EP0826025A1 - Utilisation de composes heterocycliques comme activateurs pour des composes peroxy inorganiques - Google Patents

Utilisation de composes heterocycliques comme activateurs pour des composes peroxy inorganiques

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Publication number
EP0826025A1
EP0826025A1 EP96919669A EP96919669A EP0826025A1 EP 0826025 A1 EP0826025 A1 EP 0826025A1 EP 96919669 A EP96919669 A EP 96919669A EP 96919669 A EP96919669 A EP 96919669A EP 0826025 A1 EP0826025 A1 EP 0826025A1
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EP
European Patent Office
Prior art keywords
groups
group
atoms
radicals
alkyl
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EP96919669A
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German (de)
English (en)
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EP0826025B1 (fr
Inventor
Reinhard Müller
Thomas Wehlage
Wolfgang Trieselt
Alfred Oftring
Elisabeth Kappes
Günter OETTER
Dieter Boeckh
Roland Ettl
Albert Hettche
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/393—Phosphorus, boron- or silicium-containing compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/614—Optical bleaching or brightening in aqueous solvents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/657—Optical bleaching or brightening combined with other treatments, e.g. finishing, bleaching, softening, dyeing or pigment printing
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/671—Optical brightening assistants, e.g. enhancers or boosters

Definitions

  • the present invention relates to the use of certain heterocyclic compounds based on cyclic carbamates, lactones or lactams as activators for inorganic per-compounds, in particular as cold bleach activators or optical brighteners in washing, cleaning and bleaching agents and in disinfectants.
  • the present invention further relates to certain technical preparations which contain these heterocyclic compounds.
  • N-acyllactarne e.g. N-acetylcaprolactam
  • bleaching organic peroxyacid e.g. N-acetylcaprolactam
  • the object of the present invention was to improve the bleaching, oxidation and cleaning action of a system of activator and inorganic per-compounds in the lower
  • Temperature range in particular from 15 to 60 ° C, bring about.
  • T is hydrogen or C 1 to C 4 alkyl
  • X is an oxygen-containing group of the formula means where
  • Y represents hydrogen, ammonium, which can optionally be substituted by organic radicals, or C 1 - to C 4 -alkyl and
  • A is a C 1 to C 18 alkylene group, a C 2 to
  • C 18 alkenylene group a C 5 to C 32 cycloalkylene group, a C 7 to C 30 aralkylene group, a C 6 to C 18 arylene group or a C 3 to C 18 heteroarylene group, wherein aliphatic structural units additionally to five hydroxyl groups, C 1 by a - to C 4 -alkoxy groups, amino groups, C 1 - to C 4 alkylamino groups, di-C 1 - C 4 alkylamino groups to, chlorine atoms, bromine atoms, nitro groups, cyano groups , Carboxyl groups, sulfo groups, carboxy-C 1 to C 4 -alkyl groups, carboxamide groups or phenyl, tolyl or benzyl radicals, where aromatic, cycloaliphatic and heteroaromatic structural units can also be substituted by the radicals mentioned, or by a up to eight non-adjacent oxygen atoms, amino groups, C 1 -C 4
  • Group X -CO- means the following:
  • C 3 to C 18 heteroaryl aliphatic radicals additionally having one to five hydroxyl groups, C 1 to C 4 alkoxy groups, amino groups, C 1 to C 4 alkylamino groups, di-C 1 to C 4 groups alkylamino groups, chlorine atoms, bromine atoms, nitro groups, cyano groups, carboxyl groups,
  • the variables Z 1 to Z 3 in the heterocyclic systems (a) to (c) can in particular mean C 2 to C 10 alkylene groupings of the following structure:
  • the variables Z 1 to Z 3 can be functionalized or interrupted as indicated.
  • bridge link A Typical examples of bridge link A are as follows:
  • methylene as a linear or branched C 1 to C 18 alkylene group, in particular C 6 to C 12 alkylene group,
  • 2,3-butylene pentamethylene, 3-methyl-1,5-pentylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene or octadecamethylene occur;
  • a linear or branched C 2 - to C 18 -alkenylene group in particular C 6 - to C 12 -alkenylene group, bridge members with one, two or three olefinic double bonds or also acetylenic double bonds can occur, for example 1,2-ethenylene, 1,3 Propenylene, 1,4-but-2-enylene, 1,6-hex-3-enylene,
  • C 10 -cycloalkylene groups are 1,2- or 1,3-cyclopentylene, 1,2-, 1,3- or 1,4-cyclohexylene, 1,2-, 1,3- or 1,4-cyclo-heptylene , 1,2-, 1,3-, 1,4- or 1, 5-cyclooctylene or groupings of the formula
  • C 7 to C 30 aralkylene groups in particular optionally alkyl-substituted C 7 to C 22 phenylalkylene and diphenylalkylene groups, groups of the formula come into consideration
  • ⁇ 1,4-, 1,3- and 1,2-phenylene are particularly suitable as C 6 to C 18 arylene groups, in particular optionally alkyl-substituted phenylene, bisphenylene or naphthylene groups, but also groups of the formula
  • C 3 - to C 18 -heteroarylene groups in particular five- or six-membered C 3 - to C 12 -heteroarylene groups with one or two heteroatoms from the group consisting of nitrogen, oxygen and sulfur, are suitable groups of the formula
  • the following structures can be considered as structures interrupted by oxygen or amino groups, in particular NH or N (CH 3 ) groups:
  • C 1 - to C 30 alkyl or C 9 - to C 30 alkyl group are, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert .-Butyl, n-pentyl, iso-pentyl, sec.-pentyl, tert.-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecy
  • C 7 - to C 18 aralkyl in particular C 7 - to C 12 aralkyl, in particular alkyl-substituted phenylalkyl groups, for example benzyl; 2-, 3- or 4-methylbenzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 2-, 3- or 4-ethylbenzyl, 3- or 4-isopropylbenzyl or 3- or 4-butylbenzyl;
  • C 14 aryl or C 10 to C 14 aryl groups especially in the former case phenyl and alkyl-substituted phenyl;
  • - As a C 3 - to C 18 -heteroaryl group, in particular five- or six-membered C 3 - to C 12 -heteroaryl groups with one or two heteroatoms from the group nitrogen, oxygen and sulfur come into question, examples of which are:
  • variables Z 1 to Z 3 , A, R 1 and R 2 defined above can additionally be functionalized by the groups indicated.
  • C 1 - to C 4 -alkoxy groups mean in particular methoxy
  • Preferred amino groups are -NH 2 , -NH (CH 3 ), -NH (CH 2 CH 3 ), -N (CH 3 ) 2 and -N (CH 2 CH 3 ) 2 .
  • Carboxy-C 1 - to C 4 -alkyl groups are, for example, carboxymethyl, Carboxyethyl, carboxypropyl, carboxybutyl or carboxy-tert-butyl.
  • the oxygen-containing group X in which one or two oxygen atoms are bonded to carbon, sulfur or phosphorus atoms by a double bond, that is to say represent carbonyl or heterocarbonyl functionalities, preferably means
  • the two heterocyclic radicals L bonded to the group X are preferably the same.
  • heterocyclic compounds I are preferably used:
  • the radical R 1 in the structure types (1) to (8) and (10) stands in particular for methyl, ethyl, n-butyl, tert-butyl, n-heptyl, n-nonyl, n-undecyl, cyclohexyl, benzyl, Phenyl or 2-, 3- or 4-methylphenyl.
  • the radical R 1 in structure type (11) stands in particular for n-nonyl, n-undecyl or cyclohexyl.
  • the bridge member A in the structure types (24) to (33) stands in particular for hexamethylene, octamethylene, decamethylene, dodecamethylene, 1,3- or 1,4-cyclohexylene or 1,4-, 1,3- or
  • 1, 2-phenylene; of special interest for A is 1,4-phenylene (derived from terephthalic acid).
  • the compounds I can be used as activators for inorganic per-compounds wherever a particular increase in the oxidation effect of the inorganic per-compounds at low temperatures is important, e.g. in the bleaching of textiles, hair or hard surfaces, in the oxidation of organic or inorganic intermediates and in disinfection. Most of them outperform
  • the compounds I are odorless or pleasant-smelling substances which can therefore also be used without difficulty in detergents and cleaning agents which are intended for use in the household.
  • the conditions can be varied widely depending on the intended use.
  • mixtures of water and suitable organic solvents e.g. for use in disinfection or in the oxidation of intermediates, as a reaction medium.
  • the pH of the reaction medium can be selected within wide limits, from the weakly acidic range (pH 4) to the strongly alkaline range (pH 13), depending on the application.
  • the alkaline range from pH 8 to pH 11 is preferred since it is particularly advantageous for the activation reaction and the stability of the per compound formed.
  • the activator described is also preferably used together with a sodium perborate or with sodium carbonate perhydrate, which already have pH values in this range in their solutions.
  • suitable per compounds are phosphate perhydrates and urea perhydrate.
  • the amounts of per compounds are generally chosen so that between 10 and 10,000 ppm of active oxygen, preferably between 50 and 5000 ppm of active oxygen, are present in the solutions. The amount of activator used also depends on the application.
  • the compounds I can be used for activation in pure form or, if this is expedient, for example, to increase the storage stability, in special forms of supply such as tablets, granules or in finely divided coated form (so-called prills). Such granular forms, which are produced by agglomeration granulation, are of particular importance. Liquid ones are suitable for machine dosing
  • Activators as such or solutions in organic solvents or liquid dispersions containing the activator It is preferably used in pre-assembled agents in a mixture with the per compounds to be activated and, if appropriate, further components required for the desired bleaching, oxidation or cleaning process, such as pH regulating agents and stabilizers for per compounds.
  • further components required for the desired bleaching, oxidation or cleaning process such as pH regulating agents and stabilizers for per compounds.
  • other customary activators can also be present. Mixing with selected amounts of per-compounds and other additives makes the application easier and the user achieves the desired result more reliably, since the optimal conditions are obtained when the agents are dissolved without further action.
  • Such agents are in solid, preferably scatterable form, but also as liquids.
  • polyacylated sugars for example pentaacetyl glucose; - Acyloxybenzenesulfonic acids and their alkali and alkaline earth metal salts, for example sodium p-isononanoyloxy-benzenesulfonate or sodium p-benzoyloxy-benzenesulfonate; - N-diacylated and N, N'-tetracylated amines, for example N, N, N ', N'-tetraacetyl-methylenediamine and -ethylenediamine, N, N-diacetylaniline, N, N-diacetyl-p-toluidine or 1,3-diacylated hydantoins such as 1,3-diacetyl-5, 5-dimethylhydantoin;
  • N-alkyl-N-sulfonyl-carbonamides e.g. N-methyl-N-mesyl-acetamide or N-methyl-N-mesyl-benzamide;
  • N-acylated cyclic hydrazides acylated triazoles or urazoles, e.g. Monoacetyl maleic acid hydrazide;
  • N, N-trisubstituted hydroxy amines e.g. 0-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinyl-hydroxylamine or
  • N, N'-diacylsulfurylamides e.g. N, N '-dimethyl-N, N'-diacetylsulfurylamide or N, N'-diethyl-N, N'-dipropionylsulfurylamide;
  • Triacylcyanurates e.g. Triacetyl cyanurate or tribenzoyl cyanurate
  • Carboxylic anhydrides e.g. Benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride; - 1,3-diacyl-4,5-diacyloxy imidazolines, e.g. 1,3-diacetyl-4,5-diacetoxyimidazoline;
  • ⁇ -acyloxy polyacyl malonamides e.g. ⁇ -acetoxy-N, N'-diacetylma lonamide
  • Diacyl-dioxohexahydro-1,3,5-triazines e.g. 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine;
  • heterocyclic compounds I as cold bleach activators or optical brighteners in washing, cleaning and bleaching agents, especially in washing and Bleaching agents and bleach additives for textile washing, as well as in disinfectants.
  • Activators can be combined with almost all common ingredients of detergents and bleaches. In this way it is possible to build up means which are particularly suitable for textile treatment at low temperatures and also means which are suitable in a number of temperature ranges up to the traditional area of washing dishes.
  • the main components of detergents, bleaching agents and cleaning agents are, in addition to per-compounds and activators, framework substances
  • Builder i.e. inorganic builders and / or organic cobuilders, and surfactants, especially anionic and / or nonionic surfactants.
  • other customary auxiliaries and accompanying substances such as bulking agents, complexing agents, phosphonates, dyes, corrosion inhibitors, graying inhibitors, bleaching catalysts, peroxide stabilizers, electrolytes, optical brighteners, enzymes, perfume oils, foam regulators and activating agents
  • Inorganic builders All conventional inorganic builders such as aluminosilicates, silicates, carbonates and phosphates are suitable as inorganic builders.
  • Suitable inorganic builders are e.g. Alumosilicates with ion exchange properties such as Zeolites.
  • zeolites are suitable, in particular zeolite A, X, B, P, MAP and HS in their Na form or in forms in which Na is partly replaced by other cations such as Li, K, Ca, Mg or ammonium.
  • Suitable zeolites are described, for example, in EP-A 038 591, EP-A 021 491, EP-A 087 035, US-A 4 604 224, GB-A 2 013 259, EP-A 522 726, EP-A 384 070 and WO-A 94/24 251.
  • Suitable inorganic builders are e.g. amorphous or crystalline silicates such as e.g. amorphous disilicates, crystalline disilicates such as the layered silicate SKS-6 (manufacturer Hoechst).
  • the silicates can be used in the form of their alkali, alkaline earth or ammonium salts. Na, Li and
  • Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, for example C 9 to C 11 alcohol sulfates, C 12 to C 13 alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.
  • Suitable anionic surfactants are sulfated ethoxylated C 8 to C 22 alcohols (alkyl ether sulfates) or their soluble salts.
  • Compounds of this type are prepared, for example, by first alkoxylating a C 8 to C 22 , preferably a C 10 to C 18 alcohol, for example a fatty alcohol, and then sulfating the alkoxylation product.
  • Ethylene oxide is preferably used for the alkoxylation, 2 to 50, preferably 3 to 20, moles of ethylene oxide being used per mole of fatty alcohol.
  • the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide.
  • Alkoxylated C 8 to C 22 alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide are also suitable.
  • the alkoxylated C 8 or to C 22 alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in statistical distribution.
  • alkanesulfonates such as
  • C 8 - to C 24 - preferably C 10 - to C 18 -alkanesulfonates and soap such as the salts of C 8 - to C 24 -carboxylic acids.
  • Other suitable anionic surfactants are C 9 to C 20 linear alkylbenzenesulfonates (LAS).
  • the anionic surfactants are preferably added to the detergent in the form of salts.
  • Suitable cations in these salts are alkali metal salts such as sodium, potassium and lithium and
  • Ammonium salts such as Hydroxethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.
  • Suitable nonionic surfactants are, for example, alkoxylated C 8 -C 22 -alcohols such as fatty alcohol alkoxylates or oxalcohol alkoxylates.
  • the alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as the surfactant.
  • Block polymers of ethylene oxide also come here, Propylene oxide and / or butylene oxide or adducts which contain the alkylene oxides mentioned in a statistical distribution. 2 to 50, preferably 3 to 20, moles of at least one alkylene oxide are used per mole of alcohol.
  • Ethylene oxide is preferably used as the alkylene oxide.
  • the alcohols preferably have 10 to 18 carbon atoms.
  • nonionic surfactants are alkyl phenol ethoxylates with C 6 to C 14 alkyl chains and 5 to 30 moles of ethylene oxide units.
  • alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain. These compounds usually contain 1 to 20, preferably 1.1 to 5, glucoside units.
  • N-alkyl glucamides of general structure II or III
  • R 4 is C 6 to C 22 alkyl, R 5 H or C 1 to C 4 alkyl and R 6 is a polyhydroxyalkyl radical having 5 to 12 C atoms and at least
  • R 3 is hydroxy groups.
  • R 4 is preferably C 10 to C 18 alkyl, R 5 is methyl and R 6 is a C 5 or C 6 radical.
  • R 4 is preferably C 10 to C 18 alkyl, R 5 is methyl and R 6 is a C 5 or C 6 radical.
  • such compounds are obtained by acylation of reducing
  • aminated sugars with acid chlorides of C 10 -C 18 carboxylic acids aminated sugars with acid chlorides of C 10 -C 18 carboxylic acids.
  • the detergents according to the invention preferably contain C 10 -C 16 alcohols ethoxylated with 3-12 mol ethylene oxide, particularly preferably ethoxylated fatty alcohols as nonionic surfactants.
  • C 4 - to C 20 -di, tri and tetracarboxylic acids such as succinic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and alkyl and alkylene succinic acids
  • C 2 to C 16 alkyl or alkylene radicals C 4 to C 20 hydroxycarboxylic acids such as malic acid, tartaric acid, gluconic acid, glutaric acid, citric acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid;
  • Aminopolycarboxylates such as nitrilotriacetic acid, methylglycine diacetic acid, alanine diacetic acid, ethylenediaminetetraacetic acid and serine diacetic acid;
  • Salts of phosphonic acids such as e.g. Hydroxyethane diphosphonic acid, ethylenediaminetetra (methylene phosphonate) and diethylene triamine penta (methylene phosphonate).
  • Suitable oligomeric or polymeric polycarboxylates as organic cobuilders are:
  • Copolymers and terpolymers of unsaturated C 4 -C 8 dicarboxylic acids the comonomers being monoethylenically unsaturated monomers from group (i) in amounts of up to 95% by weight from group (ii) in amounts of up to 60% by weight %
  • polymerized from group (iii) in amounts of up to 20% by weight.
  • suitable unsaturated C 4 -C 8 dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleic acid is preferred.
  • Group (i) includes monoethylenically unsaturated C 3 -C 8 -monocarboxylic acids such as, for example, acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. Acrylic acid and methacrylic acid from group (i) are preferably used.
  • Group (ii) includes monoethylenically unsaturated
  • Group (iii) comprises (meth) acrylic esters of C 1 to C 8 alcohols, (meth) acrylonitrile, (meth) acrylamides of C 1 -C 8 amines, N-vinylformamide and vinylimidazole.
  • polymers of group (ii) contain vinyl esters in copolymerized form, these can also be partially or completely hydrolyzed to vinyl alcohol structural units.
  • Suitable copolymers and terpolymers are known, for example, from US Pat. No. 3,887,806 and DE-A 43 13 909.
  • Suitable copolymers of dicarboxylic acids as organic cobuilders are preferably:
  • the weight ratio of acrylic acid to vinyl esters can vary in the range from 20:80 to 80:20, and particularly preferably terpolymers of maleic acid, acrylic acid and vinyl acetate or vinyl propionate in a weight ratio of 20 (maleic acid): 80 (acrylic acid + vinyl ester) to 90 (maleic acid): 10 (acrylic acid + Vinyl ester), the weight ratio of acrylic acid to vinyl ester being in the range of
  • Suitable unsaturated carboxylic acids are, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid and mixtures of acrylic acid and maleic acid, which are present in amounts of 40 to 95% by weight, based on the component to be grafted, are grafted on.
  • Suitable modifying monomers are the above-mentioned monomers of groups (ii) and (iii).
  • Ethylene oxide / propylene oxide or ethylene oxide / butylene oxide block copolymers statistical ethylene oxide / propylene oxide or ethylene oxide / butylene oxide copolymers, alkoxylated mono- or polybasic C 1 -C 22 alcohols, cf. No. 4,746,456.
  • Grafted degraded or degraded reduced starches and grafted polyethylene oxides from this group are preferably used, 20 to 80% by weight of monomers based on the graft component being used in the graft polymerization.
  • a mixture of maleic acid and acrylic acid in a weight ratio of 90:10 to 10:90 is preferably used for the grafting.
  • Polyglyoxylic acids as organic cobuilders are described, for example, in EP-B 001004, US-A 5399286, DE-A 4106355 and
  • EP-A 656914 The end groups of the polyglyoxylic acids can have different structures.
  • Polyamidocarboxylic acids and modified polyamidocarboxylic acids as organic cobuilders are known, for example, from
  • Condensation products of citric acid with hydroxycarboxylic acids or polyhydroxy compounds as organic cobuilders are known, for example, from WO-A 93/22362 and WO-A 92/16493.
  • Such carboxyl Condensates containing groups usually have molecular weights of up to 10,000, preferably up to 5,000.
  • Suitable soil release polymers and / or graying inhibitors for detergents are, for example:
  • Polyester made of polyethylene oxides which are end group-capped with di- and / or polyhydric alcohols and dicarboxylic acid.
  • polyesters are known, for example from
  • soil release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides (cf. US Pat. No. 4,746,456, US Pat. No. 4,846,995, DE-A 3711299,
  • US-A 4904408, US-A 4846994 and US-A 4849126 or modified celluloses such as e.g. Methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.
  • Color transfer inhibitors examples are homopolymers and copolymers of vinylpyrrolidone, vinylimidazole, vinyloxazolidone and 4-vinylpyridine-N-oxide with molecular weights from 15,000 to 100,000, and crosslinked, finely divided polymers based on these monomers.
  • the use of such polymers mentioned here is known, cf. DE-B 2232353, DE-A 2814287,
  • Enzymes Suitable enzymes are proteases, lipases, amylases and cellulases.
  • the enzyme system can work on a single one of the enzymes
  • Suitable bleaching catalysts are quaternized imines and sulfonimines (cf. US-A 5360568, US-A 5360569 and EP-A 453003) and manganese complexes (cf. WO-A 94/21777).
  • the present invention also relates to washing and
  • Bleaching agents for textile washing which contain 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the total amount of the preparation, of one or more heterocyclic compounds I.
  • Typical textile detergents and bleaches of this type have the following composition:
  • anionic and / or nonionic surfactants 0.5 to 20% by weight, preferably 5 to 15% by weight of anionic and / or nonionic surfactants
  • framework substances from the group of condensed phosphates, alkali silicates, alkali carbonates, sodium aluminum silicates and mixtures thereof,
  • framework substances from the group salts of amino carboxylic acids, salts of polyphosphonic acids, salts of polycarboxylic acids and mixtures thereof, 2 to 35% by weight, preferably 5 to 30% by weight .-% inorganic per compounds,
  • the activators I according to the invention are preferably used in powdered or granular detergents. It can be classic heavy-duty detergents or concentrated or compacted detergents.
  • a typical powdery or granular heavy-duty detergent according to the invention can have, for example, the following composition: 0.5 to 50, preferably 5 to 30% by weight of at least one anionic and / or nonionic surfactant,
  • Color transfer inhibitors - 0 to 1.5% by weight, preferably 0.1 to 1.0% by weight of protease, - 0 to 1.5% by weight, preferably 0.1 to 1.0% by weight other detergent enzymes, in particular lipase, 0 to 1.5% by weight, preferably 0.2 to 1.0% by weight, of a soil release polymer, ad 100% customary auxiliaries and accompanying substances and water.
  • Inorganic builders preferably used in detergents are sodium carbonate, sodium bicarbonate, zeolite A and P and amorphous and crystalline Na silicates, in particular layered silicates such as SKS-6 (manufacturer: Hoechst AG),
  • Organic cobuilders preferably used in detergents are acrylic acid / maleic acid copolymers, acrylic acid / maleic acid / vinyl ester terpolymers such as acrylic acid / maleic acid / vinyl acetate terpolymers, polyaspartic acid and citric acid.
  • Inorganic bleaching agents preferably used in detergents are sodium perborate and sodium carbonate perhydrate.
  • Inorganic surfactants preferably used in detergents are fatty alcohol sulfates, linear alkylbenzenesulfonates (LAS) and soaps, the proportion of LAS preferably being less than 8% by weight, particularly preferably less than 4% by weight.
  • Nonionic surfactants preferably used in detergents are C 11 to C 17 oxo alcohol ethoxylates with 3-13 ethylene oxide units, C 10 to C 16 fatty alcohol ethoxylates with 3-13 ethylene oxide units units and additionally ethoxylated fatty or oxo alcohols alkoxylated with 1-4 propylene oxide or butylene oxide units.
  • Enzymes which are preferably used in detergents are protease, lipase and cellulase. Of the commercially available enzymes, amounts of 0.1 to 1.5% by weight, preferably 0.2 to 1.0% by weight, of the made-up enzyme are generally added to the detergents.
  • Suitable proteases are e.g. Savinase and Esperase (manufacturer Novo Nordisk).
  • a suitable lipase is e.g. Lipolase
  • a suitable cellulase is e.g.
  • Graying inhibitors and soil release polymers preferably used in detergents are graft polymers of vinyl acetate on polyethylene oxide with a molecular weight of 2500-8000 in a weight ratio
  • Molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate from 8: 1 to 1: 1 and block polycondensates according to DE-A 4403866.
  • Color transfer inhibitors preferably used in detergents are soluble vinylpyrrolidone and vinylimidazole copolymers with molar masses above 25,000 and finely divided crosslinked polymers based on vinylimidazole.
  • the detergents described preferably contain
  • the powdered or granular detergents according to the invention can contain up to 60% by weight of inorganic adjusting agents. Sodium sulfate is usually used for this. However, the detergents according to the invention are preferably low in adjusting agents and contain only up to 20% by weight, particularly preferably only up to 8% by weight, of adjusting agents.
  • the detergents according to the invention can have different bulk densities in the range from 300 to 1200, in particular 500 to 950 g / l.
  • Modern compact detergents generally have high bulk densities and show a granular structure.
  • the formulations of the activators described for textile washing can also be agents which are used as additives to peroxide-containing or peroxide-free detergents. They essentially contain activator or a mixture of activator and per Compound and optionally other auxiliaries and additives, in particular stabilizers, pH regulators, thickeners and surfactants.
  • the present invention also relates to bleach additives for textile washing which contain 1 to 30% by weight, preferably 5 to 25% by weight, based on the total amount of the additive preparation, of one or more heterocyclic compounds I.
  • Typical bleach additives of this type have the following
  • agents intended for cleaning hard surfaces contain, in particular, surfactants, framework substances and, in the case of polishing and abrasive agents, abrasive components. Since these agents are often used at room temperature, the use of the activators according to the invention has a particularly advantageous effect on the bleaching and germicidal action.
  • Disinfectants based on the activators described generally contain, in addition to these and inorganic per-compounds, other auxiliaries and additives such as pH-regulating substances, stabilizers and surfactants. In special cases, they can additionally contain special microbicides which increase the very broad killing effect of the activated per-compound against certain germs.
  • the present invention also relates to disinfectants which contain 1 to 40% by weight, preferably 5 to
  • Typical disinfectants of this type have the following
  • the use of the activators described according to the invention is in no way limited to the use in a ready-made form of these described or other types.
  • the focus is generally on the individual metering of reagents, since it is often the more cost-effective method.
  • heterocyclic compounds I are predominantly known from the literature and syntheses for their preparation have been described.
  • heterocyclic compounds I With the heterocyclic compounds I, a significant improvement in the bleaching, oxidation and cleaning action in the lower temperature range can be achieved in the technical applications described.
  • pantolactone 0.5 mol was dissolved in 500 ml of toluene in a stirring flask with a stirring motor, thermometer, dropping funnel and cooler. 0.51 mol of triethylamine was added and the mixture was heated to 50.degree. There were now 0.51 mol of benzoyl chloride at this temperature
  • the preparation was carried out in analogy to Example 1 from pantolactone and octanoic acid chloride.
  • the preparation is carried out analogously to Example 3 from 1,3-oxazolidone (2) and pivalic acid chloride (H 3 C) 3 C-COCl.
  • Example 6 The preparation is carried out in analogy to Example 3 from 1,3-oxazolidone (2) and benzoyl chloride.
  • the title compound was prepared by conventional methods from phenyl chloroformate and ⁇ -butyrolactam (2-pyrrolidone). Examples of use
  • Examples 2, 4, 5 and 6 were used to carry out washing tests with test soiling of red wine, tea or grass on cotton fabric, in which in most cases better bleaching effects could be achieved than with the activator N, N, N 'which represents the prior art.
  • N'-tetraacetylethylenediamine (TAED) N'-tetraacetylethylenediamine
  • Examples A and B In addition to washing tests with test soiling of grass on cotton, examples 6 and B also carried out tests with a colored fabric (EMPA 115). In the case of the colored fabric, it can be seen that the undesired bleaching of the color in the activators used according to the invention is at a comparable or lower level compared to TAED.
  • the test was carried out in a Launder-O-meter, type Atlas Standard, using a phosphate-free detergent I under the following conditions:
  • Washing time 30 min (including heating up time)
  • Detergent composition I (% by weight): linear alkylbenzenesulfonate (Na salt) 6.25
  • Examples 6 and 7 were used to carry out further washing tests with test soiling of tea or red wine on cotton fabric, in which in most cases better bleaching effects could be achieved than with TAED (comparative examples C and D).
  • Table 2 below shows typical modern heavy-duty detergent formulation amounts II to VIII.
  • the compositions IV and V were used in the washing tests.
  • SKS-6 commercially available layered silicate
  • Soil release polymer graft polymer of vinyl acetate
  • Dequest ® 2046 ethylenediamine-N, N, N ', N'-tetra- (methylenephosphonate)
  • the color strength of the test fabric was measured photometrically. From the reflectance values measured at the individual test fabrics at 18 wavelengths in the range from 400 to 700 nm at a distance of 20 nm, the methods described in A. Kud, Seifen, ⁇ le, Fette Wachsen 119, pp. 590-594 (1993) respective color strengthening the test stains before and after washing and determining the absolute bleaching effect A abs in%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne l'utilisation de composés hétérocycliques de la formule (I) R1-X-L, dans laquelle L désigne un reste carbamate cyclique, un reste lactone-oxy ou un reste lactame, X désigne un groupe contenant de l'oxygène d'une des formules (a), (b), (c), (d), (e) ou (f), où A représente un groupe de pontage, et R1 désigne un reste organique ou un groupement L, comme activateurs pour des composés peroxy inorganiques, en particulier comme activateurs de blanchiment à froid ou comme agents d'azurage optique dans des produits de lavage, de nettoyage et de blanchiment, ainsi que dans des produits désinfectants.
EP96919669A 1995-05-17 1996-05-04 Utilisation de composes heterocycliques comme activateurs pour des composes peroxy inorganiques Expired - Lifetime EP0826025B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19518039A DE19518039A1 (de) 1995-05-17 1995-05-17 Verwendung von heterocyclischen Verbindungen als Aktivatoren für anorganische Perverbindungen
DE19518039 1995-05-17
PCT/EP1996/001863 WO1996036686A1 (fr) 1995-05-17 1996-05-04 Utilisation de composes heterocycliques comme activateurs pour des composes peroxy inorganiques

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EP0826025A1 true EP0826025A1 (fr) 1998-03-04
EP0826025B1 EP0826025B1 (fr) 2000-03-01

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EP (1) EP0826025B1 (fr)
JP (1) JPH11505281A (fr)
DE (2) DE19518039A1 (fr)
ES (1) ES2144246T3 (fr)
WO (1) WO1996036686A1 (fr)

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DE19541012A1 (de) * 1995-11-03 1997-05-07 Basf Ag Verwendung von Oximestern als Aktivatoren für anorganische Perverbindungen
DE19609953A1 (de) * 1996-03-14 1997-09-18 Basf Ag Feste Zusammensetzung aus heterocyclischen Verbindungen und/oder Oximestern und inerten porösen Trägermaterialien und ihre Verwendung als stabile Bleichaktivator-Komponente in Wasch-, Bleich- und Reinigungsmitteln
WO2000002990A1 (fr) * 1998-07-08 2000-01-20 The Procter & Gamble Company Activateurs de blanchiment a base d'imido cyclique et compositions contenant de tels activateurs
US6448394B1 (en) * 1998-09-24 2002-09-10 Dsm N.V. Process for the preparation of an N-alkyl or N-aryl carbamoyl derivative
US20030215441A1 (en) * 1999-03-05 2003-11-20 Laboratories Anios, Societe Anonyme Process for preparing an antimicrobial composition
NL1013728C2 (nl) * 1999-12-02 2001-06-06 Dsm Nv Werkwijze voor de bereiding van een carbonzuurderivaat.
FR2808274B1 (fr) 2000-04-28 2002-07-12 Poudres & Explosifs Ste Nale Procede de preparation des n, n'-carbonylbislactames
GB0020489D0 (en) * 2000-08-18 2000-10-11 Univ Leeds Use of percarbamic acids and precursors therefor
DE10105030A1 (de) * 2001-02-05 2002-08-08 Basf Ag Verfahren zur Herstellung von N,N'-Carbonylbis-Epsilon-caprolactam
DE10105029A1 (de) * 2001-02-05 2002-08-08 Basf Ag Verfahren zur Herstellung von N,N'-Carbonylbis-Epsilon-caprolactam
US7435269B2 (en) * 2004-11-05 2008-10-14 Combe Incorporated Bismuth dye system for human hair
JP2015091992A (ja) * 2015-01-27 2015-05-14 三浦工業株式会社 殺菌性洗浄剤
US20220000108A1 (en) * 2018-11-12 2022-01-06 Diversey, Inc. C3-c6 n-alkyl-gamma-butyrolactam- and peroyxgen-containing antimicrobial compositions
MX2021003723A (es) 2018-12-04 2021-05-13 Virox Tech Inc Composiciones antimicrobianas que contienen n-alquil gamma butirolactama de c3-c5 y usos de las mismas.
US11820737B2 (en) 2020-01-31 2023-11-21 Ecolab Usa Inc. Generation of peroxyhydroxycarboxylic acid and the use thereof
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Publication number Publication date
WO1996036686A1 (fr) 1996-11-21
DE19518039A1 (de) 1996-11-21
JPH11505281A (ja) 1999-05-18
US5972237A (en) 1999-10-26
ES2144246T3 (es) 2000-06-01
EP0826025B1 (fr) 2000-03-01
DE59604544D1 (de) 2000-04-06

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