EP1249489A1 - Corps moules d'agents de lavage et de nettoyage présentant des proprietés de décomposition améliorées - Google Patents

Corps moules d'agents de lavage et de nettoyage présentant des proprietés de décomposition améliorées Download PDF

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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
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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.)
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EP02007552A
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German (de)
English (en)
Inventor
Ditmar Kischkel
Manfred Dr. Weuthen
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BASF Personal Care and Nutrition GmbH
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Cognis Deutschland GmbH and Co KG
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Publication of EP1249489A1 publication Critical patent/EP1249489A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP02007552A 2001-04-12 2002-04-03 Corps moules d'agents de lavage et de nettoyage présentant des proprietés de décomposition améliorées Withdrawn EP1249489A1 (fr)

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US20160145542A1 (en) * 2014-11-25 2016-05-26 Milliken & Company Cleaning Composition
US10022691B2 (en) 2015-10-07 2018-07-17 Elementis Specialties, Inc. Wetting and anti-foaming agent
IT201900022392A1 (it) * 2019-11-28 2021-05-28 Salros S R L Composizione di lavaggio liquida a componenti separati, per bucato in macchine lavatrici automatiche

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