Composition for impregnation of fibers, fabrics and nettings imparting a protective activity against pests

Abstract

Insecticide composition for application to a textile material or plastics material selected from the group consisting of fibers, fabric, knitgoods, nonwovens, netting material, foils, and tarpaulins, which composition comprises a mixture including at least one insecticide and/or at least one repellent, and at least one binder; an impregnated textile material or plastics material comprising at least one insecticide and/or at least one repellent, and at least one binder; processes for impregnation of a textile material or plastics material and a process for coating of a textile material or plastics material.

1 . An insecticide composition for application to a textile material or plastics material which composition comprises a mixture including 
 a) at least one insecticide and/or at least one repellent as component A, and 
 b1) at least one acrylic binder as component B1 obtainable by emulsion polymerisation of the following components: 
 b1a) n-butyl acrylate as component B1A,  
 b1b) at least one monomer of formula I as component B1B  
                     
 
    wherein     R 1 , R 2  and R 3  are independently selected from C 1 - to C 10 -alkyl which may be linear or branched; substituted or unsubstituted aryl;     R 1  and R 2  may further be H;     except of R 3 =n-butyl, when R 1  and R 2  are H; 
 b1c) at least one monomer of formula II as component B1C  
                     
    wherein     R 4 , R 5 , R 6  and R 7  are independently selected from the group consisting of H, C 1 - to C 10 -alkyl which may be linear or branched; substituted or unsubstituted aryl; 
 b1d) optionally at least one momomer of formula III as component B1D  
                     
   wherein     R 8  and R 9  are independently selected from the group consisting of H, C 1 - to C 10 -alkyl which may be linear or branched; substituted or unsubstituted aryl;     X is selected from the group consisting of H, OH, NH 2 , OR 11 OH, glycidyl, hydroxypropyl,                           groups of the formula                          wherein     R 10  is selected from the group consisting of C 1 - to C 10 -alkyl which may be branched or linear substituted or unsubstituted aryl;     R 11  is selected from the group consisting of C 1 - to C 10 -alkylene; 
  substituted or unsubstituted arylenes; 
 b1e) further monomers which are copolymerizable with the monomers mentioned above selected from 
 b1e1) polar monomers as component B1E1; and/or  
 b1e2) non polar monomers as component B1E2;  
 
 
   and/or 
 b2) at least one polyurethane as component B2, obtainable by reaction of the following components: 
 b2a) at least one diisocyanate or polyisocyanate as component B2A;  
 b2b) at least one diol, triol or polyol as component B2B, preferably aliphatic, cycloaliphatic and/or araliphatic diols having 2 to 14, preferably 4 to 10 carbon atoms, more preferably 1,6-hexanediol or neopentyl glycol;  
 b2c) optionally further components as component B2C; and  
 b2d) optionally further additives as component B2D.  
 
   
     
     
         2 . The insecticide composition as claimed in  claim 1 , Wherein the acrylic binder is obtainable by emulsion polymerization of the following components; 
 b1a) 10 to 90% by weight, preferably 15 to 80% by weight, mone preferably 20 to 70% by weight of component B1A:    b1b) 10 to 90% by weight, preferably 12 to 85% by weight, more preferably 15 to 65% by weight of component B1B;    b1c) 1 to 5% by weight of component B1C;    b1d) 0 to 5% by weight, preferably 1 to 4% by weight more preferably 0.2 to 3% by weight of component B1D;    b1e) further monomers which are copolymerizable with the monomers menti oned above selected from 
 b1e1) 0 to 30% by weight, preferably 0 to 25% by weight, more preferably 5 to 20% by weight of component B1E1; and/or  
 b1e2) 0 to 40% by weight, preferably 0 to 30% by weight, more preferably 5 to 20% by weight of component B1E2;  
   wherein the sum of the components B1A, B1B, B1C and optionally B1D and B1E is 100% by weight.    
     
     
         3 . The insecticide composition as claimed in  claim 1 , wherein the polyurethane is obtainable by reaction of the following components: 
 b2a) 55 to 99% by weight, preferably 70 to 98% by weight, more preferably 75 to 90 by weight based on the polyurethane of component B2A;    b2b) 10 to 90% by weight, preferably 12 to 85% by weight, more preferably 15 to 65% by weight based an the polyurethane of component B2B;    b1c) 0 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 1 to 5% by weight based on the polyurethane of component B2C; and    b1d) 0 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.5 to 5% of component B2D;    whereln the sum of the components B2A, B2B, optionally B2C and optionally B2D is 100% by weight    
     
     
         4 . The insecticide composition as claimed in  claim 1 , wherein the insecticide is selected from 
 pyrethroid compounds such as    Ethofenprox: 2-(4-ethoxyphenyl)-2-methylpropyl-3-phenoxybenzyl ether,    Fenvalerate: (RS)-alpha-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3 methylbutyrate,    Esfenvalerate: (S)-alpha-cyano-3-phenoxybenzyl (S)-2-(4-chlorophenyl)-3-methylbuty-rate,    Fenpropathrin: (RS)-alpha-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropane-carboxylate,    Cypermethrin: (RS)-alpha-cyano-3-phenoxybenzyl (1RS)-cis, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, alpha-Cypermethrin,    Permethrin: 3-phenoxybenzyl (1RS)-cis, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,    Cyhalothrin: (RS)-alpha-cyano-3-phenoxybenzyl (Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopro panecarboxylate,    Deltamethrin: (S)-alpha-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate,    Cycloprothrin: (RS)-alpha-cyano-3-phenoxybenzyl (RS)-2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarboxylate,    Fluvalinate: alpha-cyano-3-phenoxybenzyl N-(2-chloro-alpha, alpha, alpha, alpha-trifluoro-p-tolyl)-D-valinate,    Bifenthrin: 2-methylbiphenyl-3-ylmethyl)0(Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate,    2-methyl-2-(4-bromodifluoromethoxyphenyl)propyl (3-phenoxybenzyl)ether,    Tralomethrin; (S)-alpha-cyano-3-phenoxybenzyl (1R-cis)3((1′RS)(1′,2′,2′,2′-tetrabromoethyl))-2,2-dimethylcyclopropanecarboxylate,    Silafluofen: 4-ethoxyphenyl(3-(4fluoro-3phenoxyphenyl)propyl}dimethylsilane,    D-fenothrin: 3-phenoxybenzyl (1R)-cis, trans)-chrysanthemate,    Cyphenothrin: (RS)-alpha-cyano-3-phenoxybenzyl (1R-cis, trans)-chrysanthemate, D-resmethrin: 5-benzyl-3-furylmethyl (1R-cis, trans)-chrysanthemate,    Acrinathrin: (S)-alpha-cyano-3-phenoxybenzyl (1R-cis(Z))-2,2-dimethyl-3-(oxo-3-(1,1,1,3,3,3-hexafluoropropyloxy)propenyl(cyclopropanecarboxylate,    Cyfluthrin: (RS)-alpha-cyano-4-fluoro-3-phenoxybenzyl 3-(2,2dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,    Tefluthrin: 2,3,5,6-tetrafluoro-4-methylbenzyl (1RS-cis (Z))-3-(2-chloro-3,3,3-trifluoro-prop-1-enyl)-2,2-dimethylcyclopropanecarboxylate,    Transfluthrin: 2,3,5,6-tetrafluorobenzyl (1R-trans)-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate,    Tetramethrin: 3,4,5,6-tetrahydrophthalimidomethyl (1RS)-cis, trans-chrysanthemate,    Allethrin: (RS)-3-allyl-2-methyl-4-oxocyclopent-2-enyl (1RS)-cis, trans-chrysanthemate,    Prallethrin: (S)-2-methyl-4-oxo-3-(2-propynyl)cyclopent-2-enyl (1R)-cis, trans-chrysanthemate,    Empenthrin: (RS)-1-ethynyl-2-methyl-2-pentenyl (1R)-cis, trans-chrysanthemate,    Imiprothrin: 2,5-dioxo-3-(prop-2-ynyl)imidazolidin-1-ylmethyl (1R)-cis, trans-2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropanecarboxylate,    D-flamethrin: 5-(2-propynyl)-furfuryl (1R)-cis, trans-chrysanthemate, and 5-(2-propynyl)furfuryl 2,2,3,3-tetramethylcyclopropanecarboxylate;    Carbamate compounds such as    Alanycarb: S-methyl-N[[N-methyl-N-[N-benzyl-N(2-ethoxy-carbonylethyl)amino-thio]carbamoyl]thioacetimidate,    Bendiocarb: 2,2-dimethyl-1,3-benzodioxol-4-yl-methylcarbamate),    Carbaryl(1-naphthyl N-methylcarbamate,    Isoprocarb: 2-(1-methylethyl)phenyl methylcarbamate,    Carbosulfan: 2,3 dihydro-2,2-dimethyl-7-benzofuranyl[(dibutylamino)thio]methylcarbamate,    Fenoxycarb: Ethyl[2-(4-phenoxyphenoxy)ethyl]carbamate,    Indoxacarb: Methyl-7-chloro-22,3,4°,5tetrahydro-2[methoxycarbonyl (-4-trifluoromethoxyphenyl)]   Propoxur 2-isopropyloxyphenol methylcarbamate,    Pirimicarb: 2-dimethylamino-5,6-dimethyl-4-pyrimidinyl-dimethylcarbamate,    Thiodiocarb: Dimethyl N,N′(thiobis((methyl-imino)carbonoyloxy)bisethanimidiothioate),    Methomyl: S-methyl N-((methylcarbamoyl)oxy)thioacetamidate,    Ethiofencarb: 2-((ethylthio)methyl)phenyl methylcarbamate,    Fenothiocarb; S-(4-phenoxybutyl)-N,N-dimethyl thiocarbamate,    Cartap: S,S′-(2-5 dimethylamino)trimethylene)bis (thiocarbamate)hydrochloride,    Fenobucarb: 2-sec-butylphenylmethyl carbamate,    XMC: 3,5-dimethylphenyl-methyl carbamate,    Xylylcarb: 3,4-dimethylphenylmethylcarbamate,    organophosphorous compounds such as    Fenitrothion: O,O-dimethyl O-(4nitro-m-tolyl)phosphorothiote,    Diazinon: O,O-diethyl-O-(2-isopropyl-6-methyl-4-pyrimidinyl)phosphorothioate,    Pyridaphenthion: O-(1,6-dihydro-6-oxo-1-phenylpyrazidin-3-yl) O,O-diethyl phosphorothioate,    Pirimiphos-Etyl: O,O-diethyl O-(2-(diethylamino)6-methyl-pyrimidinyl)phosphorothioate, Pirimiphos-Methyl: O-[2-(diethylamino)-6-methyl-4-pyrimidinyl]O,O-dimethyl phosphorothioate,    Etrimphos: O-6-ethoxy-2-ethyl-pyrimidin-4-yl-O,O-dimethyl-phosphorothioate,    Fenthion: O,O-dimethyl-O-[3-methyl-4-methylthio)phenyl phosphorothioate,    Phoxim: 2-(diethoxyphosphinothoyloxyimino)-2-phenylacetonitrile,    Chlorpyrifos: O,O-diethyl-O-(3,5,6-trichloro-2-pyrinyl)phosphorothioate,    Chloropyriphosmethyl: O,O-dimethyl, O-(3,5,6-trichloro-2-pyridinyl)phosphorothioate,    Cyanophos: O,O-dimethyl O-(4 cyanophenyl)phosphorothioate,    Pyraclofos: (R,S)[4-chlorophenyl)-pyrazolyl-4-yl]-ethyl-S-n-propyl phosphorothioate,    Acephate: O,S-dimethyl acetylphosphoroamidothioate,    Azamethiphos: S-(6-chloro-2,3-dihydro-oxo-1,3-oxazolo[4,5-b]pyridine-3ylmethyl phosphorothioate,    Malathion: O,O-dimethyl phosphorodithioate ester of diethyl mercaptosuccinate,    Temephos: (O,O′(thiodi-4-1-phenylene) O,O,O,O-tetramethyl phosphorodithioate,    Dimethoate: ((O,O-dimethyl S-(n-methylcarbamoylethyl)phosphorodithioate,    Formothion: S[2-formylmethylamino]-2-oxoethyl]-O,O-dimethyl phosphorodithioate,    Phenthoate: O,O-dimethyl S-(alpha ethoxycarbonylbenzal)-phosphorodithioate;    Insecticides with a sterilising effect on adult mosquitoes such as    1-(alfa-(chloro-alpha-cyclopropylbenzylidenamino-oxy)-p-tolyl)-3-(2,6-difluorobenzoyl)urea,    Diflubenzuron: N-(((3,5-dichloro-4-(1,1,2,2-tetraflouroethoxy)phenylamino)carbonyl)2,6 difluoro benzamid,    Triflumuron: 2-Chloro-N-(((4-(triflouromethoxy)phenyl)-amino-)carbonyl)benzamide, or a triazin such as N-cyclopropy-1,3,5-triazine-2,4,6-triamin; and    α-cyano-3-phenophenoxybenzyl-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropane carboxylate, as a 1:1 mixture of (Z)-(1R,3R), R-ester and (Z)-(1S,3S), S-ester;    Lambda-cyhalothrine:    α-cyano-3-phenoxybenzyl-3-(2chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropane carboxylate, as a 1:1 mixture of (Z)-(1R,3R), R-ester and (Z)-(1S,3S), S-ester;    the repellent is selected from N,N-Diethyl-meta-toluamide (DEET), N,N-diethylphenylacetamide (DEPA), 1-(3-cyclohexan-1-yl-carbonyl)-2-methylpiperine, (2-hydroxymethylcyclohexyl) acetic acid lactone, 2-ethyl-1,3-hexandiol, indalone, Methylneodecanamide (MNDA), a pyrethroid not used for insect control such as {(+/−)-3-allyl-2-methyl-4-oxocyclopent-2-(+/−)enyl-(+/−)trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant extracts like limonene, eugenol, (+)-Eucamalol (1), (−)-1-epi-eucamalol or crude plant extracts from plants like  Eucalyptus maculata, Vitex rotundifolia, Cymbopogan martinii, Cymbopogan citratus  (lemon grass), Cymopogan nartdus  (citronella).    
     
     
         5 . The insecticide composition as claimed in any of  claims 1  to  4 , wherein the particle size of the insecticide and/or repellent is from 50 nm to 20 μm, preferably 50 nm to 8 μm, more preferably 50 nm to 4 μm, most preferably 50 nm to 500 nm.  
     
     
         6 . The insecticide composition as claimed in  claim 1 , further comprising one or more component selected from water, preservatives, detergents, stabilizers, agents having UV-protecting properties, optical brighteners, spreading agents, anti-migrating agents, foam-forming agents, wetting agents, anti-soiling agents, thickeners, further biozides, plasticizers, adhesive agents, pigments and dyestuffs.  
     
     
         7 . The insecticide composition as claimed in  claim 1  comprising from about 0.001 to 95% by weight of the insecticide and/or repellent.  
     
     
         8 . The insecticide-composition as claimed in  claim 1  which is provided as a kit for impregnation by the end-user.  
     
     
         9 . The insecticide composition as claimed in  claim 7  wherein the composition in the kit is adapted for preparing a solution or emulsion by adding water.  
     
     
         10 . An impregnated textile material or plastics material for insect killing and/or repellence of an insect comprising 
 a) at least one insecticide and/or at least one repellent, and    b1) at least one acrylic binder as claimed in  claim 1;     and/or    b2) at least one polyurethane as claimed in  claim 1 .    
     
     
         11 . The impregnated textile material or plastics material as claimed in  claim 9  comprising an insecticide and/or repellent as defined in  claim 4 .  
     
     
         12 . The impregnated textile material or plastics material as claimed in  claim 9  further comprising one or more components selected from preservatives, detergents, stabilizers, agents having UV-protecting properties, optical brighteners, spreading agents, anti-migrating agents, foam-forming agents, wetting agents, anti-soiling agents, thickeners, further biocides, plasticizers, adhesive agents, pigments and dyestuffs.  
     
     
         13 . The impregnated textile material or plastics material as claimed in  claim 9  comprising from about 0.001 to 10% by weight of the weight of thetextile material or plastics material of at least one insecticide and/or at least one repellent.  
     
     
         14 . A process for impregnation of a textile material or plastics material comprising the steps 
 i) forming an aqueous formulation comprising at least one insecticide and/or at least one repellent and at least one acrylic binder and/or at least one polyurethane as defined in the present invention and optionally further ingredients;    ii) applying the aqueous formulation to the textile material or plastics material by 
 iia) passing the textile material or plastics material through the aqueous formulation; p 2  or  
 iib) bringing the textile material or plastics material in contact with a roller that is partly or fully dipped into the aqueous formulation and drawing the aqueous formulation to the side of the textile material or plastics material in contact with the roller;  
 or  
 iic) double-side coating of the textile material or plastics material  
 or  
 iid) spraying the aqueous formulation onto the textile material or plastics material;  
 or  
 iie) applying the aqueous formulation in form of a foam;  
 or  
 iif) submerging the textile material or plastics material into the aqueous formulation;  
 or  
 iig) brushing the aqueous formulation onto or into the textile material or plastics material;  
 or  
 iih) pouring the aqueous formulation onto the textile material or plastics material;  
   iii) optionally removing surplus aqueous formulation; and    iv) drying and/or curing the textile material or plastics material.    
     
     
         15 . The process as claimed in  claim 13 , wherein step iia) is carried out by completely submerging the textile material or plastics material in the aqueous formulation either in a trough containing the aqueous formulation or passing the textile material or plastics material through the aqueous formulation which is held between two horizontally oriented rollers.  
     
     
         16 . The process as claimed in  claim 13 , wherein the insecticide and/or repellent is an insecticide and/or repellent as defined in  claim 4 .  
     
     
         17 . The process as claimed in  claim 13 , wherein the aqueous formulation further comprises one or more ingredients selected from the group consisting of detergents, stabilizers, agents having UV-protecting properties, optical brighteners, spreading agents, anti-migrating agents, preservatives, foam-forming agents, wetting agents, thickeners, further biozides, plasticizers, adhesive agents, anti-soiling agents, pigments and dyestuffs.  
     
     
         18 . The process as claimed in  claim 13  wherein the impregnating composition is provided as a kit for impregnation by the end-user.  
     
     
         19 . The process as claimed in  claim 13 , wherein the dying of the textile material or plastics material is carried out simultaneously with the impregnation of the textile material or plastics material, wherein an aqueous formulation is formed further comprising at least one dyestuff and/or at least one pigment.  
     
     
         20 . A process for coating a textile material or plastics material by applying a composition comprising at least one insecticide and/or at least one repellent and at least one acrylic binder as defined in  claim 1  and/or at least one polyurethane as defined in  claim 1  to the textile material or plastics material.  
     
     
         21 . The process as claimed in  claim 19 , wherein the composition further comprises one or more ingredients selected from the group consisting of detergents, stabilizers, agents having UV-protecting properties, optical brighteners, spreading agents, anti-migrating agents, preservatives, foam-forming agents, anti-soiling agents, wetting agents, thickeners, further biozides, plasticizers, adhesive agents, pigments and dyestuffs.  
     
     
         22 . An exhaust process for impregnation of a textile material or plastics material comprising the steps 
 i) placing the textile material or plastics material in an aqueous bath optionally comprising further additives contained in a pressure-proof vessel;    ii) adding an aqueous formulation comprising at least one insecticide and/or repellent;    iii) heating the aqueous bath to a temperature of 100 to 140° C. and keeping the temperature for 20 to 120 minutes;    and    iv) cooling and draining the bath, and rinsing and drying the impregnated textile material or plastics material.    
     
     
         23 . The process as claimed in  claim 21 , wherein the aqueous bath comprises as further additives one or more components selected from preservatives, detergents, fillers, impact modifiers, anti-fogging agents, blowing agents, clarifiers, nucleating agents, coupling agents, conductivity-enhancing agents (antistats), stabilizers such as anti-oxidants, carbon and oxygen radical scavengers and peroxide decomposing agents and the like, flame retardants, mould release agents, agents having UV protecting properties, optical brighteners, spreading agents, anti-blocking agents, anti-migrating agents, foam-forming agents, anti-soiling agents, thickeners, further biocides, wetting agents, plasticizers and film forming agents, adhesive or anti-adhesive agents, optical brightening (fluorescent whitening) agents, pigments and dyestuff.  
     
     
         24 . The process as claimed in  claim 21 , wherein the aqueous formulation comprising at least one insecticide and/or repellent comprises 0.1 to 45% by weight of water, based on the total of the components in the insecticide except of water.  
     
     
         25 . Impregnated textile material or plastics material obtainable by an exhaust process as claimed in  claim 21.