WO2008046746A2 - Matériaux synthétiques acaricides et articles fabriqués à partir de ces matériaux - Google Patents

Matériaux synthétiques acaricides et articles fabriqués à partir de ces matériaux Download PDF

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Publication number
WO2008046746A2
WO2008046746A2 PCT/EP2007/060576 EP2007060576W WO2008046746A2 WO 2008046746 A2 WO2008046746 A2 WO 2008046746A2 EP 2007060576 W EP2007060576 W EP 2007060576W WO 2008046746 A2 WO2008046746 A2 WO 2008046746A2
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WIPO (PCT)
Prior art keywords
agent
bis
silver
butyl
tert
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WO2008046746A3 (fr
Inventor
Armin Schneider
Heinz Herbst
Thi Thoa Rieffel
Markus Kolb
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BASF Schweiz AG
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Ciba Holding AG
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47C—CHAIRS; SOFAS; BEDS
    • A47C31/00—Details or accessories for chairs, beds, or the like, not provided for in other groups of this subclass, e.g. upholstery fasteners, mattress protectors, stretching devices for mattress nets
    • A47C31/007—Anti-mite, anti-allergen or anti-bacterial means
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47G—HOUSEHOLD OR TABLE EQUIPMENT
    • A47G9/00—Bed-covers; Counterpanes; Travelling rugs; Sleeping rugs; Sleeping bags; Pillows
    • A47G2009/001—Anti-allergen; Anti-mite

Definitions

  • the invention pertains to a method for reducing infestation of an article, such as a household article or garment or industrial article, by mites using a synthetic thermoplastic resin which contains a specific acaricidal first agent and optionally an antimicrobial second agent incorporated in the bulk resin; to a process for the production of such a resin, to the use of said resin for imparting acaricide properties to an article, and to acaricide articles containing said resin.
  • Dust mites are microscopic spiders, which may proliferate in fabrics and fillings (e.g pillows, bed clothes etc), carpets, and filters as long as sufficient heat, moisture and nutrient is available. More than 80% of mites present in house dust develop in the filling of bed linen. They produce strong allergenes: Dust mite allergy shows similar symptoms to hay fever, the allergenes are now recognized as one of the main triggers for asthma and eczema.
  • Known methods for reducing infestation with dust mites include treatment of the surface of articles such as fibers, fabrics, carpets etc. with certain insecticides and/or fungicides or inclusion of such components in cavities of a corresponding fiber. While these methods require repeated treatment of the surfaces or more complex processes for the shaping of the articles, incorporation of an acaricide agent into the bulk polymer material of the article within the shaping process, e.g. during solution spinning as proposed in WO 99/21421 , may lead to a long lasting effect.
  • a further result of an effective incorporation of a suitable agent into the bulk material can be the reduction of peak concentrations on the surface and thus the reduction of a potential toxicity or allergy risk by an antimicrobial agent.
  • acaricide agent e.g. good acaricide action, stability under processing conditions
  • an especially effective reduction of the mite population in contact with a synthethic thermoplastic polymer material may be achieved by incorporation of an agent selected from Propiconazole, Cyproconazole, Difenoconazole, Fludioxonil, Thiabendazole, Tebuconazole, Zinc Pyrithione, 2-n-Octyl-4-isothiazolin-3-on, 4,5-Di-chlor-N-n-octyl-isothiazolin-3-on, 2,4- bis(alkylamino)pyrimidines of the formulae
  • the acaricide effect becomes manifest in the efficient reduction or elemination of mite population on the surface of an article containing the present acaricide agent.
  • this surface may be an external surface, like the surface of a sheet or fiber, or an internal surface, like the surface of an open volume within a foam, or within a yarn, fabric or garment.
  • elemental silver or silver glass or silver zeolite e.g. in the form of microparticles or nanoparticles, which may (especially the microparticles) be used as such or as a dispersion in a suitable liquid such as silicone oils (e.g. polymethyldisiloxane) or white oil.
  • More preferred agents are Thiabendazol, Tebuconazol, Zinc Pyrithione, 2-n-Octyl-4- isothiazolin-3-on, 4,5-Di-chlor-N-n-octyl-isothiazolin-3-on, 2,4-bis(alkylamino)pyrimidines of formula lib, Nc, Nd, Propiconazole, Cyproconazole, Difenoconazole, Fludioxonil; especially Thiabendazol, Tebuconazol, Zinc Pyrithione, 2,4-bis(alkylamino)pyrimidines of formula lib, Nc, Nd), Propiconazole, Cyproconazole, Difenoconazole, Fludioxonil.
  • Also preferred agents are elemental silver or silver glass or silver zeolite.
  • benzimidazole is a compound of the formula:
  • a further (second) antimicrobial agent which is preferably selected from phenolic antimicrobial compounds of the formula (I)
  • n is 0 or preferably 1 ,
  • Ri and R 2 are hydrogen or chloro
  • R 3 is hydroxyl or preferably hydrogen
  • R 4 , R5 and R 6 are hydrogen or chloro
  • R 7 is hydroxyl, and - A -
  • X is a direct bond, -NHCONH-, -CH 2 - or preferably -0-; and/or silver or a silver complexes or salts.
  • Preferred examples for the antimicrobial component include
  • 2-phenylphenol 2.4.4'-trichloro-2'-hydroxy-diphenylether, 4,4'-dichloro-2-hydroxy- diphenylether, 2,2'-methylene-bis-(4-chloro-phenol), 4-(2-t-butyl-5-methylphenoxy)-phenol, 3- (4-chlorophenyl)-1-(3,4-dichloro-phenyl)-urea, 2,4,6-trichlorophenol, AgCI, AgNO 3 , Ag 2 SO 4 , silver-zeolites, silver-glass, silver-zirconates, silver dispersed in white oil.
  • Triclosan 2,4,4'- trichloro-2'-hydroxy-diphenylether
  • the silver containing zeolites may be those described in U.S. Patent Nos. 4,775,585, 4,911 ,898, 4,91 1 ,899 and 6,071 ,542, the disclosures of which are hereby incorporated by reference.
  • a zeolite is generally alumosilicate having a three dimensionally grown skeleton structure and is generally represented by xM 2/n O-AI 2 O 3 -ySiO 2 -zH 2 O, written with AI 2 O 3 as a basis, wherein M represents an ion-exchangeable metal ion, which is usually the ion of a monovalent or divalent metal; n corresponds to the valence of the metal; x is a coefficient of the metal oxide; y is a coefficient of silica; and z is the number of water of crystallization.
  • the zeolites of the present invention have a specific surface area of at least 150m 2 /g.
  • Single compounds or mixtures of each component may be used.
  • using a combination of a phenolic antibacterial and a silver component as recited above may provide further advantages.
  • one or more further components may be added selected from zinc oxide, copper and copper compounds.
  • Silver in general includes colloidal silver, silver nitrate, silver sulphate, silver chloride, silver complexes, metal-containing zeolites and surface-modified metal-containing zeolites.
  • the first and, if present, second agent are preferably contained in the ratio (weight/weight) from 0.5 / 20 to 20 / 0.5, especially in a ratio from 1 : 10 to 10 : 1.
  • first agent or first and second agent 0.02 % to 5 % by weight of the final material.
  • the final material i.e. the article containing the synthetic polymer resin, which is equipped with the present agent(s), or a material for the production of such an article, e.g. the yarn for the production of a carpet
  • the exact amount of agent contained in the resin is often determined by the percentage of resin used in the final article or on its surface; for a good anti-mite effect, the amount of agent in the polymer resin usually is higher, if the article contains only a minor amount of the acaricide resin, and smaller, if the final article contains high amounts of the acaricide resin or consists thereof.
  • the present agents as well as the polymer resins containing them combine good long-term activity and a good toxicological profile with good compatibility in the polymer substrate and further components thereof (such as pigments or other colorants) and good use properties of the polymer resin.
  • the acaricide agent(s) of the invention may be incorporated into a plastic resin prior to its being manufacturing process such as rotational molding, fiber spinning, etc.
  • the agent is able to withstand demanding processing conditions such as high temperature, e.g. temperatures greater than 200 0 C.
  • the invention also pertains to a process for the preparation of an acaricide material, characterized in that a first agent as defined above, and optionally a further antibacterial (second) agent, is incorporated therein, as well as to the use of an agent as defined above, and optionally a further antibacterial agent, in the bulk of a synthetic polymer for reducing the infestation by mite, e.g. after addition as a melt additive during the production of the acaricide material.
  • a synthetic polymer for characterized in that a first agent as defined above, and optionally a further antibacterial (second) agent, is incorporated therein, as well as to the use of an agent as defined above, and optionally a further antibacterial agent, in the bulk of a synthetic polymer for reducing the infestation by mite, e.g. after addition as a melt additive during the production of the acaricide material.
  • the polymers, especially synthetic thermoplastic polymers, which may be equipped with the present acaricide agent are:
  • Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, po- lybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene
  • HDPE high density polyethylene
  • HDPE-HMW high density and high molecular weight polyethylene
  • HDPE-UHMW high density and ultrahigh molecular weight polyethylene
  • MDPE medium density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE very low density polyethylene
  • Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
  • a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table.
  • These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
  • These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide.
  • These catalysts may be soluble or insoluble in the polymerisation medium.
  • the catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, Na and/or Ilia of the Periodic Table.
  • the activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard
  • Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g.
  • ethylene/norbornene like COC ethylene/1 -olefins copolymers, where the 1 -olefin is generated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vi- nylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1 ) above, for example polypropylene/ethy- lene-propylene copolymers, LD
  • Hydrocarbon resins for example C 5 -Cg
  • hydrogenated modifications thereof e.g. tackifiers
  • mixtures of polyalkylenes and starch
  • Homopolymers and copolymers from 1.) - 4.) may have any stereostructure including syndio- tactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Polystyrene poly(p-methylstyrene), poly( ⁇ -methylstyrene).
  • Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Ste- reoblock polymers are also included.
  • Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/bu- tadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhy- dride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/pro- pylene/diene terpoly
  • Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6. especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
  • PCHE polycyclohexylethylene
  • PVCH polyvinylcyclohexane
  • Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Graft copolymers of vinyl aromatic monomers such as styrene or ⁇ -methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acry- lonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpoly
  • Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo- chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride (PVC), polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
  • PVC polyvinyl chloride
  • PVF polyvinylidene chloride
  • polyvinyl fluoride polyvinylidene fluoride
  • copolymers thereof such as vinyl chloride/viny
  • Polymers derived from ⁇ , ⁇ -unsatu rated acids and derivatives thereof such as polyacry- lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni- triles, impact-modified with butyl acrylate.
  • Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.
  • Polymers derived from unsaturated alcohols and amines or the acyl derivatives or ace- tals thereof for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1 ) above.
  • Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • Polyureas Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
  • Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate (PET), polybutylene terephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, polylactic acid (PLA), as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
  • PET polyethylene terephthalate
  • PAN polybutylene terephthalate
  • PAN poly-1 ,4-dimethylolcyclohexane terephthalate
  • PAN polyalkylene naphthalate
  • PDA polyhydroxybenzoates
  • block copolyether esters derived from hydroxyl-terminated polyethers and also polyesters modified with polycarbonates or MBS.
  • Natural polymer naterials such as leather, cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
  • Blends of the aforementioned polymers for example PP/EPDM, PoIy- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
  • polyblends for example PP/EPDM, PoIy- amide/EPDM or ABS
  • PVC/EVA PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/
  • Preferred substrates are polyethylene (PE) such as LDPE or HDPE; polypropylene (PP; homo or copolymer); ethylene vinylacetate (EVA); polyesters such as polyethylene terephthalate (PET), PET-G, polylactic acid (PLA), polytrimethylene terephthalate (PTT); polyol; polyoxymethylene (POM); thermoplastic polyolefin (TPO); polyurethane (PUR); thermoplastic polyurethane (TPU); polyvinyl chloride (PVC); polyamide (PA) such as PA 6 or PA 6.6; or corresponding blends. Most preferred are PP, PE, PET, PA, PUR, PLA, PTT.
  • Substrates often are in the form of fibers, fabrics, nonwovens, foams.
  • the materials, especially the polymer substrates, may also have incorporated therein one or more of the following known additives:
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu- tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethyl- phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth- oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 '-methylundec
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl- thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4- nonylphenol.
  • Hydroquinones and alkylated hydroquinones for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-bu- tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hy- droxyphenyl) adipate.
  • 2,6-di-tert-butyl-4-methoxy- phenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amyl
  • Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
  • Hvdroxylated thiodiphenyl ethers for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)- disulfide.
  • 2,2'-thiobis(6-tert-butyl-4-methylphenol 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis
  • Alkylidenebisphenols for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)- phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4- methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-bu- tylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-( ⁇ -methyl- benzyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ -dimethyl
  • Hydroxybenzylated malonates for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di- dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1 ,1 ,3,3-te- tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
  • Aromatic hydroxybenzyl compounds for example 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame- thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
  • Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy- anilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1 ,3,5-tri- azine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxyben- zyl)isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl
  • Benzylphosphonat.es for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl- ⁇ -tert-butyl ⁇ -hydroxy-S-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
  • Acylaminophenols for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
  • esters of ⁇ -(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9- nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy- lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hy- droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol- propane, 4-hydroxy
  • esters of ⁇ -(5-tert-butyl-4-hvdroxy-3-methylphenyl)propionic acid with mono- or poly- hydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanedi- ol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis- (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyl- olpropane, 4-hydroxymethyl-1
  • esters of ⁇ -(3,5-dicvclohexyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1 -phospha ⁇ j-trioxabi
  • esters of 3,5-di-tert-butyl-4-hvdroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[
  • Aminic antioxidants for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec- butyl-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1- ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naph- thyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl)- N'
  • 2-(2'-Hvdroxyphenyl)benzotriazoles for example 2-(2'-hydroxy-5'-methylphenyl)benzo- triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe- nyl)benzotriazole, 2-(2'-hydroxy-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di- tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphe- nyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-sec-
  • 2-Hvdroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl- oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
  • Esters of substituted and unsubstituted benzoic acids for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben- zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo- ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxyben- zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Acrylates for example ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, isooctyl ⁇ -cyano- ⁇ , ⁇ -diphe- nylacrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinna- mate, butyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, methyl ⁇ -carbomethoxy-p-methoxycin- namate and N-( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methylindoline.
  • Nickel compounds for example nickel complexes of 2,2'-thiobis[4-(1 ,1 ,3,3-tetramethyl- butyl)phenol], such as the 1 :1 or 1 :2 complex, with or without additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert- butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphe- nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or with- out additional ligands.
  • additional ligands such as n- butylamine, triethanolamine or N-cyclohexyld
  • Sterically hindered amines for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1 -octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1 ,2,2,6,6-pentamethyl-4-piperi- dyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)- 2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-
  • N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide N-(1 ,2,2,6,6- pentamethyl ⁇ -piperidyO-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1 -oxa-3,8-di- aza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa- 3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 1 ,1-bis(1 , 2,2,6, 6-pentamethyl-4- piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'-bis-formyl-N,N'-bis(2,2,6,
  • the sterically hindered amine may also be one of the compounds described in GB-A-2 301 106 as component l-a), l-b), l-c), l-d), l-e), l-f), l-g), l-h), l-i), l-j), l-k) or l-l), in particular the light stabilizer 1-a-1 , 1-a-2, 1-b-1 , 1-C-1 , 1-C-2, 1-d-1 , 1-d-2, 1-d-3, 1-e-1 , 1 -f - 1 , 1-g-1 , 1-g-2 or 1-k-1 listed on pages 68 to 73 of said GB-A-2 301 106.
  • the sterically hindered amine may also be one of the compounds described in
  • EP-A-O 782 994 for example compounds as described in claims 10 or 38 or in Examples 1- 12 or D- 1 to D-5 therein.
  • Sterically hindered amines substituted on the N-atom by a hydroxy-substituted alkoxy group for example compounds such as 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-
  • 2,2,6,6-tetramethylpiperidine 1-(2-hydroxy-2-methylpropoxy)-4-hexadecanoyloxy-2,2,6,6- tetramethylpiperidine, the reaction product of 1-oxyl-4-hydroxy-2,2,6,6-tetramethylpiperidine with a carbon radical from t-amylalcohol, 1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2, 2,6,6- tetramethylpiperidine, 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1-(2- hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis(1 -(2-hydroxy-2- methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis(
  • Oxamides for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • Metal deactivators for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1 ,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl- oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
  • Phosphites and phosphonites for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di- cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphos
  • Tris(2,4-di-tert-butylphenyl) phosphite (lrgafos ® 168, Ciba Specialty Chemicals Inc.), tris(no- nylphenyl) phosphite,
  • Hydroxylamines for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N, N- dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-di- hexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxyl- amine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
  • Hydroxylamines for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N, N- dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,
  • Nitrones for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl- alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N- hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-al- pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta- decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N
  • Amine oxides for example amine oxide derivatives as disclosed in U.S. Patent Nos. 5,844,029 and 5,880,191 , didecyl methyl amine oxide, tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amine oxide.
  • Thiosynergists for example dilauryl thiodipropionate or distearyl thiodipropionate.
  • Peroxide scavengers for example esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mer- captobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetra- kis( ⁇ -dodecylmercapto)propionate.
  • 1 Polyamide stabilizers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
  • Basic co-stabilisers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
  • Basic co-stabilisers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ric
  • Nucleating agents for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers).
  • inorganic substances such as talcum
  • metal oxides such as titanium dioxide or magnesium oxide
  • phosphates carbonates or sulfates of, preferably, alkaline earth metals
  • organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
  • polymeric compounds such as ionic copolymers (
  • Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
  • additives for example plasticisers, lubricants, emulsifiers, pigments, dyes, rheolo- gy additives, catalysts, flow-control agents, optical brighteners, slip agents, crosslinking agents, crosslinking boosters, halogen scavengers, smoke inhibitors, flameproofing agents, antistatic agents, clarifiers such as substituted and unsubstituted bisbenzylidene sorbitols, benzoxazinone UV absorbers such as 2,2'-p-phenylene-bis(3,1-benzoxazin-4-one), Cya- sorb ® 3638 (CAS# 18600-59-4), and blowing agents.
  • plasticisers for example plasticisers, lubricants, emulsifiers, pigments, dyes, rheolo- gy additives, catalysts, flow-control agents, optical brighteners, slip agents, crosslinking agents, crosslinking boosters, halogen scavengers, smoke
  • biocides for example fungicides such as 3,5-dimethyl-tetrahydro-1 ,3,5-2H-thio- diazin-2-thione, Bis-tributyltinoxide, 4.5-dichlor-2-n-octyl-4-isothiazolin-3-one, N-butyl-benz- isothiazoline, 10.10'-oxybisphenoxyarsine, zinc-2-pyridinthiol-1 -oxide, etc., and algicides such as 2-methylthio-4-cyclopropylamino-6-( ⁇ , ⁇ -dimethylpropylamino)-s-triazine, 2-methyl- thio-4-cyclopropylamino-6-tert-butylamino-s-triazine, 2-methylthio-4-ethylamino-6-( ⁇ , ⁇ -di- methylpropylamino)-s-triazine, etc.
  • fungicides such as 3,5-dimethyl-t
  • additives are often contained in amounts ranging from 0.01 to 10 % by weight of the material; usual amounts for these additional additives are ranging from about 0.05 to 5 % by weight. Fillers may be contained in higher amounts, e.g. 1-50% b.w.
  • Preferred additional additives are selected from the group consisting of antioxidants, ultraviolet light absorbers, hindered amines, phosphites or phosphonites, hydroxylamines, ni- trones, benzofuran-2-ones, thiosynergists, polyamide stabilizers, metal stearates, nucleating agents, fillers, reinforcing agents, lubricants, emulsifiers, dyes, pigments, optical brighteners, flame retardants, antistatic agents and blowing agents.
  • acaricide agent(s) of the invention and optional further additives may be added to the plastic resin, e.g. the polyolefin, individually or mixed with one another. If desired, the individual components of an additive mixture can be mixed with one another in the melt (melt blending) before incorporation into the plastic material.
  • the acaricide agent(s) of the invention and optional further additives into the plastic material may be carried out by known methods such as dry mixing in the form of a powder, or wet mixing in the form of solutions or suspensions.
  • the agent(s) and optional further additives may be incorporated, for example, before or after molding or also by applying the dissolved or dispersed additive to the plastic material, with or without subsequent evaporation of the solvent.
  • the acaricide agent(s) of the invention and optional further additives can also be added to the plastic material in the form of a masterbatch which contains these components in a concentration of about 1 to 80%, for example 2.5 % to 70 %, especially 5 % to 50 % by weight of the loaded carrier; in such operations, the polymer can be used in the form of powder, granules, solutions, suspensions or in the form of latices.
  • the invention thus embraces a process for the production of an acaricide material, e.g.
  • thermoplastic polymer carrier in an amount ranging from 1 to 80% by weight of the carrier, and the loaded carrier is subsequently incorporated into the material, where both steps are carried out with application of heat.
  • the present acaricide agent preferably is added via carriers such as LDPE, HDPE, MDPE, PP, EVA, ABS, SAN, PS, acrylates, PMMA, polyamide, polyesters, PVC, latex, styrene, polyol, PUR, TPU, unsaturated esters, urea, paraformaldehyde, water emulsion, etc.; especially preferred are LDPE, HDPE, PP, PA 6, PA 6.6, PET, PET-G (i.e. glycol-modified PET), PUR.
  • carriers such as LDPE, HDPE, MDPE, PP, EVA, ABS, SAN, PS, acrylates, PMMA, polyamide, polyesters, PVC, latex, styrene, polyol, PUR, TPU, unsaturated esters, urea, paraformaldehyde, water emulsion, etc.; especially preferred are LDPE, HDPE, PP, PA 6, PA 6.6, PET, PET-
  • present acaricide agent and optional further additives can also be added before, during or after polymerization or crosslinking.
  • the present acaricide agent and optional further additives can be incorporated into the plastic material in pure form or encapsulated in waxes, oils or polymers.
  • the present acaricide agent and optional further additives can also be sprayed onto the material. They are able to dilute other additives (for example the conventional additives in- icated above) or monomers or their melts so that they can be sprayed also together with these additives onto the material. Addition by spraying during the deactivation of the polymerization catalysts is particularly advantageous, it being possible to carry out spraying using, for example, the steam used for deactivation. In the case of spherically polymerized polyolefins it may, for example, be advantageous to apply the additives of the invention, optionally together with other additives, by spraying.
  • the additives of the invention and optional further components may be added to the polymer material individually or mixed with one another. If desired, the individual components can be mixed with one another before incorporation into the polymer for example by dry blending, compaction or in the melt.
  • the incorporation of the additives of the invention and optional further components into the polymer is carried out by known methods such as dry blending in the form of a powder, or wet mixing in the form of solutions, dispersions or suspensions for example in an inert solvent, water or oil.
  • the additives of the invention and optional further additives may be incorporated, for example, before or after molding or also by applying the dissolved or dispersed additve or additive mixture to the polymer material, with or without subsequent evaporation of the solvent or the suspension/dispersion agent. They may be added directly into the processing apparatus (e.g. extruders, internal mixers, etc), e.g. as a dry mixture or powder or as solution or dispersion or suspension or melt.
  • the incorporation can be carried out in any heatable container equipped with a stirrer, e.g. in a closed apparatus such as a kneader, mixer or stirred vessel.
  • a stirrer e.g. in a closed apparatus such as a kneader, mixer or stirred vessel.
  • the incorporation is preferably carried out in an extruder or in a kneader. It is immaterial whether processing takes place in an inert atmosphere or in the presence of oxygen.
  • the addition of the additive or additive blend to the polymer can be carried out in all customary mixing machines in which the polymer is melted and mixed with the additives. Suitable machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders.
  • Incorporation is preferably carried out in an extruder by introducing the additive during processing.
  • processing machines are single-screw extruders, contrarotating and corotating twin-screw extruders, planetary-gear extruders, ring extruders or cokneaders. It is also possible to use processing machines provided with at least one gas removal compartment to which a vacuum can be applied.
  • the screw length is 1 - 60 screw diameters, preferably 35-48 screw diameters.
  • the rotational speed of the screw is preferably 10 - 600 rotations per minute (rpm), very particularly preferably 25 - 300 rpm.
  • the maximum throughput is dependent on the screw diameter, the rotational speed and the driving force.
  • the process of the present invention can also be carried out at a level lower than maximum throughput by varying the parameters mentioned or employing weighing machines delivering dosage amounts.
  • the polymer resins containing the additive(s)/agent(s) of the invention described herein can be used for the production inter alia of moldings, rotomolded articles, injection molded articles, blow molded articles, films, tapes, mono-filaments, fibers, nonwovens, foams, profiles, adhesives or putties, surface coatings and the like.
  • the articles containing the present anti-mite agent thus include synthetic fibers and fabrics including woven, nonwoven and knitted, as well as mattresses and foams.
  • the effect of the invention is of particular interest in applications like filters, bed clothes including sheets, blankets mattress covers or pillowcases, upholstery fabrics or foams, textiles, and floor coverings including carpets, backing material like backing for flooring, underlay for carpets, textile back coating.
  • the agent or agent combination according to the invention is incorporated into the polymer resin, which thereby becomes a reservoir for the controlled release of the agent over a long period of time. Mite populations are thus effectively reduced or removed on the surface of an article, in the bulk of an article containing hollow spaces, as well as in a fabric or pile, e.g. of a bedding, upholstery, mattress, garment, or carpet.
  • Most preferred articles containing or consisting of the present anti-mite resin are fibers, foams or articles containing these fibers and/or foams including fabrics and nonwovens.
  • the agent is mixed with polypropylene pellets (Moplen HP 451 N, Albis Impex AG) at room temperature and extruded via a twin-screw extruder at 230 0 C.
  • the molten polymer and agent exit via a round die and is immediately cooled and solidified in a cold- water through.
  • the solidified strand is fed into a pelletizer.
  • Fiber spinning process Continuous polypropylene multifilament fibers are prepared using a fiber spinning line under the following conditions: Extruder temperature of 24O 0 C, 40 filaments. Spinning pump speed is adjusted to produce fibers with a specific weight of 4.5 dpf. The fibers are then knitted to socks. 2) Example with PET substrate:
  • the agent(s) and the polyester pellets are dried at 120 0 C until a remaining humidity less than 50-100 ppm is reached.
  • the agent is mixed with pellets at room temperature and extruded via a twin-screw extruder at 270 0 C.
  • the molten polymer with agent exit via a round die and is immediately cooled and solidified in a cold-water through.
  • the solidified strand is fed into a pelletizer.
  • Continuous polyester multifilament fibers are prepared using a fiber spinning line under the following conditions: Extruder temperature of 285 0 C, 40 filaments. Spinning pump speed is adjusted to produce fibers with a specific weight of 4.5 dpf. The fibers are then knitted to socks.
  • the agent(s) and the polyamide pellets are dried at 80°C until 500 ppm of rest of humidity is reached.
  • the agent is mixed with pellets at room temperature and extruded via a twin-screw extruder at 260°C.
  • the molten polymer with agent exit via a round die and is immediately cooled and solidified in a cold-water through.
  • the solidified strand is fed into a pelletizer.
  • Continuous polyamide multifilament fibers are prepared using a fiber spinning line under the following conditions: Extruder temperature of 265 0 C, 40 filaments. Spinning pump speed is adjusted to produce fibers with a specific weight of 4.5 dpf. The fibers are then knitted to socks. B) Testing
  • the knitted samples are evaluated on their anti-mite behavior.
  • Experimental set-up 10x10 cm samples are tested in triplicate for each formulation.
  • the samples are soiled with natural dust and acclimated to a specific humidity prior to inoculation with mites.
  • skin scales and powdered yeast are added to the dust in the ratio of 3:1 :12 (w/w). Soiled units are placed on the bottom of a glass Petri dish (diameter 15 cm).
  • the different samples are then placed for one week into an incubator at specific mite optimal growth conditions (i.e. for the Dermatophagoides pteronyssinus species a temperature of 25°C and 75% relative humidity).
  • specific mite optimal growth conditions i.e. for the Dermatophagoides pteronyssinus species a temperature of 25°C and 75% relative humidity.
  • each sample is inoculated with 50 mites (25 male and 25 female young adults) picked from a flourishing culture.
  • results achieved with the polypropylene substrate (1 ) are summarized in Table 1 ; results achieved with the polyethyleneterephthalate substrate (2) are summarized in Table 2; results achieved with the polyamide substrate (3) are summarized in Table 3.
  • Table 1 Efficacy of anti-mite treatments applied on textile samples based on PP substrate.
  • Table 2 Efficacy of anti-mite treatments applied on textile samples based on PET substrate.
  • Table 3 Efficacy of anti-mite treatments applied on textile samples based on PA6 substrate.

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  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Toxicology (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des articles en polymère thermoplastique synthétique, lesdits articles étant protégés efficacement contre l'infestation par les acariens tels que les acariens de la poussière de maison ou les acariens de lit, par incorporation d'un agent choisi parmi Propiconazole, Cyproconazole, Difénoconazole, Fludioxonil, Thiabendazole, Tébuconazole, Zinc Pyrithione, 2-n-Octyl-4-isothiazolin-3-one, 4,5-Di-chlor-N-n-octyl-isothiazolin-3-one, certaines 2,4-bis(alkylamino)pyrimidines ou argents selon la revendication 1, Carbendazim, 10,10'-oxy-bis-phénoxyarsène et/ou n-butyl-1,2-benzisothiazolin-3-one et éventuellement un agent antimicrobien dans la masse de la résine. Les articles finaux peuvent être des filtres, des rembourrages et du linge de lit, des matelas, des couvertures, des taies d'oreiller, des mousses et des tissus d'ameublement, des textiles, des revêtements de sol, notamment des tapis, des matériaux de renfort pour sols, sous-couches.
PCT/EP2007/060576 2006-10-16 2007-10-05 Matériaux synthétiques acaricides et articles fabriqués à partir de ces matériaux Ceased WO2008046746A2 (fr)

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WO2010071671A1 (fr) 2008-12-19 2010-06-24 Eastman Kodak Company Compositions antimicrobiennes polyoléfiniques et procédés de traitement par fusion
US20100173121A1 (en) * 2009-01-07 2010-07-08 Beaulieu Group, Llc Method and Treatment Composition for Imparting Durable Antimicrobial Properties to Carpet
WO2012076529A1 (fr) * 2010-12-07 2012-06-14 Sanitized Ag Procédé de traitement antimicrobien de tissus avec des compositions d'adhésif fusible, compositions d'adhésif fusible et leur utilisation
WO2012152871A1 (fr) 2011-05-10 2012-11-15 Dsm Ip Assets B.V. Fil, procédé de fabrication du fil, et produits contenant le fil
EP2749167A1 (fr) 2012-12-28 2014-07-02 Sanitized AG Formulation destinée à l'équipement antimicrobien de compositions à base de chlorure de polyvinyle
WO2014102228A1 (fr) 2012-12-28 2014-07-03 Sanitized Ag Formulation d'apprêt antimicrobien de compositions polymériques
WO2017137157A1 (fr) * 2016-02-12 2017-08-17 Thor Gmbh Composition contenant 2-n-octylisothiazolin-3-one et 4,5-dichlor-2-n-octylisothiazolin-3-one pour produire des composites bois-plastique
US20190133089A1 (en) * 2016-03-30 2019-05-09 Osaka Gas Chemicals Co., Ltd. Beekeeping member and method for producing same
US11332646B2 (en) * 2016-12-19 2022-05-17 Henkel Ag & Co. Kgaa Hot melt adhesive comprising isothiazolinone fungicides
CN115197543A (zh) * 2021-04-14 2022-10-18 上海沪正实业有限公司 防螨远红外发射功能填充母粒及其用途
CN115957569A (zh) * 2022-12-09 2023-04-14 广州领音航复合材料有限公司 Cn95空调滤清器

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US8338514B2 (en) 2008-12-19 2012-12-25 Eastman Kodak Company Polyolefin antimicrobial compositions and melt-processing methods
WO2010071671A1 (fr) 2008-12-19 2010-06-24 Eastman Kodak Company Compositions antimicrobiennes polyoléfiniques et procédés de traitement par fusion
US9493908B2 (en) 2009-01-07 2016-11-15 Beaulieu Group, Llc Method and treatment composition for imparting durable antimicrobial properties to carpet
US20100173121A1 (en) * 2009-01-07 2010-07-08 Beaulieu Group, Llc Method and Treatment Composition for Imparting Durable Antimicrobial Properties to Carpet
US8586145B2 (en) * 2009-01-07 2013-11-19 Beaulieu Group, Llc Method and treatment composition for imparting durable antimicrobial properties to carpet
WO2012076529A1 (fr) * 2010-12-07 2012-06-14 Sanitized Ag Procédé de traitement antimicrobien de tissus avec des compositions d'adhésif fusible, compositions d'adhésif fusible et leur utilisation
WO2012152871A1 (fr) 2011-05-10 2012-11-15 Dsm Ip Assets B.V. Fil, procédé de fabrication du fil, et produits contenant le fil
EP2749167A1 (fr) 2012-12-28 2014-07-02 Sanitized AG Formulation destinée à l'équipement antimicrobien de compositions à base de chlorure de polyvinyle
WO2014102228A1 (fr) 2012-12-28 2014-07-03 Sanitized Ag Formulation d'apprêt antimicrobien de compositions polymériques
WO2017137157A1 (fr) * 2016-02-12 2017-08-17 Thor Gmbh Composition contenant 2-n-octylisothiazolin-3-one et 4,5-dichlor-2-n-octylisothiazolin-3-one pour produire des composites bois-plastique
US20190133089A1 (en) * 2016-03-30 2019-05-09 Osaka Gas Chemicals Co., Ltd. Beekeeping member and method for producing same
US11332646B2 (en) * 2016-12-19 2022-05-17 Henkel Ag & Co. Kgaa Hot melt adhesive comprising isothiazolinone fungicides
CN115197543A (zh) * 2021-04-14 2022-10-18 上海沪正实业有限公司 防螨远红外发射功能填充母粒及其用途
CN115957569A (zh) * 2022-12-09 2023-04-14 广州领音航复合材料有限公司 Cn95空调滤清器
CN115957569B (zh) * 2022-12-09 2023-08-18 广州领音航复合材料有限公司 Cn95空调滤清器

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