohlenwasserstoffen gehören hauptsächlich die Terpene wie Limonen und Pinen, Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen. Solche Parfümöle können auch natürliche Riechstoffgemische enthalten, wie sie aus pflanzlichen Quellen zugänglich sind, z.B. Pine-, Citrus-, Jasmin-, Patchouly-, Rosen- oder Ylang-Ylang-Öl. Ebenfalls geeignet sind Muskateller, Salbeiöl, Kamillenöl, Nelkenöl, Melissenöl, Minzöl, Zimtblätteröl, Lindenblütenöl, Wacholderbeeröl, Vetiveröl, Olibanumöl, Galbanumöl und Labdanumöl sowie Orangenblütenöl, Neroliol, Orangenschalenöl und Sandelholzöl. Die Duftstoffe können direkt in die erfindungsgemäßen Mittel eingearbeitet werden, es kann aber auch vorteilhaft sein, die Duftstoffe auf Träger aufzubringen, welche die Haftung des Parfüms auf der Wäsche verstärken und durch eine langsamere Duftfreisetzung für langanhaltenden Duft der Textilien sorgen. Als solche Trägermaterialien haben sich beispielsweise Cyclodextrine bewährt, wobei die Cyclodextrin-Parfüm-Komplexe zusätzlich noch mit weiteren Hilfsstoffen beschichtet werden können.Individual fragrance compounds , for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances . Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, allylcyclohexylpropylatepylatepylatepylatepionate, stally. The ethers include, for example, benzyl ethyl ether, the aldehydes include, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, and the ketones include, for example, the jonones, α-isomethylionone and methylcedryl ketone the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene, but preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil. The fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
Falls gewünscht können die Endzubereitungen noch anorganische Salze als Füll- bzw. Stellmittel enthalten, wie beispielsweise Natriumsulfat, welches vorzugsweise in Mengen von 0 bis 20, insbesondere 1 bis 12 Gew.-% - bezogen auf den Formkörper - enthalten ist.If desired, the final preparations can also contain inorganic salts as fillers or fillers , for example sodium sulfate, which is preferably present in amounts of 0 to 20, in particular 1 to 12,% by weight, based on the shaped body.
Die Herstellung von Formkörpern, vorzugsweise solchen in Tablettenform, erfolgt in der Regel durch Tablettierung bzw. Pressagglomerierung. Die erhaltenen teilchenförmigen Pressagglomerate können entweder direkt als Waschmittel eingesetzt oder zuvor nach üblichen Methoden nachbehandelt und/oder aufbereitet werden. Zu den üblichen Nachbehandlungen zählen beispielsweise Abpuderungen mit feinteiligen Inhaltsstoffen von Wasch- oder Reinigungsmitteln, wodurch das Schüttgewicht im Allgemeinen weiter erhöht wird. Eine bevorzugte Nachbehandlung stellt jedoch auch die Verfahrensweise gemäß den deutschen Patentanmeldungen 19524287 A1 und 19547457 A1 dar, wobei staubförmige oder zumindest feinteilige Inhaltsstoffe (die sogenannten Feinanteile) an die erfindungsgemäß hergestellten teilchenförmigen Verfahrensendprodukte, welche als Kern dienen, angeklebt werden und somit Mittel entstehen, welche diese so genannten Feinanteile als Außenhülle aufweisen. Vorteilhafterweise geschieht dies wiederum durch eine Schmelzagglomeration. Zur Schmelzagglomerierung der Feinanteile an wird ausdrücklich auf die Offenbarung in den deutschen Patentanmeldungen 19524287 A1 und 19547457 A1 verwiesen. In der bevorzugten Ausführungsform der Erfindung liegen die festen Waschmittel in Tablettenform vor, wobei diese Tabletten insbesondere aus lager- und transporttechnischen Gründen vorzugsweise abgerundete Ecken und Kanten aufweisen. Die Grundfläche dieser Tabletten kann beispielsweise kreisförmig oder rechteckig sein. Mehrschichtentabletten, insbesondere Tabletten mit 2 oder 3 Schichten, welche auch farblich verschieden sein können, sind vor allem bevorzugt. Die Farben Blau, Grün, Weiß, Pink und deren Farbkombinationen sind dabei besonders bevorzugt. Die Tabletten können dabei auch gepresste und ungepresste Anteile enthalten. Formkörper mit besonders vorteilhafter Auflösegeschwindigkeit werden erhalten, wenn die granularen Bestandteile vor dem Verpressen einen Anteil an Teilchen, die einen Durchmesser außerhalb des Bereiches von 0,02 bis 6 mm besitzen, von weniger als 20, vorzugsweise weniger als 10 Gew.-% aufweisen. Bevorzugt ist eine Teilchengrößenverteilung im Bereich von 0,05 bis 2,0 und besonders bevorzugt von 0,2 bis 1,0 mm. Shaped bodies, preferably tablets, are generally produced by Tableting or press agglomeration. The particulate press agglomerates obtained can either used directly as a detergent or previously treated by customary methods and / or processed. The usual post-treatments include powdering with finely divided ingredients of detergents or cleaning agents, which means the bulk density in general is further increased. However, the procedure is also a preferred aftertreatment according to German patent applications 19524287 A1 and 19547457 A1, being dust-like or at least finely divided ingredients (the so-called fine fractions) of those produced according to the invention Particulate process end products, which serve as the core, are glued and thus Means are created which have these so-called fines as an outer shell. advantageously, this in turn occurs through melting agglomeration. For melt agglomeration of the fines is expressly referred to the disclosure in German patent applications 19524287 A1 and 19547457 A1. In the preferred embodiment of the invention, the solid detergents are in tablet form, these tablets in particular from storage and transport technology Reasons preferably have rounded corners and edges. The base of these tablets can be circular or rectangular, for example. Multi-layer tablets, especially tablets with 2 or 3 layers, which can also have different colors, are particularly preferred. The Colors blue, green, white, pink and their color combinations are particularly preferred. The Tablets can also contain pressed and unpressed parts. Molded body with special advantageous dissolution rates are obtained if the granular components before pressing a proportion of particles having a diameter outside the range of 0.02 to 6 mm have less than 20, preferably less than 10 wt .-%. A particle size distribution is preferred in the range from 0.05 to 2.0 and particularly preferably from 0.2 to 1.0 mm.
Formkörper können durch vorbestimmte Raumformen in vorbestimmter Größe und Form gefertigt werden. Als Raumform kommen praktisch alle sinnvoll handhabbaren Ausgestaltungen in Betracht, beispielsweise also die Ausbildung als Tafel, die Stab- bzw. Barrenform, Würfel, Quader und entsprechende Raumelemente mit ebenen Seitenflächen sowie insbesondere zylinderförmige Ausgestaltungen mit kreisförmigem oder ovalem Querschnitt. Diese letzte Ausgestaltung erfaßt dabei die Darbietungsform von der Tablette bis zu kompakten Zylinderstücken mit einem Verhältnis von Höhe zu Durchmesser oberhalb 1.Shaped bodies can be produced in a predetermined size and shape by predetermined spatial shapes. Practically all expediently manageable configurations come into consideration as the spatial shape, for example So the training as a board, the rod or bar shape, cubes, cuboids and the like Room elements with flat side surfaces and, in particular, cylindrical configurations circular or oval cross section. This last embodiment covers the form of presentation from tablets to compact cylinder pieces with a ratio of height to diameter above 1.
Die portionierten Preßlinge können dabei jeweils als voneinander getrennte Einzelelemente ausgebildet sein, die der vorbestimmten Dosiermenge der Wasch- und/oder Reinigungsmittel entspricht. Ebenso ist es aber möglich, Preßlinge auszubilden, die eine Mehrzahl solcher Masseneinheiten in einem Preßling verbinden, wobei insbesondere durch vorgegebene Sollbruchstellen die leichte Abtrennbarkeit portionierter kleinerer Einheiten vorgesehen ist. Für den Einsatz von Textilwaschmitteln in Maschinen des in Europa üblichen Typs mit horizontal angeordneter Mechanik kann die Ausbildung der portionierten Preßlinge als Tabletten, in Zylinder- oder Quaderform zweckmäßig sein, wobei ein Durchmesser/Höhe-Verhältnis im Bereich von etwa 0,5 : 2 bis 2 : 0,5 bevorzugt ist. Handelsübliche Hydraulikpressen, Exzenterpressen oder Rundläuferpressen sind geeignete Vorrichtungen insbesondere zur Herstellung derartiger Preßlinge.The portioned compacts can each be designed as separate individual elements be, which corresponds to the predetermined dosage of detergents and / or cleaning agents. Likewise but it is possible to form compacts that have a plurality of such mass units in one compact connect, the portionability being easy to separate, in particular by predetermined predetermined breaking points smaller units is provided. For the use of textile detergents in machines of In Europe, the usual type with horizontally arranged mechanics can be the portioned Moldings as tablets, in cylindrical or cuboid form, are expedient, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, especially for manufacturing such compacts.
Die Raumform einer anderen Ausführungsform der Formkörper ist in ihren Dimensionen der Einspülkammer von handelsüblichen Haushaltswaschmaschinen angepaßt, so dass die Formkörper ohne Dosierhilfe direkt in die Einspülkammer eindosiert werden können, wo sie sich während des Einspülvorgangs auflöst. Selbstverständlich ist aber auch ein Einsatz der Waschmittelformkörper über eine Dosierhilfe problemlos möglich und im Rahmen der vorliegenden Erfindung bevorzugt.In terms of its dimensions, the spatial shape of another embodiment of the shaped bodies is the induction chamber adapted from commercially available household washing machines, so that the moldings without metering aid can be dosed directly into the induction chamber, where they are during the induction process dissolves. Of course, it is also possible to use the detergent tablets via a metering aid easily possible and preferred in the context of the present invention.
Ein weiterer bevorzugter Formkörper, der hergestellt werden kann, hat eine platten- oder tafelartige Struktur mit abwechselnd dicken langen und dünnen kurzen Segmenten, so dass einzelne Segmente von diesem "Riegel" an den Sollbruchstellen, die die kurzen dünnen Segmente darstellen, abgebrochen und in die Maschine eingegeben werden können. Dieses Prinzip des "riegelförmigen" Formkörperwaschmittels kann auch in anderen geometrischen Formen, beispielsweise senkrecht stehenden Dreiecken, die lediglich an einer ihrer Seiten längsseits miteinander verbunden sind, verwirklicht werden. Another preferred shaped body that can be produced has a plate-like or sheet-like shape Structure with alternating thick long and thin short segments, so that individual segments broken off from this "bolt" at the predetermined breaking points, which represent the short, thin segments and can be entered into the machine. This principle of the "bar-shaped" shaped body detergent can also be in other geometric shapes, for example vertical triangles, which are connected to each other only on one of their sides, can be realized.
Durch Abmischung von tensidhaltigen Granulaten mit pulverförmigen Aufbereitungskomponenten wurden
Vorgemische hergestellt, die in einer Kilian-Tablettenpresse zu Waschmittel-Tabletten von je 40g
verpresst wurden. Dabei wurde der Pressdruck empirisch so eingestellt, dass jeweils drei Serien von
Presslingen erhalten wurden, die sich nur in ihrer Härte unterscheiden.
Anschließend wurden die Tabletten luftdicht verpackt und für 2 Wochen bei 40 °C gelagert. Die Zusammensetzungen
der Waschmitteltabletten sind der Tabelle 1 zu entnehmen. Die Rezepturen 1 bis
6 sind erfindungsgemäß, die Rezepturen V1 bis V4 dienen zum Vergleich. Der Tensidgehalt (waschaktive
Substanzen) wurde als Aktivsubstanz berechnet.By mixing surfactant-containing granules with pulverulent preparation components, premixes were produced which were compressed in a Kilian tablet press into detergent tablets of 40 g each. The pressure was set empirically in such a way that three series of compacts were obtained, which differ only in their hardness.
The tablets were then packed airtight and stored at 40 ° C. for 2 weeks. The compositions of the detergent tablets are shown in Table 1. Formulations 1 to 6 are according to the invention, formulations V1 to V4 are used for comparison. The surfactant content (washing-active substances) was calculated as the active substance.
Zur Beurteilung des Auflöseverhaltens wurde eine Tablette auf ein Drahtgestell gelegt, welches in Wasser (0 °dH, 25 °C) stand. Die Tablette war dabei vollständig von Wasser umgeben. Gemessen wurde die Zerfallszeit vom Eintauchen bis zur vollständigen Auflösung. Die Zerfallszeiten sind ebenfalls der Tabelle 1 zu entnehmen.To assess the dissolution behavior, a tablet was placed on a wire frame, which was in water (0 ° dH, 25 ° C). The tablet was completely surrounded by water. Was measured the decay time from immersion to complete dissolution. The disintegration times are the same Table 1.
In Tabelle 1 sind Testrezepturen für Waschmitteltabletten und deren Löslichkeiten dargestellt. Die Angaben
beziehen sich auf Gew.% bezogen auf den Formkörper, zusätzlich wurden die waschaktiven
Substanzen (Kokosalkoholsulfat-Natriumsalz, LAS, Fettalkoholalkoxylat FAAO, C12/14 - Alkylpolyglucopsid
APG) auf Aktivsubstanz (*) berechnet. Die Aktivsubstanz beschreibt den absoluten Gehalt an
waschaktiven Substanzen. Ein Bilanzierung der Rezepturen auf 100% erfolgt durch Natriumsulfat
(ad 100).
Die Formkörper können bis zu 15 Gew.% freies oder gebundenes Wasser enthalten, das z.B. durch den
Einsatz von Buildern oder Sprengmitteln eingebracht wird.
Die Härte der Tabletten wurde durch Verformung der Tablette bis zum Bruch gemessen, wobei die Kraft
auf die Seitenflächen der Tablette einwirkte und die maximale Kraft, der die Tablette standhielt, ermittelt
wurde.
The moldings can contain up to 15% by weight of free or bound water, which is introduced, for example, by using builders or disintegrants.
The hardness of the tablets was measured by deforming the tablet to fracture, the force acting on the side surfaces of the tablet and the maximum force that the tablet was able to withstand.
Claims (9)
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DE10118270 | 2001-04-12 |
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ES2776635T3 (en) | 2015-10-07 | 2020-07-31 | Elementis Specialties Inc | Wetting and defoaming agent |
IT201900022392A1 (en) * | 2019-11-28 | 2021-05-28 | Salros S R L | LIQUID WASHING COMPOSITION WITH SEPARATE COMPONENTS, FOR LAUNDRY IN AUTOMATIC WASHING MACHINES |
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DE19616693A1 (en) * | 1996-04-26 | 1997-11-06 | Henkel Kgaa | Enol esters as bleach activators for detergents and cleaning agents |
US6566317B2 (en) * | 2000-04-25 | 2003-05-20 | Cognis Corporation | Process for inhibiting gel formation of hydrated detergent tablets containing nonionic surfactant ethoxylates |
-
2001
- 2001-04-12 DE DE10118270A patent/DE10118270A1/en not_active Withdrawn
-
2002
- 2002-04-03 EP EP02007552A patent/EP1249489A1/en not_active Withdrawn
- 2002-04-12 US US10/122,482 patent/US20030027740A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19754289A1 (en) * | 1997-12-08 | 1999-06-10 | Henkel Kgaa | Detergent tablets with improved disintegration properties |
WO1999042556A1 (en) * | 1998-02-20 | 1999-08-26 | Henkel Kommanditgesellschaft Auf Aktien | Shaped bodies of detergent with improved properties |
DE19934704A1 (en) * | 1999-07-23 | 2001-01-25 | Henkel Kgaa | Washing or detergent agent molded article comprises particles of average size below 800 microns containing a non-surfactant solid dispersant not from mono-, di-, tri-, oligo- and poly-saccharides or paraffin |
EP1074608A1 (en) * | 1999-08-02 | 2001-02-07 | Robert McBride Ltd | Detergent tablets |
Also Published As
Publication number | Publication date |
---|---|
DE10118270A1 (en) | 2002-10-17 |
US20030027740A1 (en) | 2003-02-06 |
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