EP3617299B1 - Agents actifs polymères améliorant le pouvoir détergeant primaire - Google Patents

Agents actifs polymères améliorant le pouvoir détergeant primaire Download PDF

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Publication number
EP3617299B1
EP3617299B1 EP18190901.1A EP18190901A EP3617299B1 EP 3617299 B1 EP3617299 B1 EP 3617299B1 EP 18190901 A EP18190901 A EP 18190901A EP 3617299 B1 EP3617299 B1 EP 3617299B1
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Prior art keywords
weight
mol
polymer
acid
alkylene oxide
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EP18190901.1A
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German (de)
English (en)
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EP3617299A1 (fr
Inventor
Alejandra Garcia Marcos
Stephan Hueffer
Thomas Wesley Holcombe
Roland Ettl
Alexander Panchenko
Susanne Carina ENGERT
Stefanie Juntermanns
Frank Janssen
Michael Dreja
Nadine BLUHM
Christa JUNKES
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Henkel AG and Co KGaA
BASF SE
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Henkel AG and Co KGaA
BASF SE
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Priority to EP18190901.1A priority Critical patent/EP3617299B1/fr
Application filed by Henkel AG and Co KGaA, BASF SE filed Critical Henkel AG and Co KGaA
Priority to ES18190901T priority patent/ES2934333T3/es
Priority to PL18190901.1T priority patent/PL3617299T3/pl
Priority to MX2021002372A priority patent/MX2021002372A/es
Priority to US17/270,644 priority patent/US20210207062A1/en
Priority to PCT/EP2019/071357 priority patent/WO2020043458A1/fr
Priority to CN201980055958.1A priority patent/CN112639066B/zh
Priority to JP2021510395A priority patent/JP2021535253A/ja
Priority to PCT/EP2019/071367 priority patent/WO2020043460A1/fr
Priority to BR112021003603-2A priority patent/BR112021003603A2/pt
Publication of EP3617299A1 publication Critical patent/EP3617299A1/fr
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    • 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
    • C11D1/38—Cationic compounds
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • 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
    • C11D1/008—Polymeric surface-active agents

Definitions

  • the present invention relates to the use of certain polymers to enhance the primary detergency of detergents when washing textiles against surfactant- or enzyme-sensitive soiling.
  • washing auxiliaries In addition to the ingredients that are essential for the washing process, such as surfactants and builder materials, detergents usually contain other components that can be summarized under the term washing auxiliaries and that include such different groups of active ingredients as foam regulators, graying inhibitors, bleaching agents, bleach activators and color transfer inhibitors. Such auxiliaries also include substances whose presence enhances the detergency of surfactants without generally having to exhibit pronounced surfactant behavior themselves. Such substances are often referred to as detergency boosters.
  • the polymers are (mono)amino-based alkoxylates, preferably propoxylates, with an average molecular weight M w of 600-10000 g/mol, preferably 1300-6000 g/mol, particularly preferably 1400-4500 g/mol.
  • the polymers according to the invention contain only one amino group, ie only one nitrogen atom per molecule.
  • alkoxylated amino alcohols with a molecular weight M w of more than 600 g/mol after alkoxylation, the amino nucleus having a molecular weight of less than 200 g/mol and containing only one amino group, and the amino nucleus having a Alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and mixtures thereof is alkoxylated, preferably with a mixture containing propylene oxide, particularly preferably with propylene oxide.
  • the alkoxylated amino alcohols can have block or random structures.
  • an alkoxylated amino alcohol obtainable starting from triethanolamine (TEA) by propoxylation, preferably with a length of the three side arms of 15 propylene oxide (PO) units each.
  • TEA triethanolamine
  • PO propylene oxide
  • an alkoxylated amino alcohol obtainable starting from triisopropanolamine (TIPA) by propoxylation, preferably with a length of the three side arms of 15 propylene oxide (PO) units each.
  • TIPA triisopropanolamine
  • PO propylene oxide
  • alkoxylated alkyl monoamines with a linear, branched or cyclic alkyl group alkoxylation being carried out with an alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and mixtures thereof, preferably with a mixture containing propylene oxide, particularly preferably with propylene oxide.
  • the alkoxylated alkyl monoamines can have block or random structures.
  • alkoxylated alkyl monoamine obtainable starting from tert-butylamine (tBA) by propoxylation, preferably with a length of the two side arms of 12 propylene oxide (PO) units each.
  • the invention therefore relates to the use of polymers consisting of (mono)amino-based alkoxylates with an average molecular weight M w of 600-10000 g/mol, preferably 1300-6000 g/mol, particularly preferably 1400-4500 g/mol, to increase the primary detergency of detergents when washing textiles in particular aqueous and surfactant-containing washing liquid against surfactant- or enzyme-sensitive soiling, wherein the polymer contains two or three chains of alkylene oxide units per nitrogen atom, and wherein the polymer contains more than 90 mol% propylene oxide units, based on the sum of all alkylene oxide units, and 10 to 18 alkylene oxide units per alkylene oxide chain.
  • Another subject of the invention is a process for removing surfactant- or enzyme-sensitive soiling from textiles, in which a detergent and a polymeric active ingredient mentioned are brought into contact with soiled textiles in a particularly aqueous and surfactant-containing washing liquor.
  • This procedure can be carried out manually or by machine, for example using a domestic washing machine. It is possible in particular for liquid agents and the polymeric active substance to be used at the same time or apply sequentially. Simultaneous use can be carried out particularly advantageously by using a detergent which contains the polymeric active substance.
  • Surfactant- or enzyme-sensitive soiling is understood to mean that which can usually be at least partially removed by surfactants or with the aid of enzymes, such as soiling from oil, grease, make-up or grass, mousse au chocolat, or egg.
  • the polymers used according to the invention also contribute to the removability of such stains in the absence of enzymes or in particular in the absence of bleaches.
  • the use according to the invention and the method according to the invention are preferably realized by adding the polymer, consisting of (mono)amino-based alkoxylate, to an agent free of the corresponding polymer or to a wash liquor which contains an agent free of the corresponding polymer, the amount added of polymer, based on the total weight of the agent free of the corresponding polymer, is preferably in the range from 0.01% by weight to 20% by weight, in particular from 1% by weight to 15% by weight.
  • the polymer which is essential to the invention is particularly preferably used together with liquid detergents in particular which, based on the total weight of the detergent, have a surfactant concentration of at least 30% by weight, preferably in the range from 30% by weight to 65% by weight and in particular 50% by weight wt .-% up to 58 wt .-%. It is preferred that the wash liquor is produced by adding 7 ml to 100 ml, in particular 10 ml to 75 ml, preferably 20 ml to 50 ml, of a liquid aqueous detergent to 12 liters to 60 liters, in particular 15 liters to 20 liters of water .
  • the polymers essential to the invention can be obtained by processes which are known in principle.
  • the starter molecules especially amino-containing compounds, with alkylene oxides, such as. B. ethylene oxide (EO), propylene oxide (PO) and / or butylene oxide (BO), preferably reacted under alkaline catalysis, wherein the polymer contains two or three chains of alkylene oxide units per nitrogen atom, and wherein the polymer contains more than 90 mol% propylene oxide units, based on the sum of all alkylene oxide units, and 10 to 18 alkylene oxide units per alkylene oxide chain.
  • alkylene oxides such as. B. ethylene oxide (EO), propylene oxide (PO) and / or butylene oxide (BO)
  • the starter molecule is presented and drained.
  • the epoxides are then metered in in the desired order and quantity under alkaline catalysis, for example using KOH.
  • Suitable procedures and reaction conditions for the alkoxylation are generally known to those skilled in the art and are described, for example, in Standard work M. Ionescu, "Chemistry and technology of polyols for polyurethanes", Rapra Technology, Shrewsbury, UK, page 60 ff .
  • the following groups of compounds can serve as starters for the polymers consisting of certain alkoxylates described.
  • (Mono)amino alcohols e.g., triethanolamine, alkyl diethanolamine, alkyl diisopropanolamine, trialkylamino alcohols such as triisopropanolamine, N,N-di-(2-hydroxyethyl)cyclohexylamine, N,N-di-(2-hydroxypropyl)cyclohexylamine .
  • triethanolamine is preferred as a starter.
  • triisopropanolamine TIPA is used as the starter.
  • Alkyl monoamines such as n-butylamine, n-hexylamine, n-octylamine, isopropylamine, sec-butylamine, tert-butylamine, cyclohexylamine, 2-ethylhexylamine, 2-phenylethylamine.
  • the initiator is preferably tert -butylamine (tBA).
  • Preferred polymers used according to the invention have a weight-average molecular weight of 1300-6000 g/mol, and very particularly preferably 1400-4500 g/mol.
  • the starter is reacted with an alkylene oxide consisting of propylene oxide or mixtures containing propylene oxide.
  • an alkylene oxide consisting of propylene oxide or mixtures containing propylene oxide.
  • only propylene oxide is used for the alkoxylation.
  • two chains of alkylene oxide units are preferably attached on each nitrogen atom of the starter.
  • three chains of alkylene oxide units are attached per nitrogen atom of the starter.
  • the concentration of the polymer defined above in the aqueous washing liquor is 0.001 g/l to 5 g/l, in particular 0 .01 g/l to 2 g/l.
  • the process according to the invention and the use according to the invention are preferably carried out at temperatures in the range from 10.degree. C. to 95.degree. C., in particular in the range from 20.degree. C. to 40.degree.
  • the process according to the invention and the use according to the invention are preferably carried out at pH values in the range from pH 5 to pH 12, in particular from pH 7 to pH 11.
  • Detergents which can be used in connection with the use according to the invention or in the process according to the invention in addition to the polymer and which, in particular, are pulverulent solids, in post-compacted particle form, as solutions or suspensions, can contain all known ingredients customary in such agents.
  • the funds can in particular builder substances, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil release polymers, color transfer inhibitors, graying inhibitors, wrinkle-reducing and shape-retaining polymeric active ingredients, and other auxiliaries, such as optical brighteners , foam regulators, colorants and fragrances.
  • the agents can contain one or more surfactants, with anionic surfactants, nonionic surfactants and mixtures thereof being particularly suitable, but cationic and/or amphoteric surfactants can also be present.
  • nonionic surfactants known to those skilled in the art can be used as nonionic surfactants.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols preferably having 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, such as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals from alcohols of natural origin with 12 to 18 carbon atoms for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred.
  • Preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical mean values which can correspond to a whole or a fractional number for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • alkyl glycosides of the general formula R 5 O(G) x can also be used as further nonionic surfactants, in which R 5 is a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical having 8 to 22, preferably 12 to 18 C- corresponds to atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is from 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamide type can also be used.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of it.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula in which R is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula in which R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, with C 1-4 -alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted to the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide catalyst.
  • anionic surfactants used are those of the sulfonate and sulfate type.
  • Surfactants of the sulfonate type are preferably C 9-13 -alkylbenzene sulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from C 12-18 -monoolefins with a terminal or internal double bond by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof as are obtained in the production by esterification of glycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alkyl sulfates of the general formula are also suitable RO-SO 3M , in which R is a linear, branched-chain or cyclic saturated hydrocarbon radical having 12 to 18, in particular 12 to 14, carbon atoms and M is a counter-cation leading to charge neutralization of the sulfuric acid monoester, in particular a sodium or potassium ion or an ammonium ion of the general formula R1R2R3R4N + , _ _ in which R 1 , R 2 , R 3 and R 4 independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 2 to 3 carbon atoms.
  • Preferred radicals R are derived from native C 12 -C 18 fatty alcohols, such as coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 10 -C 20 oxo alcohols or secondary alcohols of these chain lengths.
  • alkyl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis, which have a similar degradation behavior as the appropriate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 14 alkyl sulfates are particularly preferred.
  • the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, considered in themselves, represent nonionic surfactants.
  • sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk(en)ylsuccinic acid preferably having 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof.
  • Soaps come into consideration as further anionic surfactants.
  • Saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, e.g. coconut, palm kernel or tallow fatty acids, are suitable.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts, as well as soluble salts of organic bases such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • cationic and/or amphoteric surfactants can also be used.
  • Surfactants of this type are contained in detergents in amounts of preferably 5% by weight to 65% by weight.
  • particularly preferred detergents are liquid and have surfactant contents of at least 30% by weight, preferably in the range from 30% by weight to 60% by weight and in particular from 50% by weight to 58% by weight.
  • Such concentrated liquid detergents are advantageous because they use fewer resources, which is due in particular to the lower transport weight and reduced consumption size. In comparison to detergents with a lower concentration, for example, you need a smaller bottle size and therefore less packaging material to achieve the same application performance .
  • highly concentrated agents are preferred by consumers because they take up little storage space in the household.
  • Textile-softening compounds can be used to care for the textiles and to improve the textile properties, such as a softer "handle” (finish) and reduced electrostatic charging (increased wearing comfort).
  • the active ingredients of these formulations are quaternary ammonium compounds with two hydrophobic residues, such as disteraryldimethylammonium chloride, which, however, is increasingly being replaced by quaternary ammonium compounds that contain ester groups in their hydrophobic residues as predetermined breaking points for biodegradation because of its insufficient biodegradability.
  • esters with improved biodegradability can be obtained, for example, by esterifying mixtures of methyldiethanolamine and/or triethanolamine with fatty acids and then quaternizing the reaction products with alkylating agents in a manner known per se.
  • Dimethylolethylene urea is suitable as a finishing agent.
  • a detergent preferably contains at least one water-soluble and/or water-insoluble, organic and/or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, especially citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, especially methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid, and polyaspartic acid, polyphosphonic acids, especially aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly)carboxylic acids, in particular polycarboxylates accessible by oxidation of polysaccharides or dextrins, and/or polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers of these, which can also contain small amounts of polymerizable substances without carboxylic acid functionality as
  • the relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g/mol and 200,000 g/mol, that of the copolymers between 2,000 g/mol and 200,000 g/mol, preferably 50,000 g/mol to 120,000 g/mol. mol, in each case based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 g/mol to 100,000 g/mol.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight.
  • vinyl ethers such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene
  • Terpolymers which contain two unsaturated acids and/or their salts as monomers and vinyl alcohol and/or an esterified vinyl alcohol or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth)acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C 4 -C 8 -dicarboxylic acid, maleic acid being particularly preferred, and/or a derivative of an allylsulfonic acid which is substituted in the 2-position with an alkyl or aryl radical.
  • Such polymers generally have a relative molecular weight of between 1000 g/mol and 200,000 g/mol.
  • copolymers are those which contain acrolein and acrylic acid/acrylic acid salts or vinyl acetate as monomers.
  • the organic builder substances can be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions, particularly for the production of liquid agents. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • Such organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 0.5% by weight to 8% by weight. Amounts in the upper half of the ranges mentioned are preferably used in paste-like or liquid, in particular aqueous, agents.
  • water-soluble inorganic builder materials are polymeric alkali metal phosphates, which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions, in particular from 1% by weight to 5% by weight, are used as water-insoluble, water-dispersible inorganic builder materials.
  • the crystalline detergent grade sodium aluminosilicates particularly zeolite A, P and optionally X, are preferred. Amounts close to the upper limit mentioned are preferably used in solid, particulate compositions.
  • suitable aluminosilicates do not have any particles with a particle size of more than 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size of less than 10 ⁇ m.
  • Their calcium binding capacity is usually in the range of 100 mg to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali metal silicates, which can be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates which can be used as builders preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1:1.1 to 1:12, and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na 2 O:SiO 2 of 1:2 to 1:2.8.
  • Crystalline phyllosilicates of the general formula Na 2 Si x O 2x+1 y H 2 O are preferably used as crystalline silicates, which can be present alone or in a mixture with amorphous silicates, in which x, the so-called modulus, is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates are those in which x has the value 2 or 3 in the general formula mentioned.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O
  • crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1 and produced from amorphous alkali metal silicates can also be used.
  • a crystalline layered sodium silicate with a modulus of 2 to 3 is used, such as can be produced from sand and soda.
  • crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used.
  • a granular compound of alkali metal silicate and alkali metal carbonate is used, as is commercially available, for example, under the name Nabion® 15.
  • the weight ratio of aluminosilicate to silicate is preferably 1:10 to 10:1.
  • the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1:2 to 2:1 and in particular 1:1 to 2:1.
  • Detergents preferably contain builder substances in amounts of up to 60% by weight, in particular from 0.5% by weight to 40% by weight.
  • component a) in a preferred embodiment, 15% by weight to 25% by weight alkali metal carbonate, which can be replaced at least partially by alkali metal bicarbonate, and up to 5% by weight, in particular 0.5% by weight 2.5% by weight of citric acid and/or alkali citrate.
  • component a) contains 5% by weight to 25% by weight, in particular 5% by weight to 15% by weight, of citric acid and/or alkali metal citrate and up to 5% by weight, in particular 1% by weight .-% to 5 wt .-% alkali metal carbonate, which can be replaced at least partially by alkali metal bicarbonate included. If both alkali metal carbonate and alkali metal bicarbonate are present, component a) preferably has alkali metal carbonate and alkali metal bicarbonate in a weight ratio of from 10:1 to 1:1.
  • a preferred embodiment contains 1% by weight to 5% by weight of alkali metal silicate with a modulus in the range from 1.8 to 2.5.
  • a preferred embodiment contains 0.05% by weight to 1% by weight of phosphonic acid and/or alkali metal phosphonate.
  • Phosphonic acids are also understood as meaning optionally substituted alkyl phosphonic acids which can also have several phosphonic acid groups (so-called polyphosphonic acids).
  • hydroxy and/or aminoalkylphosphonic acids and/or their alkali metal salts such as dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic acid, 1-hydroxyethane -1,1-diphosphonic acid, amino-tris(methylenephosphonic acid), N,N,N',N'-ethylenediamine-tetrakis-(methylenephosphonic acid) and acylated derivatives of phosphorous acid, which can also be used in any mixtures.
  • alkali metal salts such as dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic acid, 1-hydroxyethane -1,1-diphosphonic acid, amino-tris(methylenephosphonic acid), N,N,N',N'-ethylenedi
  • a preferred embodiment contains 15% by weight to 35% by weight of alkali metal phosphate, in particular trisodium polyphosphate.
  • Alkaline phosphate is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 can be distinguished in addition to higher-molecular representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts and lime incrustations in fabrics and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60°) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white powders, very easily soluble in water, which lose the water of crystallization when heated and are converted into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ) at 200°C and into sodium trimetaphosphate (Na 3 P 3 O 9 ) and Madrell's salt.
  • NaH 2 PO 4 is acidic; it is formed when phosphoric acid with caustic soda to a pH of 4.5 adjusted and the mash is sprayed.
  • Potassium dihydrogen phosphate (potassium phosphate primary or monobasic, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt with a density of 2.33 gcm -3 , a melting point of 253° (decomposes to form (KPO 3 ) x , potassium polyphosphate) and is easily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colourless, very easily water-soluble crystalline salt.
  • Disodium hydrogen phosphate is produced by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm -3 and a melting point of 73-76°C (decomposition), as decahydrate (equivalent to 19-20% P 2 O 5 ) have a melting point of 100°C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) a density of 2.536 gcm -3 .
  • Trisodium phosphate is easily soluble in water with an alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (potassium tertiary or tribasic phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 gcm -3 , has a melting point of 1340° and is readily soluble in water with an alkaline reaction. It is formed, for example, when Thomas slag is heated with coal and potassium sulphate. Despite the higher price, the more easily soluble and therefore highly effective potassium phosphates are often preferred over the corresponding sodium compounds.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988°, also given as 880°) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94° with loss of water) .
  • Substances are colorless crystals that are soluble in water with an alkaline reaction.
  • Na 4 P 2 O 7 is formed when disodium phosphate is heated to >200°C or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardeners and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colourless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water at a pH of 1% solution at 25° is 10.4. Condensation of the NaH 2 PO 4 or the KH 2 PO 4 results in higher molecular weight sodium and potassium phosphates, in which one can distinguish between cyclic representatives, the sodium or potassium metaphosphates, and chain-type types, the sodium or potassium polyphosphates.
  • Pentapotassium triphosphate K 5 P 3 O 10 (potassium tripolyphosphate) is commercially available, for example, in the form of a 50% by weight solution (>23% P 2 O 5 , 25% K 2 O).
  • sodium potassium tripolyphosphates which can also be used within the scope of the present invention. These arise, for example, when sodium trimetaphosphate is hydrolyzed with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
  • a preferred embodiment of the agent contains 1.5% by weight to 5% by weight of polymeric polycarboxylate, selected in particular from the polymerization or copolymerization products of acrylic acid, methacrylic acid and/or maleic acid.
  • polymeric polycarboxylate selected in particular from the polymerization or copolymerization products of acrylic acid, methacrylic acid and/or maleic acid.
  • the homopolymers of acrylic acid and among these, in turn, those with an average molar mass in the range from 5,000 D to 15,000 D (PA standard) are particularly preferred.
  • Enzymes that can be used in the agents are those from the class of lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof, for example amylases such as Termamyl® , Amylase- LT® , Maxamyl® , Duramyl ® and/or Purafect ® OxAm, lipases such as Lipolase ® , Lipomax ® , Lumafast ® , Lipozym ® and/or Lipex ® , cellulases such as Celluzyme ® and/or Carezyme ® .
  • amylases such as Termamyl® , Amylase- LT® , Maxamyl® , Duramyl ® and/or Purafect ® OxAm
  • lipases such as Lipolase ® , Lipomax ® , Lumafast
  • Enzymatic active substances obtained from fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia are particularly suitable. Any enzymes used can be adsorbed on carriers and/or embedded in encapsulating substances in order to protect them against premature inactivation. Detergents preferably contain them in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight.
  • the agent contains 5% by weight to 65% by weight, in particular 8 to 55% by weight, of anionic and/or nonionic surfactant, up to 60% by weight, in particular 0.5 to 40% by weight. -% builder and 0.2% to 5% by weight enzyme from the lipases, cutinases, amylases, pullulases, mananases, cellulases, oxidases and peroxidases and mixtures thereof.
  • the organic solvents that can be used in the detergents include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the ethers which can be derived from the classes of compounds mentioned.
  • Such water-miscible solvents are preferably present in the compositions in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.
  • Polymers originating from nature that can be used as thickeners in aqueous liquid agents are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatine and casein, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl and propyl cellulose, and polymeric polysaccharide thickeners such as xanthan gum; fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes can also be used as thickeners.
  • the agents can contain acids that are compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and/or adipic acid, but also contain mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
  • acids that are compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and/or adipic acid, but also contain mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators are preferably contained in the agents in not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
  • Polymers capable of releasing dirt which are often referred to as "soil release” active substances or as “soil repellents” because of their ability to make the treated surface, for example the fiber, dirt-repellent, are, for example, nonionic or cationic cellulose derivatives.
  • the particularly polyester-active soil release polymers include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol.
  • the preferably used dirt-removing polyesters include those compounds that are formally accessible by esterification of two monomer parts, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO-(CHR 11 -) a OH, which can also be used as a polymeric diol H-(O-(CHR 11 -) a ) b OH may be present.
  • Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R 11 is hydrogen
  • a is a number from 2 to 6 and b a number from 1 to 300.
  • the polyesters obtainable from these preferably contain both monomer diol units -O-(CHR 11 -) a O- and polymer diol units -(O-(CHR 11 -) a ) b O-.
  • the molar ratio of monomer diol units to polymer diol units is preferably 100:1 to 1:100, in particular 10:1 to 1:10.
  • the degree of polymerization b in the polymer diol units is preferably in the range from 4 to 200, in particular from 12 to 140.
  • the molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil-removing polyesters is in the range from 250 to 100,000, in particular from 500 to 50,000
  • the acid on which the radical Ph is based is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably present in salt form, in particular as an alkali metal or ammonium salt. Among these, the sodium and potassium salts are particularly preferred.
  • HOOC-Ph-COOH monomer small proportions, in particular not more than 10 mol % based on the proportion of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be present in the soil-removing polyester.
  • these include, for example, alkylene and alkenylenedicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • Preferred diols HO-(CHR 11 -) a OH include those in which R 11 is hydrogen and a is from 2 to 6 and those in which a is 2 and R 11 is selected from hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 carbon atoms is selected.
  • R 11 is hydrogen and a is from 2 to 6
  • R 11 is selected from hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 carbon atoms is selected.
  • those of the formula HO-CH 2 -CHR 11 -OH, in which R 11 has the meaning given above are particularly preferred.
  • diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
  • Particularly preferred among the polymeric diols is polyethylene glycol with an average molar mass in the range from 1000 to 6000.
  • these polyesters can also be end-capped, suitable end groups being alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids.
  • the end groups bonded via ester bonds can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms.
  • alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms.
  • These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, eleostearic acid, arachidic acid , Gadoleic acid, ar
  • the end groups can also be based on hydroxymonocarboxylic acids with 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid and o-, m- and p-hydroxybenzoic acid.
  • the hydroxy monocarboxylic acids can in turn via their hydroxyl group and their carboxyl group can be connected to one another and are therefore present several times in an end group.
  • the number of hydroxymonocarboxylic acid units per end group, i.e. their degree of oligomerization, is preferably in the range from 1 to 50, in particular from 1 to 10.
  • the color transfer inhibitors suitable for use in detergents for washing textiles include, in particular, polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly(vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and optionally other monomers.
  • the agents can contain anti-crease agents, since textile fabrics, especially those made from rayon, wool, cotton and mixtures thereof, can tend to wrinkle because the individual fibers are sensitive to bending, buckling, pressing and squeezing transversely to the fiber direction.
  • These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty acid alkylol esters, fatty acid alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
  • Graying inhibitors have the task of keeping the dirt detached from the hard surface and in particular from the textile fibers suspended in the liquor.
  • Water-soluble colloids usually of an organic nature, are suitable for this purpose, for example starch, 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.
  • starch derivatives other than those mentioned above can be used, for example aldehyde starches.
  • Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used, for example in amounts of 0.1 to 5% by weight, based on the detergent.
  • the agents can contain optical brighteners, including, in particular, derivatives of diaminostilbene disulfonic acid or their 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 similarly constructed compounds that instead of morpholino - carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type can also be present, for example the alkali metal salts of 4,4'-bis(2-sulfostyryl)diphenyl, 4,4'-bis(4-chloro-3-sulfostyryl)diphenyl, or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)diphenyls. Mixtures of the aforementioned optical brighteners can also be used.
  • foam inhibitors are soaps of natural or synthetic origin which have a high proportion of C 18 -C 24 fatty acids.
  • suitable non-surfactant foam inhibitors are organopolysiloxanes and mixtures thereof with microfine, optionally silanated silica, and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bis-fatty acid alkylenediamides. Mixtures of different foam inhibitors are also used with advantage, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone- and/or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or water-dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamide are particularly preferred.
  • Peroxygen compounds which may be present in the detergents, in particular the detergents in solid form include, in particular, organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing conditions, such as perborate, percarbonate and/or or persilicate. Hydrogen peroxide can also be generated with the help of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle.
  • Alkali metal percarbonate, alkali metal perborate monohydrate, alkali metal perborate tetrahydrate or, in particular in liquid compositions, hydrogen peroxide in the form of aqueous solutions containing 3% by weight to 10% by weight of hydrogen peroxide is particularly preferably used.
  • Peroxygen compounds are preferably present in detergents in amounts of up to 50% by weight, in particular from 5% by weight to 30% by weight.
  • customary bleach activators which form peroxocarboxylic acids or peroxoimidic acids under perhydrolysis conditions, and/or customary bleach-activating transition metal complexes can be used.
  • the component of the bleach activators which is optionally present, in particular in amounts of from 0.5% by weight to 6% by weight, comprises the N- or O-acyl compounds which are customarily used, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium isononanoyl phenolsulfonate, and acylated sugar derivatives, especially pentaacety
  • the bleach activators can be coated with encapsulating substances in a known manner have been coated or granulated, with the aid of carboxymethylcellulose granulated tetraacetylethylenediamine with an average grain size of 0.01 mm to 0.8 mm, granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and/ or trialkylammonium acetonitrile formulated in particulate form is particularly preferred.
  • Such bleach activators are preferably present in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the detergent as a whole.
  • compositions presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation.
  • a process having an extrusion step is preferred.
  • Detergents in the form of aqueous solutions or solutions containing other customary solvents are particularly advantageously produced by simply mixing the ingredients, which can be added to an automatic mixer as such or as a solution.
  • the agents in particular in concentrated liquid form, are present as a portion in a completely or partially water-soluble envelope. The portioning makes it easier for the consumer to dose.
  • the funds can be packed in foil bags, for example.
  • Pouch packaging made from water-soluble film eliminates the need for the consumer to tear open the packaging. In this way, a single portion measured for a wash cycle can be conveniently dosed by placing the bag directly in the washing machine or by throwing the bag into a certain amount of water, for example in a bucket, bowl or hand wash basin.
  • the film bag surrounding the wash portion dissolves without leaving any residue when a certain temperature is reached.
  • water-soluble detergent portions which are in principle also suitable for producing detergents which can be used within the scope of the present invention.
  • the best-known methods are the tubular film method with horizontal and vertical sealing seams.
  • the thermoforming process deep-drawing process
  • the water-soluble envelopes do not necessarily have to consist of a film material, but can also be dimensionally stable containers that can be obtained, for example, by means of an injection molding process.
  • the filling material is injected into the capsule that is being formed, with the injection pressure of the filling liquid pressing the polymer strips into the cavities of the hemisphere.
  • a process for the production of water-soluble capsules in which first the filling and then the sealing takes place, is based on the so-called Bottle-Pack ® process.
  • a tube-like preform is fed into a two-part cavity. The cavity is closed, with the lower tube section being sealed, the tube is then inflated to form the capsule shape in the cavity, filled and finally sealed.
  • the casing material used to produce the water-soluble portion is preferably a water-soluble polymeric thermoplastic, particularly preferably selected from the group (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, blends and composites, inorganic salts and mixtures of the materials mentioned, preferably hydroxypropylmethylcellulose and/or polyvinyl alcohol blends.
  • Polyvinyl alcohols are commercially available, for example under the trademark Mowiol® (Clariant).
  • polyvinyl alcohols are, for example, Mowiol® 3-83 , Mowiol® 4-88, Mowiol® 5-88 , Mowiol® 8-88 and Clariant L648.
  • the water-soluble thermoplastic used to produce the portion can optionally also contain polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and/or mixtures of the above polymers.
  • the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis is 70 mol% to 100 mol%, preferably 80 mol% to 90 mol%, particularly preferably 81 mol% to 89 mol% and in particular 82 mol -% to 88 mol%. It is further preferred that the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 g/mol to 100,000 g/mol, preferably from 11,000 g/mol to 90,000 g/mol, particularly preferably 12,000 g /mol to 80,000 g/mol and in particular from 13,000 g/mol to 70,000 g/mol.
  • thermoplastics are used in amounts of at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight and in particular at least 90% by weight, in each case based on the weight the water-soluble polymeric thermoplastic.
  • GPC Gel Permeation Chromatography
  • the hydroxyl number was determined titrimetrically based on ASTM E 1899-97.
  • the amine number was determined by titration with trifluoromethanesulfonic acid.
  • P1 74.6 g (0.50 mol) triethanolamine and 5.53 g 50% (weight %) KOH solution were mixed and then dehydrated in an autoclave at 100° C. and ⁇ 10 mbar for two hours.
  • the autoclave was rendered inert by flushing it three times with nitrogen and an inlet pressure of 2 bar was set.
  • the reactor was then heated to 120-130°C and 1307 g (22.5 mol) of propylene oxide was added to produce three 15 PO/OH arms (total 45 PO/triethanolamine). After the end of the metering, the reaction was allowed to react until the pressure was constant. Volatile components were removed within two hours at 90 °C and 20 mbar.
  • the product was characterized by 1H-NMR, OH number, amine number and GPC.
  • P2 99.68 g (0.60 mol) triethanolamine and 6.00 g 50% strength (% by weight) KOH solution were mixed and then dehydrated in an autoclave at 100° C. and ⁇ 10 mbar for two hours.
  • the autoclave was rendered inert by flushing it three times with nitrogen and an inlet pressure of 2 bar was set.
  • the reactor was then heated to 120-130°C and 1261 g (21.7 mol) of propylene oxide was added to produce three 12 PO/OH arms (total 36 PO/triethanolamine). After the end of the metering, the reaction was allowed to react until the pressure was constant. Volatile components were removed within two hours at 90 °C and 20 mbar.
  • the product was characterized by 1H-NMR, OH number, amine number and GPC.
  • P4 104 g (0.54 mol) triisopropanolamine and 4.2 g 50% strength (% by weight) KOH solution were mixed and then dewatered in an autoclave at 100° C. and ⁇ 10 mbar for two hours.
  • the autoclave was rendered inert by flushing it three times with nitrogen and an inlet pressure of 2 bar was set.
  • the reactor was then heated to 120-130°C and 1415 g (24.4 mol) of propylene oxide was added to produce three 15 PO/OH arms (total 45 PO/triisopropanolamine). After the end of the metering, the reaction was allowed to react until the pressure was constant. Volatile components were removed within two hours at 90 °C and 20 mbar.
  • the product was characterized by 1H-NMR, OH number, amine number and GPC.
  • Table 1 Detergent composition (% by weight) Ingredient / Agent V1 w1 W2 W3 W4 Linear C 10-13 alkyl benzene sulfonate 22 22 22 22 22 C 13/15 oxo alcohol with 8 EO 24 24 24 24 24 C 12-18 fatty acid 7.5 7.5 7.5 7.5 7.5 polymer P1 - 5 - - polymer P2 - - 5 - - polymer P3 - - - 5 - Polymer P4 - - - - 5 propylene glycol 8th 8th 8th 8th glycerin 10.5 10.5 10.5 10.5 10.5 10.5 10.5 10.5 Optical brightener 0.6 0.6 0.6 0.6 0.6 monoethanolamine 6 6 6 6 6 DTPMPA 7Na 0.7 0.7 0.7 0.7 ethanol 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3

Claims (15)

  1. Utilisation de polymères, constitués d'alcoxylates à base de (mono-)amino dotés d'un poids moléculaire moyen de Mw de 600 à 10 000 g/mole,
    pour renforcer le pouvoir de lavage primaire de produits de lavage lors du lavage de textiles dans un liquide de lavage en particulier aqueux et contenant un tensioactif, contre des salissures, le polymère contenant deux ou trois chaînes de motifs d'oxyde d'alkylène par atome d'azote, les salissures étant des salissures sensibles aux tensioactifs ou aux enzymes, et le polymère contenant plus de 90 % en moles de motifs d'oxyde de propylène, par rapport à la somme de tous les motifs d'oxyde d'alkylène, et 10 à 18 motifs d'oxyde d'alkylène par chaîne d'oxyde d'alkylène.
  2. Utilisation selon la revendication 1, caractérisée en ce qu'elle est réalisée par l'ajout du polymère à un agent exempt de ce polymère ou à un bain de lavage qui contient un agent exempt de ce polymère.
  3. Utilisation selon la revendication 2, caractérisée en ce que la quantité d'ajout de polymère, par rapport à la quantité de l'agent exempt de ce polymère, se situe dans la plage de 0,01 % en poids à 20 % en poids, en particulier de 1 % en poids à 15 % en poids.
  4. Procédé pour l'élimination de salissures sensibles aux tensioactifs ou aux enzymes de textiles, caractérisé en ce qu'on met en contact un polymère, constitué d'alcoxylates à base de (mono-)amino, préférablement de propoxylates, dotés d'un poids moléculaire moyen de Mw de 600 à 10 000 g/mole, dans un bain de lavage en particulier aqueux et contenant un tensioactif, avec des textiles salis, le polymère contenant deux ou trois chaînes de motifs d'oxyde d'alkylène par atome d'azote, et le polymère contenant plus de 90 % en moles de motifs d'oxyde de propylène, par rapport à la somme de tous les motifs d'oxyde d'alkylène, et 10 à 18 motifs d'oxyde d'alkylène par chaîne d'oxyde d'alkylène.
  5. Procédé selon la revendication 4 ou utilisation selon l'une quelconque des revendications 1 à 3, caractérisé(e) en ce que l'on produit le bain de lavage en ajoutant 10 ml à 100 ml, en particulier 15 ml à 75 ml, de préférence 25 ml à 50 ml d'un agent de lavage liquide contenant de l'eau à 12 litres à 60 litres, en particulier 15 litres à 20 litres d'eau.
  6. Utilisation selon la revendication 2 ou 3 ou procédé selon la revendication 5, caractérisé(e) en ce que l'agent présente une concentration en tensioactif d'au moins 30 % en poids, en particulier dans la plage de 30 % en poids à 65 % en poids et en particulier de 50 % en poids à 38 % en poids.
  7. Utilisation ou procédé selon l'une quelconque des revendications précédentes, caractérisé(e) en ce que le polymère, constitué d'alcoxylates à base de (mono-)amino dotés d'un poids moléculaire moyen de Mw de 600 à 10 000 g/mole, contient exclusivement des motifs d'oxyde de propylène, par rapport à la somme de tous les motifs d'oxyde d'alkylène.
  8. Utilisation ou procédé selon l'une quelconque des revendications précédentes, caractérisé(e) en ce que le polymère, constitué d'alcoxylates à base de (mono-)amino dotés d'un poids moléculaire moyen de Mw de 600 à 10 000 g/mole, est à base d'un amorceur qui est choisi dans la liste constituée par la triéthanolamine, la triisopropanolamine et la tert-butylamine.
  9. Utilisation ou procédé selon la revendication 8, caractérisé(e) en ce que le polymère, constitué d'alcoxylates à base de (mono-)amino dotés d'un poids moléculaire moyen de Mw de 600 à 10 000 g/mole, est à base de triéthanolamine.
  10. Utilisation ou procédé selon la revendication 8, caractérisé(e) en ce que le polymère, constitué d'alcoxylates à base de (mono-)amino dotés d'un poids moléculaire moyen de Mw de 600 à 10 000 g/mole, est à base de triisopropanolamine.
  11. Utilisation ou procédé selon la revendication 8, caractérisé(e) en ce que le polymère, constitué d'alcoxylates à base de (mono-)amino dotés d'un poids moléculaire moyen de Mw de 600 à 10 000 g/mole, est à base de tert-butylamine.
  12. Utilisation ou procédé selon l'une quelconque des revendications précédentes, caractérisé(e) en ce que le polymère, constitué d'alcoxylates à base de (mono-)amino dotés d'un poids moléculaire moyen de Mw de 600 à 10 000 g/mole, contient 12 à 16 motifs d'oxyde d'alkylène et préférablement 12 à 15 motifs d'oxyde d'alkylène par chaîne d'oxyde d'alkylène.
  13. Utilisation ou procédé selon la revendication 12, caractérisé(e) en ce que le polymère, constitué d'alcoxylates à base de (mono-)amino dotés d'un poids moléculaire moyen de Mw de 600 à 10 000 g/mole, contient 12 motifs d'oxyde d'alkylène par chaîne d'oxyde d'alkylène.
  14. Utilisation ou procédé selon la revendication 12, caractérisé(e) en ce que le polymère, constitué d'alcoxylates à base de (mono-)amino dotés d'un poids moléculaire moyen de Mw de 600 à 10 000 g/mole, contient 15 motifs d'oxyde d'alkylène par chaîne d'oxyde d'alkylène.
  15. Utilisation ou procédé selon l'une quelconque des revendications précédentes, caractérisé(e) en ce que le poids molaire moyen en poids du polymère, constitué d'alcoxylates à base de (mono-)amino dotés d'un poids moléculaire moyen de Mw de 600 à 10 000 g/mole, se situe dans la plage de 1 300 à 6 000 g/mole, et préférablement de 1 400 à 4 500 g/mole.
EP18190901.1A 2018-08-27 2018-08-27 Agents actifs polymères améliorant le pouvoir détergeant primaire Active EP3617299B1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
ES18190901T ES2934333T3 (es) 2018-08-27 2018-08-27 Ingredientes activos poliméricos que mejoran el poder de lavado primario
PL18190901.1T PL3617299T3 (pl) 2018-08-27 2018-08-27 Polimerowe składniki aktywne polepszające podstawową zdolność piorącą
EP18190901.1A EP3617299B1 (fr) 2018-08-27 2018-08-27 Agents actifs polymères améliorant le pouvoir détergeant primaire
US17/270,644 US20210207062A1 (en) 2018-08-27 2019-08-08 Polymeric active ingredients which improve detergency
PCT/EP2019/071357 WO2020043458A1 (fr) 2018-08-27 2019-08-08 Principes actifs polymères améliorant le pouvoir détergent
CN201980055958.1A CN112639066B (zh) 2018-08-27 2019-08-08 改进去污力的聚合物活性成分
MX2021002372A MX2021002372A (es) 2018-08-27 2019-08-08 Ingredientes activos polimericos que mejoran la detergencia.
JP2021510395A JP2021535253A (ja) 2018-08-27 2019-08-08 洗浄力を向上させるポリマー活性成分
PCT/EP2019/071367 WO2020043460A1 (fr) 2018-08-27 2019-08-08 Principes actifs polymères améliorant le pouvoir détergent
BR112021003603-2A BR112021003603A2 (pt) 2018-08-27 2019-08-08 uso de polímeros, e, método para remover sujeira sensível a tensoativo ou enzima de têxteis.

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EP18190901.1A EP3617299B1 (fr) 2018-08-27 2018-08-27 Agents actifs polymères améliorant le pouvoir détergeant primaire

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EP3617299B1 true EP3617299B1 (fr) 2022-11-30

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Publication number Priority date Publication date Assignee Title
GB776661A (en) * 1954-01-28 1957-06-12 Wyandotte Chemical Corp Improved polyoxypropylene-polyoxyalkylene surface-active agents
DE3832589A1 (de) * 1988-09-24 1990-03-29 Henkel Kgaa Waschmittel fuer niedrige temperaturen
US6146427A (en) * 1997-12-04 2000-11-14 Crutcher; Terry Method for cleaning hydrocarbon-containing greases and oils from fabric in laundry washing applications
US20060293212A1 (en) * 2005-05-05 2006-12-28 Ecolab Inc. Stable solid compositions of spores, bacteria, fungi and/or enzyme
DE102011089948A1 (de) * 2011-12-27 2013-06-27 Henkel Ag & Co. Kgaa Die Primärwaschkraft verbessernde polyalkoxylierte Polyamine
KR20150135489A (ko) 2013-03-27 2015-12-02 바스프 에스이 세탁 과정에서 오염물 방출제로서 블록 공중합체
RU2714202C2 (ru) 2015-07-09 2020-02-13 Басф Се Способ очистки посуды

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EP3617299A1 (fr) 2020-03-04
PL3617299T3 (pl) 2023-04-24

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