Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/20—Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease

Definitions

• the invention is in the field of detergents and relates to corresponding liquid or solid preparations containing special copolymers and to their use for the preparation of the compositions.
• Modern liquid or solid detergents represent complex mixtures of active ingredients, which in their entirety should cover the complex profile of requirements for these products.
• the focus of consumers' wishes is furthermore to equip the laundry, for example, to prevent dirt from being re-absorbed, and to give the fibers an anti-static and anti-static treatment , which makes ironing easier ("easy ironing") or - in the case of liquid products - the setting of a sufficiently high and storage-stable viscosity so that the agents can be applied easily.
• the object of the present invention was therefore to provide polymers for the production of solid, but preferably liquid detergents, which furnish fibers or textile fabrics made therefrom in such a way that they significantly reduce the re-uptake of dirt particles and reduce the static charge and thus make ironing easier and increase the viscosity of the preparations - provided they are liquid products - permanently and stably.
• R 1 is hydrogen or a methyl group
• R 2 is a linear or branched alkyl radical with 1 to 6 carbon atoms
• R 3 and R 4 are independently hydrogen or a linear or branched, optionally hydroxy substituted alkyl radical with 1 to 12 carbon atoms or alone or together represents part of an aliphatic or aromatic ring system
• n represents numbers from 1 to 6
• X represents halide.
• the polymers in detergents satisfactorily meet the desired requirement profile.
• the polymers are suitable for building up viscosity in liquid formulations and also stabilizing them against the effects of temperature and storage time. They absorb both natural and synthetic fibers and, on the one hand, reduce re-soiling ("soil repellant” effect) and on the other hand reduce the static charge by film formation and thereby facilitate ironing ("easy ironing" effect).
• the copolymers may contain methacrylic acid as monomer component (a), but preferably acrylic acid.
• Suitable monomer components (b) are esters of acrylic or methacrylic acid with lower linear or branched alcohols with 1 to 6 carbon atoms or fatty alcohols with 8 to 22 carbon atoms. They are preferably esters of acrylic acid with methanol, ethanol, or the isomeric butanols.
• Homopolymers based on the cationic component (c) and their use for the preparation of agents for cleaning hard surfaces or as rinse aids are already known from the prior art (cf. EP 0876460 B1, EP 0876459 B1, EP 0248185 B1).
• Preferred monomer components (c) are those quaternary ammonium compounds of the formula (I) in which R 1 , R 2 , R 3 and R 4 are methyl, n is 3 and X is chloride.
• the three components can be polymerized in a manner known per se.
• the monomer components (a), (b) and (c) can usually be in a weight ratio of 1: (0.5 to 10): (0.5 to 10), preferably 1: (2 to 7): (2 to * 7 ) and preferably 1: (4 to 6): (4 to 6) can be used.
• the polymers can have an average molecular weight of 1,000 to 50,000, preferably 5,000 to 30,000 and in particular 8,000 to 15,000 daltons.
• the proportion of the copolymers in the end products can finally be 0.1 to 10, preferably 0.5 to 5 and in particular 1 to 3% by weight, based on the composition.
• Another object of the present invention relates to the use of copolymers of
• R is hydrogen or a methyl group
• R is a linear or branched alkyl radical having 1 to 6 carbon atoms
• R 3 and R 4 are, independently of one another, hydrogen or a linear or branched, optionally hydroxyl-substituted alkyl radical having 1 to 12 carbon atoms or alone or together for the part of an aliphatic or aromatic ring system
• n for numbers from 1 to 6 and X for halide, for the production of liquid or solid detergents and of laundry aftertreatment agents, in which they can contain, for example, in amounts of 0.1 to 10, preferably 0.5 to 5 and in particular 1 to 3% by weight, based on the composition.
• Further objects of the invention also relate to their use for finishing synthetic and natural fibers and textile fabrics and as viscosity regulators for liquid surfactant preparations.
• the agents according to the invention can furthermore contain typical auxiliaries and additives, such as, for example, anionic, nonionic, cationic, amphoteric or zwitterionic surfactants, builders, co-builders, oil and fat-dissolving substances, bleaching agents, bleach activators, graying inhibitors, enzymes, enzyme stabilizers, optical brighteners , other polymers, defoamers, disintegrants, fragrances, inorganic salts and the like, as will be explained in more detail below.
• auxiliaries and additives such as, for example, anionic, nonionic, cationic, amphoteric or zwitterionic surfactants, builders, co-builders, oil and fat-dissolving substances, bleaching agents, bleach activators, graying inhibitors, enzymes, enzyme stabilizers, optical brighteners , other polymers, defoamers, disintegrants, fragrances, inorganic salts and the like, as will be explained in more detail below.
• anionic surfactants are soaps, alkyl benzene sulfonates, alkane sulfonates, olefin sulfonates, alkyl ether sulfonates, glycerol ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, alkyl sulfates, fatty alcohol ether sulfates, glycerol ether sulfates, hydroxymixed ether sulfates, fatty sulfate ethersulfate, monoglyphate sulfates, monoglyphate sulfates, and dialkyl sulfosuccinates, mono- and dialkyl sulfosuccinamates, sulfotriglycerides, amide soaps, ether carboxylic acids and their salts, fatty acid isethionates, fatty acid sarcosinates,
• anionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
• Alkyl benzene sulfonates, alkyl sulfates, soaps, alkane sulfonates, olefin sulfonates, methyl ester sulfonates and mixtures thereof are preferably used.
• R 5 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, alkylammomum, alkanolammonium or glucammonium.
• 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 and / or secondary alcohols, which preferably follow the formula (III),
• R 6 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, oleyl alcohol, oleyl alcohol, Petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol and erucyl alcohol as well as their technical mixtures, which are obtained by 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 ⁇ 6 / ⁇ 8 tallow fatty alcohols or vegetable fatty alcohols of comparable carbon chain distribution in the form of their sodium salts.
• these are oxo alcohols, as are obtainable, for example, by converting carbon monoxide and hydrogen to alpha-containing olefins using the shop process.
• Such alcohol mixtures are commercially available under the trade names Dobanol® or Neodol®.
• Suitable alcohol mixtures are Dobanol 91®, 23®, 25®, 45®.
• Another possibility are oxo alcohols, such as those created by the addition of carbon monoxide and carbon dioxide according to the classic Enichema or Condea oxo process
• Alcohol mixtures are a mixture of strongly branched alcohols. Such alcohol mixtures are commercially available under the trade name Lial®. Suitable alcohol mixtures are Lial 91®, 111®, 123®, 125®, 145®.
• R 7 CO represents a linear or branched, saturated or unsaturated acyl radical having 6 to 22 and preferably 12 to 18 carbon atoms and in turn X represents 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, elaidic acid, elaidic acid.
• Linoleic acid Linoleic acid, linolenic acid, eleostearic 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.
• nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, alk (en) yl oligoglycosides, fatty acid N-alkyl glucate acid (vegetable hydrolysate), vegetable hydrolysate, vegetable hydrolysate, protein hydrolysate, vegetable hydrolysate, vegetable hydrolysate , Sugar esters, sorbitan esters, polysorbates and amine oxides.
• nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
• Fatty alcohol polyglycol ethers, alkoxylated fatty acid lower alkyl esters or alkyl oligoglucosides are preferably used.
• the preferred fatty alcohol polyglycol ethers follow the formula (V) R 8 O (CH 2 CHR 9 O) nl H (V)
• R represents a linear or branched alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms
• R 9 represents hydrogen or methyl
• nl represents numbers from 1 to 20.
• Typical examples are the addition products of an average of 1 to 20 and preferably 5 to 10 moles of ethylene and / or propylene oxide with capron alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostanol , Oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, linolyl alcohol, linolenyl alcohol, elaeostearyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures. Addition products of 3, 5
• Suitable alkoxylated fatty acid lower alkyl esters are surfactants of the formula (VI)
• R 10 CO for a linear or branched, saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms, R for hydrogen or methyl, R for linear or branched alkyl radicals with 1 to 4 carbon atoms and n2 for numbers from 1 to
• 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, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, technical acid and erucic acid and mixtures thereof.
• the products are usually prepared by inserting the alkylene oxides into the carbonyl ester bond in the presence of special catalysts, e.g. calcined hydrotalcite. Conversion products of an average of 5 to 10 moles of ethylene oxide into the are particularly preferred
• Alkyl and alkenyl oligoglycosides which are also preferred nonionic surfactants, usually follow the formula (VII),
• R 13 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms
• G is a sugar radical having 5 or 6 carbon atoms
• p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry.
• 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.
• alkyl and or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.
• the alkyl or alkenyl radical R 13 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 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 can be obtained as described above.
• cationic surfactants are, in particular, tetraalkylammonium compounds, such as, for example, dimethyldistearylammonium chloride or hydroxyethyl hydroxycetyldimmonium chloride (Dehyquart E) or esterquats. These are, for example, quaternized fatty acid triethanolamine ester salts of the formula (VIII),
• R 1 CO for an acyl radical with 6 to 22 carbon atoms
• R 15 and R 16 independently of one another for hydrogen or R 14 CO
• ester quats which 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 , as they occur, for example, in the pressure splitting of natural fats and oils.
• 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 C 16/18 - tallow or palm fatty acid (iodine number 0 to 40).
• quaternized fatty acid triethanolamine ester salts of the formula (VIII) have proven particularly advantageous in which R 14 CO for an acyl radical having 16 to 18 carbon atoms, R 15 for R I5 CO, R 16 for hydrogen, R 17 for a methyl group , ml, m2 and m3 stands for 0 and Y for methyl sulfate.
• quaternized ester salts of fatty acids with diethanolalkylamines of the formula (IX) are also suitable as esterquats.
• R 18 CO for an acyl radical with 6 to 22 carbon atoms
• R 19 for hydrogen or R 18 CO
• R 20 and R 21 independently of one another for alkyl radicals with 1 to 4 carbon atoms
• m5 and m6 in total for 0 or numbers from 1 to 12
• Y again represents halide, alkyl sulfate or alkyl phosphate.
• ester quats are substances in which the ester bond is replaced by an amide bond and which preferably follow the formula (XI) based on diethylenetriamine,
• R 27 CO represents an acyl radical with 6 to 22 carbon atoms
• R 29 and R 30 independently of one another for alkyl radicals with 1 to 4 carbon atoms
• amide ester quats are available on the market, for example, under the Incroquat® (Croda) brand.
• Amphoteric or zwitterionic surfactants are available on the market, for example, under the Incroquat® (Croda) brand.
• amphoteric or zwitterionic surfactants are alkyl betaines, alkyl amidobetaines, aminopropionates, aminoglycinates, imidazolinium betaines and sulfobetaines.
• alkyl betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (XII)
• R 31 for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms
• R 32 for hydrogen or alkyl radicals with 1 to 4 carbon atoms
• R 33 for alkyl radicals with 1 to 4 carbon atoms
• ql 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 methylamine hexyl, hexyldimethylamine, octyldimethylamine, De-cyldimethylamin, lamin Dodecylmethy-, dodecyldimethylamine, Dodecylethylmethylamin, C 12/1 -Kokosalkyldimethylamin, ristyldimethylamin mu-, cetyldimethylamine, stearyldimethylamine, stearyl, oleyl dimethylamine, Ci 6 / 18 -Talgalkyldimethylamin and their technical mixtures.
• Carboxyalkylation products of amidoamines which follow the formula (XIII) are also suitable,
• R 34 CO for an aliphatic acyl radical with 6 to 22 carbon atoms and 0 or 1 to 3 double bonds
• R 35 for hydrogen or alkyl radicals with 1 to 4 carbon atoms
• q2 for numbers from 1 to 6
• q3 for numbers from 1 to 3 and Z again 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, arenachic acid, gadeleostearic acid, gaoleostolic acid , Behenic acid and erucic 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.
• condensation product of C 8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate is preferred.
• Imidazolinium betaines are also suitable. These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines such as, for example, aminoethylethanolamine (AEEA) or diethylenetriamine.
• the corresponding carboxyalkylation products are mixtures of different open-chain betaines.
• Typical examples are condensation products of the abovementioned fatty acids with AEEA, preferably imidazolines based on lauric acid or again C 12/1 coconut fatty acid, which are subsequently betainized with sodium chloroacetate.
• the washing, rinsing, cleaning and finishing agents according to the invention can furthermore contain additional inorganic and organic builder substances, for example in amounts of 10 to 50 and preferably 15 to 35% by weight, based on the agent, zeolites being the main inorganic builder substances crystalline layered silicates, amorphous silicates and - where permissible - also phosphates, such as Tripolyphosphate are used.
• additional inorganic and organic builder substances for example in amounts of 10 to 50 and preferably 15 to 35% by weight, based on the agent, zeolites being the main inorganic builder substances crystalline layered silicates, amorphous silicates and - where permissible - also phosphates, such as Tripolyphosphate are used.
• the amount of co-builder is to be counted against the preferred amounts of phosphates.
• 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. Of particular interest is also a cocrystallized sodium / potassium
• Aluminum silicate from zeolite A and zeolite X which is commercially available as 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 2 to 5 ethylene oxide groups, C 12 -C 1 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.
• Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x ⁇ 2 ⁇ + ryH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to Is 20 and preferred values for x are 2, 3 or 4.
• Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
• both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 ⁇ 5 -yH 2 O are preferred.
• Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here.
• Suitable sheet silicates, which belong to the group of water-swellable smectites, are, for example, those of the general formulas
• the layered silicates can also contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca 2+ .
• the amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing.
• Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
• 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 have been caused in various ways, for example by surface treatment, compounding, compacting, compaction or by overdrying.
• 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
• nm and in particular up to a maximum of 20 nm are preferred, particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.
• phosphates As builders, provided that such use should not be avoided for ecological reasons.
• the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Their content is generally not more than 25% by weight, preferably not more than 20% by weight, in each case based on the finished composition. In some cases, it has been shown that tripolyphosphates in particular, even in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances lead to a synergistic improvement in the secondary washing ability.
• Usable organic builders that are suitable as co-builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such an use is sufficient ecological reasons are 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 acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents.
• Citric acid Bern- to name succinic acid, glutaric acid, adipic acid, gluconic acid and 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 can be used.
• the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are able to oxidize at least one alcohol function of the saccharide ring to the carboxylic acid function.
• Suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate. Glycerol disuccinates and glycerol trisuccinates are also particularly preferred in this context. Suitable amounts for use in zeolite-containing and / or silicate-containing formulations are 3 to 15% by weight.
• Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
• Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular cooling mass of 800 to 150,000 (based on acid and measured against polystyrene sulfonic acid in each case).
• Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
• Their 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, with 20 to 55% by weight aqueous solutions being preferred.
• Granular polymers are usually subsequently mixed into one or more basic granules.
• Biodegradable polymers composed of more than two different monomer units are also particularly preferred.
• polymeric aminodicarboxylic acids, their salts or their precursor substances are also particularly preferred.
• Polyaspartic acids or their salts and derivatives are particularly preferred.
• polyacetals which are obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
• Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.
• the agents can also contain components which have a positive influence on the oil and fat washability from 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% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether , and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof.
• the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred. Bleaching agents and bleach activators
• 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 peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
• the bleaching agent content of the agents is preferably 5 to 35% by weight and in particular up to 30% by weight, advantageously using perborate monohydrate or percarbonate.
• Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
• Multi-acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU) are preferred , N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetate, especially triacetate, especially trihydric alcohols , 5-diacetoxy-2,5-dihydrofuran, enol est
• Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.
• sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes may also be present as so-called bleaching catalysts.
• the transition metal compounds in question include in particular manganese, iron, cobalt, ruthenium or molybdenum salen complexes and their N-analog compounds, manganese, iron, cobalt, ruthenium or molybdenum-carbonyl complexes, manganese, Iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with tripod ligands containing nitrogen, as well as cobalt, iron, copper and ruthenium amine complexes.
• Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 0.0025% by weight. % up to 0.25% by weight % and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total average.
• 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 i insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases 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
• Known cutinases are examples of such lipolytically active enzymes.
• Peroxidases or oxidases have also proven to be suitable in some cases.
• Suitable amylases include
• ⁇ -amylases 5 len in particular ⁇ -amylases, iso-amylases, PuUulanases 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 to protect them against premature decomposition.
• the proportion of the 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 stable with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme. are bilized.
• 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 HB 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, e.g. degraded starch, aldehyde starches etc. Polyvmylpyrrolidon is also useful.
• 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 Means 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-l, 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) diphenyl. 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 % by weight, preferably around 10 "5 % by weight, of a blue dye.
• a particularly preferred dye is Tinolux® (commercial product from Ciba-Geigy). polymers
• Soil repellants are substances which preferably contain ethylene terephthalate and / or polyethylene glycol terephthalate groups, the molar ratio of ethylene terephthalate to polyethylene glycol terephthalate being in the range from 50:50 to 90:10.
• the molecular weight of the linking polyethylene glycol units is in particular in the range from 750 to 5000, i.e. 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 also be used. paraffin waxes
• Suitable paraffin waxes generally represent a complex mixture of substances without a sharp melting point. For characterization, its melting range is usually determined by differential thermal analysis (DTA) 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.
• the soft waxes which have a melting point in the range from 35 to 50 ° C., preferably include the group of petrolates and their hydrogenation products. They consist of microcrystalline paraffins and up to 70% by weight of oil, have an ointment-like to plastically firm consistency and represent bitumen-free residues from petroleum processing.
• Distillation residues (petrolatum stocks) of certain paraffin-based and mixed-base crude oils are particularly preferred Vaseline to be processed. It is furthermore preferred to use bitumen-free, oil-like to solid hydrocarbons separated from distillation residues of paraffin- and mixed-base crude oils and cylinder oil distillates by means of solvents. They are of semi-solid, quick, sticky to plastic-solid consistency and have melting points between 50 and 70 ° C. These petrolates are the most important basis for the production of
• Microfaxes are also suitable.
• the solid hydrocarbons separated from highly viscous, paraffin-containing lubricating oil distillates during dewaxing with melting points between 63 and 79 ° C.
• These petrolates are mixtures of microcrystalline waxes and high-melting n-paraffins.
• paraffin wax mixtures from, for example, can be used
• 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 wt .-% to 100 wt .-%, and at 90 ° C a liquid content of 100 wt .-%.
• the temperature at which a liquid fraction of 100% by weight of the paraffin wax is reached is still below 85 ° C., in particular at 75 ° C. to 82 ° C., in particularly preferred paraffin wax mixtures.
• the paraffin waxes can be petrolatum, microcrystalline waxes or hydrogenated or partially hydrogenated paraffin waxes.
• Suitable bisamides as defoamers are those which are derived from saturated fatty acids with 12 to 22, preferably 14 to 18 C atoms and from alkylenediamines with 2 to 7 C atoms.
• Suitable fatty acids are lauric acid, myristic acid, stearic acid, arachic acid and behenic acid and mixtures thereof, as can be obtained from natural fats or hydrogenated oils, such as tallow or hydrogenated palm oil.
• Suitable diamines are, for example, ethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
• Preferred diamines are ethylenediamine and hexamethylenediamine.
• Particularly preferred bisamides are bismyristoylethylene diamine, bispalmitoylethylene diamine, bisstearoylethylene diamine and mixtures thereof and the corresponding derivatives of hexamethylene diamine.
• 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.
• Suitable 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 distearate, sorbitan dibehenate, sorbitan dioleate and mixed tallow alkyl sorbitan mono- and diesters.
• Usable glycerol esters are the mono-, di- or triesters of glycerol and the carboxylic acids mentioned, with the mono- or diesters being preferred.
• Glycerol monostearate, glycerol monooleate, glycerol monopalmitate, glycerol monobehenate and glycerol distearate are examples of this.
• 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
• 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 mixtures thereof, as can be obtained from natural fats or optionally hardened oils, such as tallow or hydrogenated palm oil.
• Saturated fatty acids with 12 to 22, in particular 18 to 22, carbon atoms are preferred.
• the corresponding fatty alcohols of the same C chain length can be used in the same way.
• Dialkyl ethers may also be present as defoamers.
• the ethers can be asymmetrical or symmetrical, i.e. contain two identical or different alkyl chains, preferably with 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 above 25 ° C, in particular above 40 ° C.
• Further suitable defoamer compounds are fatty ketones which according to relevant methods of preparative organic chemistry can be obtained. For their production, for example, carboxylic acid magnesium salts are used which are pyrolyzed at temperatures above 300 ° C. with the elimination of carbon dioxide and water.
• Suitable fat ketones are those obtained by pyrolysis of the magnesium salts of lauric acid, myristic acid, palmitic acid, palmitoleic acid,
• Suitable defoamers are fatty acid polyethylene glycol esters, which are preferably obtained by base-homogeneously catalyzed addition of ethylene oxide to fatty acids.
• the addition of ethylene oxide to the fatty acids takes place in the presence of alkanolamines as catalysts.
• alkanolamines especially triethanolamine, leads to an extremely selective ethoxylation of the fatty acids, especially when it comes to producing low-ethoxylated compounds.
• Suitable silicones are common organopolysiloxanes that contain fine particles
• Silicic acid which in turn can also be silanized, can have.
• Suitable polydiorganosiloxanes have an almost linear chain and have a degree of oligomerization of 40 to 1500. Examples of suitable substituents are methyl, ethyl, propyl, isobutyl, tert. Butyl and phenyl.
• silicones in general and the polydiorganosiloxanes in particular contain finely divided silica, which can also be silanated.
• Silicic acid-containing dimethylpolysiloxanes are particularly suitable for the purposes of the present invention.
• the polydiorganosiloxanes advantageously have a Brookfield viscosity at 25 ° C. (spindle 1, 10 rpm) in the range from 5000 mPas to 30,000 mPas, in particular from 15
• the silicones are preferably used in the form of their aqueous emulsions. As a rule, the silicone is added to the water initially introduced with stirring. If desired, thickeners, as are known from the prior art, can be added to increase the viscosity of the aqueous silicone emulsions. These can be of an inorganic and / or organic nature, particularly preferred are nonionic cellulose ethers such as methyl cellulose, ethyl cellulose and mixed ethers such as methyl hydroxyoxy cellulose, methyl hydroxypropyl cellulose, methyl hydroxybutyl cellulose and anionic carboxy cellulose types such as carboxy methyl cellulose sodium salt (abbreviation CMC).
• CMC carboxy methyl cellulose sodium salt
• Particularly suitable thickeners are mixtures of CMC to nonionic cellulose ethers in a weight ratio of 80:20 to 40:60, in particular 75:25 to 60:40.
• use concentrations of approximately 0.5 to are recommended 10, in particular from 2.0 to 6 wt .-% - calculated as a thickener mixture and based on aqueous silicone emulsion.
• the content of silicones of the type described in the aqueous emulsions is advantageously in the range from 5 to 50% by weight, in particular from 20 to 40% by weight, calculated as silicones and based on the aqueous silicone emulsion.
• the aqueous silicone solutions are given starch which is accessible from natural sources, for example from rice, potatoes, corn and wheat.
• the starch is advantageously present in amounts of 0.1 to 50% by weight, based on the silicone emulsion, and in particular in a mixture with the already described thickener mixtures of sodium carboxymethyl cellulose and a nonionic cellulose ether in the amounts already mentioned.
• To prepare the aqueous silicone emulsions the procedure is expediently such that the thickeners which may be present are allowed to swell in water before the silicones are added.
• the silicones are expediently incorporated with the aid of effective stirring and mixing devices.
• 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 wax-like 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 layer 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.
• organic carrier materials are film-forming polymers, for example polyvinyl alcohols, polyvinyl pyrrolidones, poly (meth) acrylates, polycarboxylates, cellulose sederivate and starch in question.
• 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.
• the solid preparations can further contain disintegrants or disintegrants.
• disintegrants This is to be understood as meaning substances that are added to the shaped bodies in order to accelerate their decomposition when they come into contact with water. These substances increase their volume when water enters, whereby on the one hand the own volume increases (swelling), on the other hand a pressure can be generated by the release of gases, which causes the tablet to disintegrate into smaller particles.
• disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used.
• Swelling disintegration aids are, for example, synthetic polymers such as optionally crosslinked polyvinyl pyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.
• PVP polyvinyl pyrrolidone
• cellulose-based disintegration agents are used as preferred disintegration agents. Pure cellulose has the formal gross composition (CeHioOs !) And, formally speaking, is a ß-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 therefore have average Molar masses from 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 a cellulose-based disintegrant, but are used in a mixture with cellulose.
• the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
• Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged.
• a subsequent disaggregation of the microfine celluloses produced by the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
• the disintegrants can be macroscopically homogeneously distributed in the shaped body, but microscopically they form zones of increased concentration due to the manufacturing process.
• Disintegrants which can be present in the sense of the invention are, for example, collidone, alginic acid and its alkali metal salts, amorphous or also partially crystalline layered silicates (bentonites), polyacrylates, polyethylene glycols.
• the preparations can contain the disintegrants in amounts of 0.1 to 25, preferably 1 to 20 and in particular 5 to 15% by weight, based on the moldings.
• perfume 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 methylphenyl glycinate, allyl cyclohexyl propylate propylate propionate.
• the ethers include for example, benzyl ethyl ether, for the aldehydes, for example the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, for the ketones, for example the jonones, ⁇ -isomethylionone and methylcedryl ketone, for the alcohols Anethol, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include terpenes such as limonene and pinene.
• 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, lentil flower 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.
• Suitable ingredients of the agents 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.
• Sodium sulfate for example, may also be present as a filler or filler in amounts of 0 to 10, in particular 1 to 5,% by weight, based on the agent
• the solid detergents obtainable using the additives according to the invention can be produced or used in the form of powders, extrudates, granules or agglomerates. It can be both universal and fine or color detergent, optionally in the form of compact or super-compact.
• the corresponding methods known from the prior art are suitable for producing such agents.
• the agents are preferably produced by mixing different particulate components which contain detergent ingredients.
• the particulate components can be produced by spray drying, simple mixing or complex granulation processes, for example fluidized bed granulation. It is particularly preferred that at least one surfactant-containing component is produced by fluidized bed granulation.
• aqueous preparations of the alkali silicate and the alkali carbonate are sprayed together with other detergent ingredients in a drying device, and granulation can take place simultaneously with the drying.
• the drying device into which the aqueous preparation is sprayed can be any drying apparatus.
• the drying is carried out as spray drying in a drying tower.
• the aqueous preparations are exposed to a drying gas stream in a finely divided form in a known manner.
• a patent is published in Henkel's patent publications
• Embodiment of spray drying with superheated steam is described.
• the working principle disclosed there is hereby expressly made the subject of the present disclosure of the invention.
• a particularly preferred way of producing the agents is to subject the precursors to fluidized bed granulation ("SKET" granulation).
• SKET fluidized bed granulation
• the precursors can be either in the dried state and as an aqueous preparation, preferably used fluidized bed apparatuses have base plates with dimensions from 0.4 to 5 m.
• the granulation is preferably carried out at fluidizing air speeds in the range from 1 to 8 m / s.
• the granules are preferably discharged from the fluidized bed via a size classification of the granules.
• the classification can take place, for example, by means of a sieve device or by means of an opposing air flow (classifier air) which is regulated in such a way that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed.
• the inflowing air is usually composed of the heated or unheated classifier air and the heated bottom air.
• the soil air temperature is between 80 and 400, preferably 90 and 350 ° C.
• a starting mass for example a granulate from an earlier test batch, is advantageously introduced at the start of the granulation.
• the mixtures are then subjected to a compacting step, further ingredients being added to the agents only after the compacting step.
• the ingredients are compacted in one
• the press agglomeration process to which the solid premix (dried basic detergent) is subjected can be carried out in various apparatuses. Different press agglomeration processes are distinguished depending on the type of agglomerator used. The four most common and within the
• the preferred press agglomeration processes according to the invention are extrusion, roller pressing or compacting, hole pressing (pelleting) and tableting, so that preferred press agglomeration processes within the scope of the present invention are extrusion, roll compacting, pelletizing or tableting processes.
• binders can be used as an aid to compaction. However, it should be made clear that the use of several different binders and mixtures of different binders is always possible.
• a binder is used which is already completely in the form of a melt at temperatures of up to 130 ° C., preferably up to 100 ° C. and in particular up to 90 ° C. The binder must therefore be selected depending on the process and process conditions, or the process conditions, in particular the process temperature, must - if a specific binder is desired - be adapted to the binder.
• the actual compression process preferably takes place at processing temperatures which, at least in the compression step, correspond at least to the temperature of the softening point, if not even the temperature of the melting point of the binder.
• the process temperature is significantly above the melting point or above the temperature at which the binder is in the form of a melt.
• the process temperature in the compression step is not more than 20 ° C. above the melting temperature or the upper limit of the melting range of the binder. It is technically quite possible to set even higher temperatures; However, it has been shown that a temperature difference of 20 ° C. from the melting temperature or softening temperature of the binder is generally sufficient and even higher temperatures do not bring any additional advantages. It is therefore particularly preferred, especially for energy reasons, above, but as close as possible to the melting point or to the upper temperature.
• thermoly sensitive raw materials for example peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes, can increasingly be processed without serious loss of active substance.
• peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes
• the compression that is, between the mixing / homogeneity of the premix and the shaping, permits an energetically very favorable and extremely gentle for the temperature-sensitive components of the premix, since the premix is only exposed to the higher temperatures for a short time.
• the work tools of the press agglomerator the screw (s) of the extruder
• the roller (s) of the roller compactor and the press roller (s) of the pellet press) at a maximum temperature of 150 ° C, preferably a maximum of 100 ° C and in particular a maximum of 75 ° C and the process temperature is 30 ° C and in particular maximum 20 ° C above the melting temperature or the upper temperature limit of the melting range of the binder.
• the duration of the temperature effect in the compression range of the press agglomerators is preferably a maximum of 2 minutes and is in particular in a range between 30 seconds and 1 minute.
• Preferred binders which can be used alone or in a mixture with other binders are polyethylene glycols, 1,2-polypropylene glycols and also modified polyethylene glycols and polypropylene glycols.
• the modified polyalkylene glycols include, in particular, the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12,000 and in particular between 1,000 and 4,000.
• Another group consists of mono- and / or disuccinates of the polyalkylene glycols which in turn have relative molecular weights between 600 and 6,000, preferably between 1,000 and 4,000.
• polyethylene glycols include those polymers which, in addition to ethylene glycol, also produce C 3 -C 5 -
• Glycols and glycerol and mixtures of these can be used as starting molecules. Ethoxylated derivatives such as trimethylolpropane with 5 to 30 EO are also included.
• the polyethylene glycols preferably used can have a linear or branched structure, linear polyethylene glycols being particularly preferred.
• the particularly preferred polyethylene glycols include those with relative molecular weights between 2
• polyethylene glycols with relative molecular weights below 3,500 and above 5,000, in particular in combination with polyethylene glycols with a relative molecular weight of around 4,000, can be used, and such combinations advantageously to more than 50% by weight , based on the total amount of polyethylene glycols, polyethylene glycols with a relative molecular weight between
• polyethylene glycols can also be used as binders, which are per se in liquid state at room temperature and a pressure of 1 bar; Here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600. However, these per se liquid polyethylene glycols should only be used in a mixture with at least one other binder: 5 den, whereby this mixture must again meet the requirements according to the invention, ie must have a melting point or softening point of at least above 45 ° C.
• suitable as binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights of up to a maximum of 30,000. Relative molecular weight ranges between 3,000 and 30,000, for example around 10,000 are preferred. Polyvinylpyrrolidones are preferably not used as the sole binders but in combination with others, especially in combination with polyethylene glycols.
• the compacted material preferably has temperatures not above 90 ° C., temperatures between 35 and 85 ° C. being particularly preferred. It has been found that outlet temperatures - especially in the extrusion process - from 40 to 80 ° C., for example up to 70 ° C., are particularly advantageous. extrusion
• the detergent according to the invention is produced by extrusion.
• a solid premix is pressed in the form of a strand under pressure and the strand is cut to the predeterminable size of the granulate after it has emerged from the hole shape by means of a cutting device.
• the homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work.
• Preferred plasticizers and / or lubricants are ten-
• the premix is preferably fed to a planetary roller extrader or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating screw guide, its housing and its extruder.
• pelletizing head can be heated to the predetermined extrusion temperature.
• the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used
• the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knock-off knife.
• the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension. In this way, granules of an essentially uniformly predeterminable particle size can be produced, the individual
• solute particle sizes can be adapted to the intended application.
• particle diameters up to at most 0.8 cm are preferred.
• Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from about 0.8 to 3 mm.
• the length / diameter ratio of the chopped-off primary granules is preferably in the range from about 1: 1 to about 3: 1.
• edges present on the raw extrudate are rounded off so that ultimately spherical to approximately spherical extrudate grains can be obtained.
• small amounts of dry powder for example zeolite powder such as zeolite NaA powder, can also be used in this stage. This shape can be done in standard rounding machines. It is important to ensure that only small amounts of fine grain are produced in this stage.
• a drying process which is described in the above-mentioned prior art documents is described as a preferred embodiment, is then possible, but not absolutely necessary. It may just be preferred not to carry out any drying after the compacting step.
• extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press (from Amandus Kahl) or in the Bepex extruder.
• the temperature guide in the transition region of the screw, the pre-distributor and the nozzle plate is preferably designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded.
• the duration of the temperature influence in the compression range of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.
• the detergents according to the invention can also be produced by means of roller compaction.
• the premix is metered in between two smooth rollers or with recesses of a defined shape and rolled out under pressure between the two rollers to form a sheet-like compact, the so-called Schülpe.
• the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
• smooth rollers smooth, unstructured scapular belts are obtained, while by using structured rollers, appropriately structured scuffs can be produced in which, for example, certain shapes of the later detergent particles can be specified.
• the Schülpenband is subsequently broken into smaller pieces by a knock-off and crushing process and can be processed into granules in this way, which can be refined by further surface treatment methods known per se, in particular in an approximately spherical shape.
• the temperature of the pressing tools that is to say the rollers, is preferably at a maximum of 150 ° C., preferably at a maximum of 100 ° C. and in particular at a maximum of 75 ° C.
• Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder.
• the duration of the temperature effect in the compression range of the smooth rollers or with depressions of a defined shape is a maximum of 2 minutes and in particular ranges between 30 seconds and 1 minute. > Pelleting
• the detergent according to the invention can also be produced by means of a pelletizer.
• the premix is applied to a perforated surface and pressed through the holes by means of a pressure-exerting body under plasticizing.
• the premix is compressed under pressure, plasticized, pressed through a perforated surface by means of a rotating roller in the form of fine strands and finally comminuted into granules using a knock-off device.
• roller and perforated die conceivable.
• roller and perforated die conceivable.
• the press rolls can also be conical in the plate devices, in the ring-shaped devices the dies and press roll (s) can have the same or opposite direction of rotation.
• the ring die press disclosed in this document consists of a rotating, by
• Press channels pass through the ring die and at least one press roller which is operatively connected to the inner surface thereof and presses the material supplied to the die space through the press channels into a material discharge.
• the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved.
• heatable or coolable rollers in the pelletizing in order to set a desired temperature of the premix.
• the temperature of the pressing tools that is to say the pressure rollers or pressing rollers, is preferably at a maximum of 150 ° C., preferably at a maximum of 100 ° C. and in particular at a maximum of 75 ° C.
• Particularly preferred production processes work in roller compacting with process temperatures which are 10 ° C., in particular a maximum of 5 ° C., above the melting temperature or the upper temperature limit of the melting range of the binder.
• Shaped articles are generally produced by tableting or press agglomeration.
• the particulate press agglomerates obtained can either be used directly as detergents or previously treated and / or prepared using customary methods.
• the usual aftertreatments include, for example, powdered oranges with finely divided ingredients from washing or cleaning agents, which generally further increases the bulk density is increased.
• a preferred aftertreatment is the procedure in which dusty or at least finely divided ingredients (the so-called fine fractions) are adhered to the particulate process end products produced according to the invention, which serve as the core, and thus agents are formed which have these so-called fine fractions as an outer shell. This is advantageously done again by melting agglomeration.
• the solid detergents are in tablet form, these tablets preferably having rounded corners and edges, in particular for storage and transport reasons.
• the base area of these tablets can be circular or rectangular, for example.
• Multi-layer tablets, in particular tablets with 2 or 3 layers, which can also have different colors, are particularly preferred. Blue-white or green-white or blue-green-white tablets are particularly preferred.
• the tablets can also contain pressed and unpressed parts. Shaped articles with a particularly advantageous dissolution rate are obtained if the granular constituents, prior to pressing, have a proportion of particles which have a diameter outside the range from 0.02 to 6 mm of less than 20, preferably less than 10,% by weight. A particle size distribution in the range from 0.05 to 2.0 and particularly preferably from 0.2 to 1.0 mm is preferred.
• Example 1 A number of liquid sample formulations are shown in Table 1 below. All quantities are understood as% by weight. Examples 1 to 4 represent liquid detergents, Examples 5 and 6 softeners.

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• 2002
  • 2002-06-25 EP EP02014121A patent/EP1375633B1/de not_active Expired - Lifetime
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• 2003
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