WO2016147911A1 - 防虫フィルム及び防虫カバー - Google Patents
防虫フィルム及び防虫カバー Download PDFInfo
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- WO2016147911A1 WO2016147911A1 PCT/JP2016/056811 JP2016056811W WO2016147911A1 WO 2016147911 A1 WO2016147911 A1 WO 2016147911A1 JP 2016056811 W JP2016056811 W JP 2016056811W WO 2016147911 A1 WO2016147911 A1 WO 2016147911A1
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- Prior art keywords
- group
- insect
- carbon atoms
- general formula
- film
- Prior art date
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- MQTHNQJMRRPIRP-UHFFFAOYSA-N CC(C)(C)CC(C)(C)C(CC(Cc1c(C=N)c(-[n]2nc(cccc3)c3n2)cc(C(C)(C)CC(C)(C)C)c1)=C1O)C=C1[n]1nc(cccc2)c2n1 Chemical compound CC(C)(C)CC(C)(C)C(CC(Cc1c(C=N)c(-[n]2nc(cccc3)c3n2)cc(C(C)(C)CC(C)(C)C)c1)=C1O)C=C1[n]1nc(cccc2)c2n1 MQTHNQJMRRPIRP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
- A01M29/00—Scaring or repelling devices, e.g. bird-scaring apparatus
- A01M29/06—Scaring or repelling devices, e.g. bird-scaring apparatus using visual means, e.g. scarecrows, moving elements, specific shapes, patterns or the like
- A01M29/08—Scaring or repelling devices, e.g. bird-scaring apparatus using visual means, e.g. scarecrows, moving elements, specific shapes, patterns or the like using reflection, colours or films with specific transparency or reflectivity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02B—PREPARING GRAIN FOR MILLING; REFINING GRANULAR FRUIT TO COMMERCIAL PRODUCTS BY WORKING THE SURFACE
- B02B1/00—Preparing grain for milling or like processes
- B02B1/04—Wet treatment, e.g. washing, wetting, softening
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
Definitions
- the present invention relates to an insect-repellent film and an insect-repellent cover used for light emitters, windowpanes, agricultural uses, etc., in order to keep flying insects away.
- Flying insects having phototactic properties are not only unsightly and unpleasant, but are also problematic in various fields. For example, accidents in which flying insects such as flies and mosquitoes are mixed into food factory products are a major problem in quality control from the viewpoint of hygiene. Also, in factories located in the suburbs, agricultural pests such as leafhoppers and leafhoppers from the surrounding fields and the like may be attracted by the lights and come to the factory and be mixed into the product. In suburban restaurants and convenience stores that are open all night, flying insects can fly and give customers an unpleasant impression. Furthermore, even in medical facilities such as hospitals and general houses, flying insects are not desirable from the viewpoints of hygiene and appearance, and have been a problem. Also in the cultivation of agricultural products, countermeasures against pests such as flying insects are an important issue.
- flying insects have positive phototactic properties that are highly sensitive to ultraviolet rays, and are particularly attracted to ultraviolet rays in the long wavelength region of 340 nm to 400 nm. Therefore, there has been a problem of being attracted to light emitters such as fluorescent lamps, mercury lamps, and LED lighting that emit ultraviolet rays in the long wavelength region.
- insect-proof films and insect-protecting covers that shield ultraviolet rays by containing an ultraviolet absorber have been proposed.
- These insect repellent films and insect repellent covers can be attached to light emitters such as fluorescent lamps, mercury lamps, and LED lighting, covered with light emitters, further attached to window glass, and used as agricultural films. Used to shield the ultraviolet rays that attract flying insects.
- Patent Documents 1 and 2 However, these conventional insect-proof films and insect-proof covers are not sufficient in the ability to block ultraviolet rays in the long wavelength region of 340 nm to 400 nm, and are not sufficiently effective in preventing the attracting of flying insects.
- an object of the present invention is to provide an insect repellent film and an insect repellent cover that can prevent the flying insects from being attracted to the light-emitting body, the room, and the crops, and flying.
- the present inventors have found that a triazine-based ultraviolet absorber having a specific structure is used, and have completed the present invention. That is, the present invention provides an insect repellent film or insect repellent cover containing one or more triazine compounds represented by the following general formula (1) as an ultraviolet absorber.
- R 1 to R 3 may be the same as or different from each other, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, Represents an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, or an arylalkyl group having 7 to 18 carbon atoms, provided that these alkyl groups , A cycloalkyl group, an alkenyl group, an aryl group, an alkylaryl group or an arylalkyl group may be substituted with a hydroxy group, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group, an oxygen atom, sulfur atom, a carbonyl group, an ester group, may be interrupted by an amide group or an imino group. the above-mentioned replacement
- this invention provides the said insect-control film or insect-control cover whose triazine type compound represented by the said General formula (1) is a triazine type compound represented by the following general formula (2).
- R 7 to R 9 may be the same as or different from each other, and represent a linear or branched alkyl group having 1 to 12 carbon atoms, provided that these alkyl groups are hydroxy groups. May be substituted with a halogen atom or an alkoxy group having 1 to 12 carbon atoms, and may be interrupted with an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group.
- the present invention provides the insect repellent film or insect repellent cover, wherein the transmittance of visible light having a wavelength of 500 nm is 80% or more and 100% or less, and the transmittance of ultraviolet light having a wavelength of 400 nm is 0% or more and 5.0% or less. It is to provide.
- ultraviolet rays sensitive to flying insects when used for illuminating body, window glass, and crop cultivation, ultraviolet rays sensitive to flying insects, particularly ultraviolet rays in the long wavelength region of 340 nm to 400 nm, are effectively shielded to attract flying insects. It is possible to provide an insect-proof film that can prevent flying. In addition, by covering the illuminant, it is possible to efficiently shield ultraviolet rays sensitive to flying insects, particularly ultraviolet rays in the long wavelength region of 340 nm to 400 nm, and to prevent insects from attracting and flying. be able to. Furthermore, it is possible to provide an insect repellent film and an insect repellent cover which can prevent the flying insects from attracting and flying and have excellent visible light permeability.
- the present invention relates to an insect-proof film or insect-proof cover.
- the insect repellent film has a function of preventing the flying insects from attracting and flying and has a thickness of less than 200 ⁇ m, and the insect repellent cover prevents the flying insects from attracting and flying.
- the insect repellent film and insect repellent cover of the present invention contain one or more triazine compounds represented by the following general formula (1) as an ultraviolet absorber.
- R 1 to R 3 may be the same as or different from each other, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, Represents an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms, or an arylalkyl group having 7 to 18 carbon atoms, provided that these alkyl groups , A cycloalkyl group, an alkenyl group, an aryl group, an alkylaryl group or an arylalkyl group may be substituted with a hydroxy group, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group, an oxygen atom, sulfur atom, a carbonyl group, an ester group, may be interrupted by an amide group or an imino group. the above-mentioned replacement
- Examples of the linear or branched alkyl group having 1 to 12 carbon atoms represented by R 1 to R 3 in the general formula (1) include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl.
- Linear or branched alkyl groups such as tertiary butyl, amyl, tertiary amyl, hexyl, octyl, secondary octyl, tertiary octyl, 2-ethylhexyl, decyl, undecyl, dodecyl, etc.
- Examples of the cycloalkyl group having 3 to 8 carbon atoms include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl group, etc.
- Examples of the alkenyl group having 2 to 8 carbon atoms include linear and branched propenyl, butenyl, pentenyl, hexenyl, heptenyl, and octenyl groups regardless of the position of the unsaturated bond
- Examples of the aryl group having 6 to 18 carbon atoms include phenyl, naphthyl, and biphenyl groups.
- alkylaryl group having 7 to 18 carbon atoms examples include methylphenyl, dimethylphenyl, ethylphenyl, octylphenyl groups, and the like.
- arylalkyl group having 7 to 18 carbon atoms examples include benzyl, 2-phenylethyl, 1-methyl-1-phenylethyl group and the like.
- the alkyl group, cycloalkyl group, alkenyl group, aryl group, alkylaryl group or arylalkyl group may be substituted with a hydroxy group, a halogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group, It may be interrupted by an oxygen atom, sulfur atom, carbonyl group, ester group, amide group or imide group. Also, the above substitutions and interruptions may be combined.
- alkyl group, cycloalkyl group, alkenyl group, aryl group, alkylaryl group or arylalkyl group may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group.
- cycloalkyl group, alkenyl group, aryl group, alkylaryl group or arylalkyl group is —CH 2 —, —CH ⁇ is an oxygen atom, sulfur atom, carbonyl group, ester group, amide group
- an imide group may be substituted.
- substitutions and interruptions may be combined, but two or more interruptions by the same group are consecutive, for example, the interruption by an oxygen atom is continuous, so that —O—O— is included in the group. None become.
- Examples of the alkyl group having 1 to 12 carbon atoms include the same groups as the linear or branched alkyl groups represented by R 1 to R 3 in the general formula (1).
- Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexaoxy, octoxy, nonyloxy, decyloxy, undecyloxy, and dodecyloxy groups.
- the ester group is a group formed by dehydration condensation of a carboxylic acid and an alcohol
- the amide group is a group formed by dehydration condensation of a carboxylic acid and an amine.
- substituent or interrupted alkyl group or cycloalkyl group include 2-hydroxypropyl, 2-methoxyethyl, 3-sulfonyl-2-hydroxypropyl, 4-methylcyclohexyl group, and the like.
- Examples of the aryl group having a substituent or interruption include 4-methylphenyl, 3-chlorophenyl, 4-benzyloxyphenyl, 4-cyanophenyl, 4-phenoxyphenyl, 4-glycidyloxyphenyl, 4-isocyanurate A phenyl group etc. are mentioned.
- a linear or branched alkyl group having 1 to 12 carbon atoms, particularly a hexyl group, is preferable because it is excellent in absorption of ultraviolet rays in a long wavelength region.
- Examples of the alkyl group having 1 to 8 carbon atoms represented by R 4 to R 6 include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, tert-amyl, and hexyl. , Octyl, tertiary octyl group and the like, Examples of the alkenyl group having 2 to 8 carbon atoms include alkenyl groups having 2 to 8 carbon atoms represented by R 1 to R 3 in the general formula (1).
- an alkyl group having 1 to 8 carbon atoms, particularly a methyl group is preferable because of excellent absorption of ultraviolet rays in a long wavelength region.
- R 7 to R 9 may be the same as or different from each other, and represent a linear or branched alkyl group having 1 to 12 carbon atoms, provided that these alkyl groups are hydroxy groups. And may be substituted with a halogen atom or an alkoxy group having 1 to 12 carbon atoms, and may be interrupted with an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group or an imino group.
- the linear or branched alkyl group represented by R 1 to R 3 in the general formula (1) may be used as the linear or branched alkyl group having 1 to 12 carbon atoms represented by R 7 to R 9 in the general formula (2).
- the linear or branched alkyl group represented by R 1 to R 3 in the general formula (1) may be used. Examples thereof include the same groups as the branched alkyl group.
- the alkoxy group having 1 to 12 carbon atoms that may be substituted with the above alkyl group has 1 carbon atom that may be substituted with the alkyl group represented by R 1 to R 3 in the general formula (1).
- the same group as the alkoxy group of -12 is mentioned.
- Examples of the triazine compound represented by the general formula (1) or (2) according to the present invention include the following compound No. 1-No. And the like.
- the insect repellent film of the present invention is kneaded, for example, by kneading the triazine compound represented by the general formula (1) or (2), which is an ultraviolet absorber, into a synthetic resin as it is or together with a binder resin or an additive. It can be obtained by forming and forming a film. Alternatively, it may be applied to a synthetic resin substrate by coating or the like.
- Method 1 A triazine compound represented by the general formula (1) or (2), which is an ultraviolet absorber, is blended into a synthetic resin and kneaded to form an ultraviolet absorbing resin composition, which is then heat-molded to produce a film.
- Method 2 A paint or coating liquid containing the triazine compound represented by the general formula (1) or (2), which is an ultraviolet absorber, is prepared and formed on a molded body that becomes a film based on a synthetic resin. How to coat.
- Method 3 A method for producing a laminated resin film by incorporating a triazine compound represented by the general formula (1) or (2), which is an ultraviolet absorber, in an adhesive and applying the adhesive to the film. .
- a triazine compound represented by the general formula (1) or (2) which is an ultraviolet absorber
- Method 1 in which the triazine compound represented by the general formula (1) or (2) is blended in the synthetic resin, kneaded and heat-molded, the synthetic resin is as transparent as possible when it is made into a resin film. Those having high properties are preferred.
- vinyl compounds such as polyacryl
- Polyamide such as nylon 6, nylon 66, polyimide, polyurethane, polypeptide, polyester such as polyethylene terephthalate, polyether such as polycarbonate, polyoxymethylene, polyethylene oxide, polypropylene oxide, epoxy resin, polyvinyl alcohol, polyvinyl butyral, etc. However, it is not limited to these resins.
- the processing temperature, filming conditions, and the like differ slightly depending on the base resin to be used.
- a triazine compound represented by the general formula (1) or (2) is used as the base resin.
- the film can be obtained by stretching the film uniaxially or biaxially into a film having a thickness of 10 to 200 ⁇ m.
- additives used for ordinary resin molding such as infrared absorbers, antioxidants, light stabilizers, flame retardants, plasticizers, dyes, pigments for controlling color tone, and other An ultraviolet absorber may be added.
- the addition amount of the triazine compound represented by the general formula (1) or (2) is preferably 0.001 to 20% by mass, and 0.01 to 10% by mass with respect to the synthetic resin. More preferred is 0.1 to 5% by mass. If the amount is less than 0.001% by mass, the insect-repellent effect such as prevention of attracting flying insects may not be sufficient, and if it exceeds 20% by mass, the transparency of the film may be lowered.
- a method of coating by dissolving the triazine compound represented by (1) or (2) in a binder resin and an organic solvent there is a method in which the triazine compound represented by (1) or (2) is dissolved or dispersed in a binder resin and an aqueous solvent to form an aqueous paint.
- the former method is, for example, an aliphatic ester resin, an acrylic resin, a melamine resin, a urethane resin, an aromatic ester resin, a polycarbonate resin, an aliphatic polyolefin resin, an aromatic polyolefin resin, a polyvinyl resin, Polyvinyl alcohol resin, polyvinyl-modified resin (PVB, EVA, etc.) or their copolymer resins are used as organic solvents, halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based , Ether solvents, or mixtures thereof can be used.
- the latter method is a method in which the triazine compound represented by the general formula (1) or (2) is dissolved or dispersed in the aqueous binder resin, and the triazine compound represented by the general formula (1) or (2) is used. There is a method of atomizing to several ⁇ m or less and dispersing it in an aqueous solvent using an emulsifier as necessary.
- aqueous binder resin examples include polyvinyl alcohol or a modified product thereof, polyacrylic acid or a copolymer thereof, cellulose or a modified product thereof.
- aqueous solvent examples include water or a solution obtained by adding water to an alcohol such as methyl alcohol, a ketone such as acetone, or an ether such as tetrahydrofuran.
- the emulsion include finely pulverizing a triazine compound represented by the general formula (1) or (2) in an uncolored acrylic emulsion paint such as an acrylic emulsion aqueous paint dispersed in an acrylic emulsion (50 ⁇ 500 nm) is dispersed.
- the amount of the triazine compound represented by the general formula (1) or (2) is preferably 0.001 to 20% by mass with respect to the total of the binder resin and the synthetic resin of the base material to be coated. 0.01 to 10% by mass is more preferable, and 0.1 to 5% by mass is particularly preferable. If the amount is less than 0.001% by mass, the insect-repellent effect such as prevention of attracting flying insects may not be sufficient, and if it exceeds 20% by mass, the transparency of the film may be lowered. Add additives such as near-infrared absorbers, antioxidants, and light stabilizers used in ordinary paints, and dyes, pigments, or other UV absorbers to control color tone in the paint or coating liquid. Also good.
- the coating material or coating solution prepared by the above method is a bar coater, gravure coater, comma coater, lip coater, curtain coater, roll coater, blade coater, spin coater, reverse coater on a synthetic resin film or sheet as a substrate. Coating with a die coater or spray to produce an insect repellent film.
- a protective layer may be provided, or it may be bonded to a coating surface such as a transparent resin plate or a transparent resin film.
- a cast film is also included in the method.
- Method 3 in which a triazine compound represented by the general formula (1) or (2) is contained in an adhesive to produce a laminated resin film, as the adhesive, a general silicone or urethane is used.
- Known transparent adhesives such as adhesives for resins such as acrylic and acrylic, polyvinyl butyral adhesive (PVB), and ethylene-vinyl acetate adhesives can be used.
- resin films are bonded to each other using an adhesive to which a triazine compound represented by the general formula (1) or (2) is added. There is also a method of thermocompression bonding.
- the amount of the triazine compound represented by the general formula (1) or (2) is 0.001 to 20% by mass with respect to the total of the solid content of the adhesive and the synthetic resin of the base material.
- 0.01 to 10% by mass is more preferable, and 0.1 to 5% by mass is particularly preferable. If the amount is less than 0.001% by mass, the insect-repellent effect such as prevention of attracting flying insects may not be sufficient, and if it exceeds 20% by mass, the transparency of the film may be lowered.
- the resin used as the substrate is not particularly limited, but a resin having transparency is preferable.
- resins include: cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose; polyamides such as nylon 6 and nylon 66; polyimides; polyurethanes; Polycarbonate; Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate Polystyrene, polyethylene, polypropylene, polymethylpentene, copolymers of polyethylene and cycloolefins such as norbornene, etc.
- TAC triacetylcellulose
- propionylcellulose butyrylcellulose
- acetylpropionylcellulose nitrocellulose
- polyamides such as nylon 6 and nylon
- Polyolefins vinyl compounds such as polyacrylonitrile, polyvinyl acetate, polyvinyl chloride, polyvinyl fluoride; polyvinylidene chloride, polyvinylidene fluoride, polyvinylidene polycide, vinylidene fluoride / trifluoroethylene copolymer, vinylidene fluoride / tetrafluoro Vinyl compounds such as ethylene copolymers, vinylidene cyanide / vinyl acetate copolymers, or copolymers of fluorine compounds; acrylic resins such as polyacrylic acid, polymethyl methacrylate, and polyacrylate esters; polyhexafluoropropylene, etc.
- vinyl compounds such as polyacrylonitrile, polyvinyl acetate, polyvinyl chloride, polyvinyl fluoride; polyvinylidene chloride, polyvinylidene fluoride, polyvinylidene polycide, vinylidene fluoride / tri
- polyester resins and norbornene resins acrylic resins are preferred.
- the above resins may be used alone, or may be used in the form of two or more kinds of mixtures and / or copolymers, or laminated according to the use.
- the insect-proof film of the present invention may have a single layer structure or a laminated multilayer structure.
- the triazine compound of the general formula (1) or (2) may be used in one or more layers.
- the synthetic resin used in the insect-proof film of the present invention various additives may be used as necessary, and the base resin may be subjected to a surface treatment.
- antioxidants phenolic, phosphorus-based or thioether-based
- ultraviolet absorbers other than the triazine compounds according to the present invention
- hindered amine light stabilizers nucleating agents, antistatic agents, and light absorption.
- flame retardants such as resins, metal oxides, melamine phosphate (poly), and piperazine phosphate (poly).
- phenolic antioxidant examples include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4). -Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m-cresol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl) -M-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6-tert-butyl) Eno
- Examples of the phosphorus antioxidant include trisnonylphenyl phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl].
- Phosphite tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di Tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite Phosphite, bis (2,4-dicumylphenyl) pen Erythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphit
- thioether-based antioxidant examples include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetra ( ⁇ -dodecyl mercaptopropionate). And ⁇ -alkyl mercaptopropionic esters of polyols.
- Examples of the ultraviolet absorber other than the triazine compound according to the present invention include benzotriazole-based, benzophenone-based, benzoate-based, and triazine-based ultraviolet absorbers other than the triazine-based ultraviolet absorber represented by the general formula (1) or (2). Agents.
- the benzotriazole-based ultraviolet absorber is not particularly limited, and examples thereof include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-terpolymer). Tributylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'- Tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) 2- (2′-hydroxyphenyl) such as benzotriazole, 2,2′-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol, etc. Sulfonyl) benzotriazoles, and the like.
- the benzophenone-based ultraviolet absorber is not particularly limited.
- the benzoate ultraviolet absorber is not particularly limited, and examples thereof include phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4 -Ditertiary amylphenyl-3,5-ditertiarybutyl-4-hydroxybenzoate, hexadecyl-3,5-ditertiarybutyl-4-hydroxybenzoate and the like.
- triazine-based ultraviolet absorbers other than the triazine-based ultraviolet absorber represented by the general formula (1) or (2) include 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2 , 4-Dimethylphenyl) -s-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) ) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-dibiphenyl-s-triazine, 2,4-bis (2-hydroxy-4-octoxyphenyl) -6- (2,4-dimethylphenyl) -s-triazine, 2,4,6-tris (2-hydroxy-4-octoxypheny ) -S-triazine, 2- (4-iso-o
- hindered amine light stabilizer examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Tetrakis (2,2,6,6-tetramethyl-4-piperidylbutanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidylbutanetetracarboxylate, bis (2,2, 6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2 2,6,6-pentamethyl-4-piperidyl) -di (tridecyl) -1,2,
- nucleating agent examples include metal salts of benzoic acids such as aluminum pt-butylbenzoate and sodium benzoate, sodium bis (2,4-di-tert-butylphenyl) phosphate, methylene bis (2 , 4-di-t-butylphenyl) phosphate sodium salt, bis [methylenebis (2,4-di-t-butylphenyl) phosphate ester] hydroxyaluminum, etc., aromatic phosphate metal salts and aromatic phosphates Examples thereof include mixtures of ester metal salts and alkali metal compounds, dibenzylidene sorbitols such as dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (dimethylbenzylidene sorbitol), amino acid metal salts, and rosin acid metal salts.
- benzoic acids such as aluminum pt-butylbenzoate and sodium benzoate
- the antistatic agent examples include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts; higher alcohol phosphate esters, higher alcohol EO adducts, polyethylene glycol fatty acid esters, anionic type Anionic antistatic agents such as alkyl sulfonates, higher alcohol sulfates, higher alcohol ethylene oxide adduct sulfates, higher alcohol ethylene oxide adduct phosphates; polyhydric alcohol fatty acid esters, polyglycol phosphates, poly Nonionic antistatic agents such as oxyethylene alkyl allyl ether; amphoteric antistatic agents such as amphoteric alkylbetaines such as alkyldimethylaminoacetic acid betaine and imidazoline type amphoteric surfactants. Such an antistatic agent may be used alone, or two or more kinds of antistatic agents may be used in combination.
- Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. Can be mentioned. A large number of irregularities, lines, etc. may be provided on the surface by the surface treatment.
- the method of using the insect-proof film of the present invention is not particularly limited as long as it is intended to shield ultraviolet rays and prevent the attracting and flying of flying insects.
- a light emitting body such as a fluorescent lamp, a mercury lamp, and LED lighting
- it may be used by directly pasting it, or it may be used as a cover for covering the luminous body.
- the thickness of the insect-proof film of the present invention is not particularly limited as long as it is less than 200 ⁇ m, but is preferably 10 ⁇ m or more and less than 200 ⁇ m.
- the insect-proof film of the present invention preferably shields ultraviolet rays and transmits visible light. Therefore, the transmittance of visible light having a wavelength of 500 nm is preferably 80% or more and 100% or less, and more preferably 90% or more and 100% or less. Due to the high transmittance of visible light, the brightness does not decrease when lighting is used, and the color of lighting does not become unnatural. Natural light can be taken in, and even when used for agricultural films, natural light can be taken in without adversely affecting crop growth.
- the insect-proof film of the present invention effectively shields ultraviolet rays in a long wavelength region of 380 nm to 400 nm, and the transmittance of ultraviolet rays having a wavelength of 400 nm is preferably 0% or more and 5.0% or less. Preferably they are 0% or more and 1.0% or less.
- the ultraviolet absorption rate and visible light transmittance can be adjusted by the thickness of the film and the thickness of the coating layer.
- the insect-proof cover of the present invention shields ultraviolet rays emitted from a light emitter by covering a light emitter such as a fluorescent lamp, a mercury lamp, or LED lighting.
- the insect-proof cover of the present invention can be obtained by the same method as that of the above-mentioned insect-proof film, and those having a thickness of 200 ⁇ m or more may be used. Those having a thickness of 200 ⁇ m or more are conventionally known fluorescent lamp covers. You may affix and use on the cover of lighting fixtures, such as.
- the insect-proof cover of the present invention may be obtained using the following two methods, for example.
- Method A A triazine-based compound represented by the general formula (1) or (2), which is an ultraviolet absorber, is blended in a synthetic resin and kneaded to form an ultraviolet-absorbing resin composition, which is then heat-molded to produce a cover.
- Method B A paint or coating liquid containing the triazine compound represented by the general formula (1) or (2) which is an ultraviolet absorber is prepared, and coated on a molded body based on a synthetic resin or glass. How to. Hereinafter, each method will be described in order.
- Method A in which a triazine compound represented by the general formula (1) or (2) is blended in a synthetic resin, kneaded and heat-molded, the synthetic resin is as transparent as possible when it is made into a resin film.
- the synthetic resin is as transparent as possible when it is made into a resin film.
- Those having high properties are preferred.
- Specific examples include polyethylene, polypropylene, polystyrene, copolymers of polyethylene and cycloolefins such as norbornene, polyacrylic acid, polyacrylic esters, polyvinyl acetate, polyacrylonitrile, polyvinyl chloride, polyvinyl compounds such as polyvinyl fluoride, and vinyl.
- Polyamide such as nylon 6 and nylon 66, polyimide, polyurethane, polypeptide, polyester such as polyethylene terephthalate, polyether such as polycarbonate, polyoxymethylene, polyethylene oxide, polypropylene oxide, epoxy resin, polyvinyl alcohol, polyvinyl butyral, etc. However, it is not limited to these resins.
- the processing temperature, processing conditions and the like are slightly different depending on the base resin to be used.
- the triazine compound represented by the general formula (1), particularly the general formula (2) is used.
- a molded product can be obtained by adding to a base resin powder or pellet, heating to 150 to 350 ° C., kneading, and molding.
- the molding method is not particularly limited, and examples thereof include extrusion processing, calendering processing, injection molding, roll, compression molding, blow molding, and the like, and a molded body that serves as a cover can be manufactured.
- additives used for ordinary resin molding such as infrared absorbers, antioxidants, light stabilizers, flame retardants, plasticizers, dyes, pigments for controlling color tone, and other An ultraviolet absorber may be added.
- the addition amount of the triazine compound represented by the general formula (1), in particular, the general formula (2) is preferably 0.001 to 20% by mass with respect to the synthetic resin, and 0.01 to 10 % By mass is more preferable, and 0.1 to 5% by mass is particularly preferable. If the amount is less than 0.001% by mass, the insect-repelling effect such as prevention of attracting flying insects is not sufficient, and if it exceeds 20% by mass, the transparency may be lowered.
- Method B of coating after coating a method of coating by dissolving the triazine compound represented by formula (1) or (2) in a binder resin and an organic solvent, and formula There is a method in which the triazine compound represented by (1) or (2) is dissolved or dispersed in a binder resin and an aqueous solvent to form an aqueous paint.
- the former method is, for example, an aliphatic ester resin, an acrylic resin, a melamine resin, a urethane resin, an aromatic ester resin, a polycarbonate resin, an aliphatic polyolefin resin, an aromatic polyolefin resin, a polyvinyl resin, Polyvinyl alcohol resin, polyvinyl-modified resin (PVB, EVA, etc.) or their copolymer resins are used as organic solvents, halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based , Ether solvents, or mixtures thereof can be used.
- a method of dissolving or dispersing the triazine compound represented by the general formula (1) or (2) in the aqueous binder resin, the triazine compound represented by the general formula (1) or (2) There is a method of atomizing to several ⁇ m or less and dispersing it in an aqueous solvent using an emulsifier as necessary.
- aqueous binder resin examples include polyvinyl alcohol or a modified product thereof, polyacrylic acid or a copolymer thereof, cellulose or a modified product thereof.
- aqueous solvent examples include water or a solution obtained by adding water to an alcohol such as methyl alcohol, a ketone such as acetone, or an ether such as tetrahydrofuran.
- the emulsion include finely pulverizing the triazine compound represented by the general formula (1) or (2) in an uncolored acrylic emulsion paint such as an acrylic emulsion water-based paint dispersed in an acrylic emulsion (50- 500 nm) is dispersed.
- the amount of the triazine compound represented by the general formula (1) or (2) is 0.001 to 20% by mass based on the total of the binder resin and the synthetic resin or glass of the base material to be coated. Is preferable, 0.01 to 10% by mass is more preferable, and 0.1 to 5% by mass is particularly preferable. If the amount is less than 0.001% by mass, the insect-repellent effect such as prevention of attracting flying insects may not be sufficient, and if it exceeds 20% by mass, the transparency may be lowered.
- the paint or coating solution produced by the above method is a bar coater, gravure coater, comma coater, lip coater, curtain coater, roll coater, blade coater, spin coater, reverse on a synthetic resin molding or glass as a substrate. Coat with a coater, die coater, or spray to make an insect cover.
- a protective layer may be provided, or it may be bonded to a coating surface such as a transparent resin plate or a transparent resin film.
- the resin used as the substrate is not particularly limited, but a resin having transparency is preferable.
- resins include: cellulose esters such as diacetylcellulose, triacetylcellulose (TAC), propionylcellulose, butyrylcellulose, acetylpropionylcellulose, nitrocellulose; polyamides such as nylon 6 and nylon 66; polyimides; polyurethanes; Polycarbonate; Polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate Polystyrene, polyethylene, polypropylene, polymethylpentene, copolymers of polyethylene and cycloolefins such as norbornene, etc.
- TAC triacetylcellulose
- propionylcellulose butyrylcellulose
- acetylpropionylcellulose nitrocellulose
- polyamides such as nylon 6 and nylon
- Polyolefins vinyl compounds such as polyacrylonitrile, polyvinyl acetate, polyvinyl chloride, polyvinyl fluoride; polyvinylidene chloride, polyvinylidene fluoride, polyvinylidene polycide, vinylidene fluoride / trifluoroethylene copolymer, vinylidene fluoride / tetrafluoro Vinyl compounds such as ethylene copolymers, vinylidene cyanide / vinyl acetate copolymers, or copolymers of fluorine compounds; acrylic resins such as polyacrylic acid, polymethyl methacrylate, and polyacrylate esters; polyhexafluoropropylene, etc.
- vinyl compounds such as polyacrylonitrile, polyvinyl acetate, polyvinyl chloride, polyvinyl fluoride; polyvinylidene chloride, polyvinylidene fluoride, polyvinylidene polycide, vinylidene fluoride / tri
- Polycarbonate Polysulfone, Polyethersulfone, Polyetherketone, Polyetherimide, Polyoxymethylene, Polyethyleneoxide, Polypropyleneoxide and other polyethers; Vinyl alcohol; polyvinyl butyral; norbornene resins.
- the above resins may be used alone, or may be used in the form of two or more kinds of mixtures and / or copolymers, or laminated according to the use.
- the base resin may be subjected to a surface treatment.
- antioxidants phenolic, phosphorus-based or thioether-based
- ultraviolet absorbers other than the triazine compounds according to the present invention
- hindered amine light stabilizers nucleating agents, antistatic agents, and light absorption.
- flame retardants such as resins, metal oxides, melamine phosphate (poly), and piperazine phosphate (poly).
- phenolic antioxidant examples include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4). -Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m-cresol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl) -M-cresol), 2,2'-ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6-tert-butyl) Eno
- Examples of the phosphorus antioxidant include trisnonylphenyl phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl].
- Phosphite tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di Tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite Phosphite, bis (2,4-dicumylphenyl) pen Erythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphit
- thioether-based antioxidant examples include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetra ( ⁇ -dodecyl mercaptopropionate). And ⁇ -alkyl mercaptopropionic esters of polyols.
- Examples of the ultraviolet absorber other than the triazine compound according to the present invention include benzotriazole-based, benzophenone-based, benzoate-based, and triazine-based ultraviolet absorbers other than the triazine-based ultraviolet absorber represented by the general formula (1) or (2). Agents.
- the benzotriazole-based ultraviolet absorber is not particularly limited, and examples thereof include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-terpolymer). Tributylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'- Tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) 2- (2′-hydroxyphenyl) such as benzotriazole, 2,2′-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol, etc. Sulfonyl) benzotriazoles, and the like.
- the benzophenone-based ultraviolet absorber is not particularly limited.
- the benzoate ultraviolet absorber is not particularly limited, and examples thereof include phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, 2,4 -Ditertiary amylphenyl-3,5-ditertiarybutyl-4-hydroxybenzoate, hexadecyl-3,5-ditertiarybutyl-4-hydroxybenzoate and the like.
- triazine-based ultraviolet absorbers other than the triazine-based ultraviolet absorber represented by the general formula (1) or (2) include 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2 , 4-Dimethylphenyl) -s-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) ) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-dibiphenyl-s-triazine, 2,4-bis (2-hydroxy-4-octoxyphenyl) -6- (2,4-dimethylphenyl) -s-triazine, 2,4,6-tris (2-hydroxy-4-octoxypheny ) -S-triazine, 2- (4-iso-o
- hindered amine light stabilizer examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Tetrakis (2,2,6,6-tetramethyl-4-piperidylbutanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidylbutanetetracarboxylate, bis (2,2, 6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2 2,6,6-pentamethyl-4-piperidyl) -di (tridecyl) -1,2,
- nucleating agent examples include metal salts of benzoic acids such as aluminum pt-butylbenzoate and sodium benzoate, sodium bis (2,4-di-tert-butylphenyl) phosphate, methylene bis (2 , 4-di-t-butylphenyl) phosphate sodium salt, bis [methylenebis (2,4-di-t-butylphenyl) phosphate ester] hydroxyaluminum, etc., aromatic phosphate metal salts and aromatic phosphates Examples thereof include mixtures of ester metal salts and alkali metal compounds, dibenzylidene sorbitols such as dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (dimethylbenzylidene sorbitol), amino acid metal salts, and rosin acid metal salts.
- benzoic acids such as aluminum pt-butylbenzoate and sodium benzoate
- the antistatic agent examples include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts; higher alcohol phosphate esters, higher alcohol EO adducts, polyethylene glycol fatty acid esters, anionic type Anionic antistatic agents such as alkyl sulfonates, higher alcohol sulfates, higher alcohol ethylene oxide adduct sulfates, higher alcohol ethylene oxide adduct phosphates; polyhydric alcohol fatty acid esters, polyglycol phosphates, poly Nonionic antistatic agents such as oxyethylene alkyl allyl ether; amphoteric antistatic agents such as amphoteric alkylbetaines such as alkyldimethylaminoacetic acid betaine and imidazoline type amphoteric surfactants. Such an antistatic agent may be used alone, or two or more kinds of antistatic agents may be used in combination.
- Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. Can be mentioned. A large number of irregularities, lines, etc. may be provided on the surface by the surface treatment.
- the thickness of the insect-proof cover of the present invention is not particularly limited as long as it is 200 ⁇ m or more, but preferably 200 to 500 ⁇ m.
- the insect repellent cover of the present invention is used to cover a light emitting body for the purpose of shielding ultraviolet rays and preventing flying insects from attracting and flying.
- a light emitting body such as a fluorescent lamp, a mercury lamp, and LED lighting, and a cover for lighting.
- the insect-proof film and insect-proof cover of the present invention efficiently absorb and shield ultraviolet rays, particularly ultraviolet rays in the long wavelength region of 340 nm to 400 nm. By using this for light emitters, lighting, window glass, agricultural films, etc., it is possible to prevent the flying insects from attracting and flying to the light emitters, lighting, indoors, and crops.
- the flying insect having the effect of the insect-proof film and the insect-protecting cover of the present invention may be a flying insect having positive phototactic properties with respect to ultraviolet rays.
- the leafhopper, the leafhopper, the leafhopper, the leafhopper, the apple Leafhoppers such as the spotted leafhopper, the spotted leafhopper, the leafhopper, the leafhopper, such as the leafhopper, the whitefly, the leafhopper, the leafhopper, etc.
- moss such as yotoga, suzumega, minoga, konaga, bakuga, iraga, yamayugaiga, maiigaiga, and the like.
- the present invention further includes the following other insect repellent films and insect repellent cover embodiments, methods for producing insect repellent films and insect repellent covers, and methods for preventing or preventing flying insects using insect repellent films and insect repellent covers It is about. 1. 0.001 to 20% by mass (preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass) of the triazine compound represented by the general formula (1) is added to the synthetic resin and kneaded. A method for producing an insect-repellent film or insect-repellent cover, which is made into a film by heat-molding the ultraviolet-absorbing resin composition. 2.
- the manufacturing method of an insect-proof cover 9. 8. The method for producing an insect repellent film or insect repellent cover according to 7 above, wherein a water-based acrylic resin, a water-based epoxy resin, or a water-based urethane resin is used as the water-based binder resin. 10.
- the amount of the triazine compound represented by the general formula (1) is 0.001 to 20% by mass (preferably 0.01 to 10% by mass) based on the total of the binder resin and the synthetic resin of the base material to be coated. , More preferably 0.1 to 5% by mass), and the method for producing an insect repellent film or insect repellent cover according to any one of 3 to 9 above. 11.
- the manufacturing method of the insect-proof film or insect-proof cover which makes a laminated resin film produce the laminated resin film by making the adhesive contain the triazine type compound represented by General formula (1), and apply
- 12 11.
- the amount of the triazine compound represented by the general formula (1) is 0.001 to 20% by mass (preferably 0%) based on the total of the solid content of the adhesive and the synthetic resin as the base material constituting the film.
- the method for producing an insecticidal cover according to 21 above wherein an aqueous acrylic resin, an aqueous epoxy resin, or an aqueous urethane resin is used as the aqueous binder resin.
- the amount of the triazine compound represented by the general formula (1) is 0.001 to 20% by mass (preferably 0.01 to 10%) based on the total amount of the binder resin and the base synthetic resin or glass to be coated.
- 28. 0.001 to 20% by mass (preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass) of the triazine compound represented by the general formula (1) is used for the synthetic resin.
- the method according to 27 or 28 above, wherein the synthetic resin is polyester, acrylic resin, or polycarbonate. 30. 27.
- 31. The flying insect according to any one of the above 27 to 29, wherein the transmittance of visible light having a wavelength of 500 nm is 80% or more and 100% or less, and the transmittance of ultraviolet light having a wavelength of 400 nm is 0% or more and 5.0% or less. Incentives or prevention methods.
- Example 1 With respect to 100 parts by mass of polyethylene terephthalate (intrinsic viscosity: 0.8 dL / g), compound no. 3 parts by mass of 1 was mixed and melted at 260 to 280 ° C., and an insect-proof film having a thickness of 70 ⁇ m was prepared by T-die extrusion. About the obtained insect-proof film, the transmittance
- the insect repellent effect of the obtained insect repellent film was measured as follows. That is, a wooden box with a width of 1.8 m, a depth of 1.8 m, and a height of 1.8 m is prepared, a 40 W white fluorescent lamp is installed in the center of the box ceiling, and the front center of the box is 80 cm ⁇ 80 cm. The opening was provided. The entire 40 W white fluorescent lamp was covered with the insect repellent film. After that, a box was installed outdoors, and from August 7pm to 7:30 pm (excluding rainy weather), the white fluorescent lamp was turned on, and then an insecticide was sprayed into the box, opening Closed. After the insects were killed, the number of insects in the box was counted. The measurement was carried out for 5 days with different days, and the average value is shown in Table 1.
- Example 1 An insect repellent film was produced in the same manner as in Example 1 except that no ultraviolet absorber was used. About the obtained insect-proof film, the transmittance
- Compound No. 1 is a monohydroxyphenyltriazine compound having a structure similar to that of the present triazine compound, the following compound No. 1
- An insect-proof film was produced in the same manner as in Example 1 except that 6 was used. About the obtained insect-proof film, the transmittance
- Compound No. 1 is a benzotriazole-based ultraviolet absorber, the following compound No. 1
- An insect-proof film was prepared in the same manner as in Example 1 except that 7 was used. About the obtained insect-proof film, the transmittance
- Compound No. 1 is a benzotriazole-based ultraviolet absorber, the following compound No. 1
- An insect repellent film was produced in the same manner as in Example 1 except that 8 was used. About the obtained insect-proof film, the transmittance
- Example 5 As an ultraviolet absorber, Compound No. In place of 1, a benzophenone ultraviolet absorber, the following compound No. An insect repellent film was produced in the same manner as in Example 1 except that 9 was used. About the obtained insect-proof film, the transmittance
- the insect repellent film of the present invention has excellent insect repellent effect while keeping the visible light transmission property and preventing flying insects.
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Abstract
Description
また農作物の栽培においても、飛翔昆虫等の害虫対策は重要な課題となっている。
しかし、これら従来の防虫フィルムや防虫カバーは、340nm~400nmの長波長領域の紫外線の遮光能力が充分ではなく、飛翔昆虫の誘引を阻止する効果が充分ではなかった。また、可視光線の領域(450nm~500nm)までカットしてしまうため、可視光線の光量が減衰され、照明が薄暗くなったり、照明の色が不自然になったり、窓ガラスに貼った場合、透明性に難があったり、自然光の取り入れに問題が生じていた。農業用途においても飛翔害虫の誘引を防ぐために紫外線を遮光しつつ、作物を順調に育てるために、自然光を取り入れなければならならず、これらの改善が求められていた。
即ち本発明は、紫外線吸収剤として、下記一般式(1)で表されるトリアジン系化合物の一種以上を含有する防虫フィルム又は防虫カバーを提供するものである。
本発明は、防虫フィルム又は防虫カバーに係るものである。本発明において、防虫フィルムとは、飛翔昆虫の誘引や飛来を防止する機能を有し、厚さ200μm未満の形状のものを意味し、また、防虫カバーとは、飛翔昆虫の誘引や飛来を防止する機能を有し、厚さ200μm以上の形状のものを意味する。
本発明の防虫フィルム及び防虫カバーは、紫外線吸収剤として、下記一般式(1)で表されるトリアジン系化合物の一種以上を含有する。
炭素原子数3~8のシクロアルキル基としては、例えば、シクロプロピル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチル基等が挙げられ、
炭素原子数2~8のアルケニル基としては、直鎖及び分岐のプロペニル、ブテニル、ペンテニル、ヘキセニル、ヘプテニル、オクテニル基が不飽和結合の位置によらず挙げられ、
炭素原子数6~18のアリール基としては、例えば、フェニル、ナフチル、ビフェニル基等が挙げられ、
炭素原子数7~18のアルキルアリール基としては、例えば、メチルフェニル、ジメチルフェニル、エチルフェニル、オクチルフェニル基等が挙げられ、
炭素原子数7~18のアリールアルキル基としては、例えば、ベンジル、2-フェニルエチル、1-メチル-1-フェニルエチル基等が挙げられる。
また上記の置換及び中断は組み合わされてもよいが、同じ基による中断が2つ以上連続すること、例えば、酸素原子による中断が連続して、基中に、-O-O-が含まれるようになることはない。
上記の置換基又は中断を有するアルキル基又はシクロアルキル基としては、2-ヒドロキシプロピル、2-メトキシエチル、3-スルホニル-2-ヒドロキシプロピル、4-メチルシクロヘキシル基等が挙げられ、
また、上記の置換基又は中断を有するアリール基としては、4-メチルフェニル、3-クロロフェニル、4-ベンジルオキシフェニル、4-シアノフェニル、4-フェノキシフェニル、4-グリシジルオキシフェニル、4-イソシアヌレートフェニル基等が挙げられる。
炭素原子数2~8のアルケニル基としては、上記一般式(1)におけるR1~R3が表す炭素原子数2~8のアルケニル基が挙げられる。
また、上記アルキル基を置換してもよい炭素原子数1~12のアルコキシ基としては、上記一般式(1)におけるR1~R3が表すアルキル基等を置換してもよい炭素原子数1~12のアルコキシ基と同じ基が挙げられる。
本発明の防虫フィルムは、紫外線吸収剤である一般式(1)又は(2)で表されるトリアジン系化合物を、そのまま、或いはバインダー樹脂や添加剤とともに、合成樹脂に混練する等して練り込み、成形・フィルム化することで得ることができる。また合成樹脂の基材にコーティング等によって塗布してもよい。
(方法1)紫外線吸収剤である一般式(1)又は(2)で表されるトリアジン系化合物を合成樹脂に配合、混練して紫外線吸収性樹脂組成物とし、加熱成形してフィルムを作製する方法。
(方法2)紫外線吸収剤である一般式(1)又は(2)で表されるトリアジン系化合物を含有する塗料又はコーティング液を作製し、合成樹脂を基材とするフィルムとなる成形体上にコーティングする方法。
(方法3)紫外線吸収剤である一般式(1)又は(2)で表されるトリアジン系化合物を接着剤に含有させ、その接着剤をフィルムに塗布することにより、合わせ樹脂フィルムを作製する方法。
以下、各方法について順に説明する。
合成樹脂に、一般式(1)又は(2)で表されるトリアジン系化合物を配合し、混練、加熱成形する方法1において、合成樹脂としては、樹脂フィルムにした場合にできるだけ透明性の高いものが好ましい。具体例としてポリエチレン、ポリプロピレン、ポリスチレン、ポリエチレンとノルボルネン等のシクロオレフィンとの共重合体、ポリアクリル酸、ポリアクリル酸エステル、ポリ酢酸ビニル、ポリアクリロニトリル、ポリ塩化ビニル、ポリフッ化ビニル等のビニル化合物及びビニル化合物の付加重合体、ポリメタクリル酸、ポリメタクリル酸エステル、ポリ塩化ビニリデン、ポリフッ化ビニリデン、ポリシアン化ビニリデン、フッ化ビニリデン/トリフルオロエチレン共重合体、フッ化ビニリデン/テトラフルオロエチレン共重合体、シアン化ビニリデン/酢酸ビニル共重合体等のビニル化合物又はフッ素系化合物の共重合体、ポリトリフルオロエチレン、ポリテトラフルオロエチレン、ポリヘキサフルオロプロピレン等のフッ素を含む化合物、ナイロン6、ナイロン66等のポリアミド、ポリイミド、ポリウレタン、ポリペプチド、ポリエチレンテレフタレート等のポリエステル、ポリカーボネート、ポリオキシメチレン、ポリエチレンオキシド、ポリプロピレンオキシド等のポリエーテル、エポキシ樹脂、ポリビニルアルコール、ポリビニルブチラール等を挙げることが出来るが、これらの樹脂に限定されるものではない。
塗料化後、コーティングする方法2においては、一般式(1)又は(2)で表されるトリアジン系化合物をバインダー樹脂及び有機系溶媒に溶解させて塗料化する方法と、一般式(1)又は(2)で表されるトリアジン系化合物をバインダー樹脂及び水系溶媒に溶解又は分散させて水系塗料とする方法がある。
水系溶媒としては、水又は、水にメチルアルコール等のアルコール、アセトン等のケトン、テトラヒドロフラン等のエーテルを加えたもの等が挙げられる。
また、エマルジョンの例としては、アクリルエマルジョン中に分散したアクリルエマル
ジョン系水系塗料等、未着色のアクリルエマルジョン塗料に一般式(1)又は(2)で表されるトリアジン系化合物を微粉砕(50~500nm)したものを分散させたものが挙げられる。
塗料又はコーティング液中には近赤外線吸収剤、酸化防止剤、光安定剤等の通常塗料に用いるような添加物や、色調をコントロールするための染料、顔料、或いはその他の紫外線吸収剤を加えてもよい。
一般式(1)又は(2)で表されるトリアジン系化合物を接着剤に含有させて、合わせ樹脂フィルムを作製する方法3においては、接着剤としては一般的なシリコン系、ウレタン系、アクリル系等の樹脂用接着剤、ポリビニルブチラール接着剤(PVB)、エチレン-酢酸ビニル系接着剤等の公知の透明接着剤を使用できる。方法3では、一般式(1)又は(2)で表されるトリアジン系化合物を添加した接着剤を用いて樹脂フィルム同士を接着して作製する。また熱圧着する方法もある。
上記の樹脂は、単独で用いてもよく、用途に応じて2種類以上の混合物及び/又は共重合体で、或いは積層させて用いてもよい。
本発明の防虫カバーは、蛍光灯、水銀灯、LED照明等の発光体を覆うことで、発光体から発せられる紫外線を遮光する。
本発明の防虫カバーは、上記のもの以外に、例えば、以下の2つの方法を利用して得られるものを使用してもよい。
(方法A)紫外線吸収剤である一般式(1)又は(2)で表されるトリアジン系化合物を合成樹脂に配合、混練して紫外線吸収性樹脂組成物とし、加熱成形してカバーを作製する方法。
(方法B)紫外線吸収剤である一般式(1)又は(2)で表されるトリアジン系化合物を含有する塗料又はコーティング液を作製し、合成樹脂又はガラスを基材とする成形体上にコーティングする方法。
以下、各方法について順に説明する。
合成樹脂に、一般式(1)又は(2)で表されるトリアジン系化合物を配合し、混練、加熱成形する方法Aにおいて、合成樹脂としては、樹脂フィルムにした場合にできるだけ透明性の高いものが好ましい。具体例としてポリエチレン、ポリプロピレン、ポリスチレン、ポリエチレンとノルボルネン等のシクロオレフィンとの共重合体、ポリアクリル酸、ポリアクリル酸エステル、ポリ酢酸ビニル、ポリアクリロニトリル、ポリ塩化ビニル、ポリフッ化ビニル等ビニル化合物及びビニル化合物の付加重合体、ポリメタクリル酸、ポリメタクリル酸エステル、ポリ塩化ビニリデン、ポリフッ化ビニリデン、ポリシアン化ビニリデン、フッ化ビニリデン/トリフルオロエチレン共重合体、フッ化ビニリデン/テトラフルオロエチレン共重合体、シアン化ビニリデン/酢酸ビニル共重合体等のビニル化合物又はフッ素系化合物の共重合体、ポリトリフルオロエチレン、ポリテトラフルオロエチレン、ポリヘキサフルオロプロピレン等のフッ素を含む化合物、ナイロン6、ナイロン66等のポリアミド、ポリイミド、ポリウレタン、ポリペプチド、ポリエチレンテレフタレート等のポリエステル、ポリカーボネート、ポリオキシメチレン、ポリエチレンオキシド、ポリプロピレンオキシド等のポリエーテル、エポキシ樹脂、ポリビニルアルコール、ポリビニルブチラール等を挙げることが出来るが、これらの樹脂に限定されるものではない。
塗料化後、コーティングする方法Bにおいては、一般式(1)又は(2)で表されるトリアジン系化合物をバインダー樹脂及び有機系溶媒に溶解させて塗料化する方法と、一般式(1)又は(2)で表されるトリアジン系化合物をバインダー樹脂及び水系溶媒に溶解又は分散させて水系塗料とする方法がある。
また、エマルジョンの例としては、アクリルエマルジョン中に分散したアクリルエマルジョン系水系塗料等、未着色のアクリルエマルジョン塗料に一般式(1)又は(2)で表されるトリアジン系化合物を微粉砕(50~500nm)したものを分散させたもの挙げられる。
上記の樹脂は、単独で用いてもよく、用途に応じて2種類以上の混合物及び/又は共重合体で、或いは積層させて用いてもよい。
1.合成樹脂に対し、一般式(1)で表されるトリアジン系化合物を0.001~20質量%(好ましくは0.01~10質量%、より好ましくは0.1~5質量%)添加、混練して紫外線吸収性樹脂組成物とし、該紫外線吸収性樹脂組成物を加熱成形してフィルムとする防虫フィルム又は防虫カバーの製造方法。
2.合成樹脂として、ポリエステル、アクリル系樹脂、ポリカーボネートを用いる前記1の防虫フィルム又は防虫カバーの製造方法。
3.一般式(1)で表されるトリアジン系化合物を含有する塗料又はコーティング液を作製し、塗料又はコーティング液を合成樹脂を基材とするフィルムとなる成形体上にコーティングする防虫フィルム又は防虫カバーの製造方法。
4.一般式(1)で表されるトリアジン系化合物をバインダー樹脂及び有機系溶媒に溶解させて塗料化する前記3の防虫フィルム又は防虫カバーの製造方法。
5.バインダー樹脂として、アクリル系樹脂、ポリエステルを用いる前記4の防虫フィルム又は防虫カバーの製造方法。
6.一般式(1)で表されるトリアジン系化合物をバインダー樹脂及び水系溶媒に溶解又は分散させて水系塗料とする前記3の防虫フィルム又は防虫カバーの製造方法。
7.一般式(1)で表されるトリアジン系化合物を、水系バインダー樹脂に溶解又は分散させてなる前記6の防虫フィルム又は防虫カバーの製造方法。
8.一般式(1)で表されるトリアジン系化合物を粒径50~500nmの範囲に微粒化し、水系溶媒中に、必要に応じて乳化剤を用いて、エマルジョンにして分散させてなる前記6の防虫フィルム又は防虫カバーの製造方法。
9.水系バインダー樹脂として、水系アクリル系樹脂、水系エポキシ樹脂、水系ウレタン樹脂を用いる前記7の防虫フィルム又は防虫カバーの製造方法。
10.一般式(1)で表されるトリアジン系化合物の使用量が、バインダー樹脂とコーティングする基材の合成樹脂の合計に対して、0.001~20質量%(好ましくは0.01~10質量%、より好ましくは0.1~5質量%)である前記3~9の何れかである防虫フィルム又は防虫カバーの製造方法。
11.一般式(1)で表されるトリアジン系化合物を接着剤に含有させ、その接着剤をフィルムに塗布することにより、合わせ樹脂フィルムを作製する防虫フィルム又は防虫カバーの製造方法。
12.接着剤として、アクリル系接着剤、スチレンブタジエンゴム系接着剤、エチレンー酢酸ビニル系接着剤を用いる前記11の防虫フィルム又は防虫カバーの製造方法。
13.一般式(1)で表されるトリアジン系化合物の使用量は、接着剤の固形分とフィルムを構成する基材となる合成樹脂の合計に対して、0.001~20質量%(好ましくは0.01~10質量%、より好ましくは、0.1~5質量%)である前記11又は12の防虫フィルム又は防虫カバーの製造方法。
14.基材となる樹脂として、ポリエステル、アクリル系樹脂、ポリカーボネートを用いる前記3~13の何れかである防虫フィルム又は防虫カバーの製造方法。
15.合成樹脂に対し、一般式(1)で表されるトリアジン系化合物を0.001~20質量%(好ましくは0.01~10質量%、より好ましくは0.1~5質量%)配合、混練して紫外線吸収性樹脂組成物とし、加熱成形してカバーを作製する防虫カバーの製造方法。
16.合成樹脂として、ポリエステル、アクリル系樹脂、ポリカーボネートを用いる前記15の防虫カバーの製造方法。
17.一般式(1)で表されるトリアジン系化合物を含有する塗料又はコーティング液を作製し、合成樹脂又はガラスを基材とする成形体上にコーティングする防虫カバーの製造方法。
18.一般式(1)で表されるトリアジン系化合物をバインダー樹脂及び有機系溶媒に溶解させて塗料化する前記17の防虫カバーの製造方法。
19.バインダー樹脂として、アクリル系樹脂、ポリエステルを用いる前記18の防虫カバーの製造方法。
20.一般式(1)で表されるトリアジン系化合物をバインダー樹脂及び水系溶媒に溶解又は分散させて水系塗料とする前記17の防虫カバーの製造方法。
21.一般式(1)で表されるトリアジン系化合物を、水系バインダー樹脂に溶解又は分散させてなる前記20の防虫カバーの製造方法。
22.一般式(1)で表されるトリアジン系化合物を粒径50~500nmの範囲に微粒化し、水系溶媒中に、必要に応じて乳化剤を用いて、エマルジョンにして分散させてなる前記20の防虫カバーの製造方法。
23.水系バインダー樹脂として、水系アクリル系樹脂、水系エポキシ樹脂、水系ウレタン樹脂を用いる前記21の防虫カバーの製造方法。
24.一般式(1)で表されるトリアジン系化合物の使用量が、バインダー樹脂とコーティングする基材の合成樹脂又はガラスの合計に対して、0.001~20質量%(好ましくは0.01~10質量%、より好ましくは0.1~5質量%)である前記17~23の何れかである防虫カバーの製造方法。
25.前記1~14の何れかである防虫フィルム又は防虫カバーの製造方法により製造された防虫フィルム又は防虫カバー。
26.前記15~24の何れかである防虫カバーの製造方法により製造された防虫カバー
27.紫外線吸収剤として、一般式(1)で表されるトリアジン系化合物の一種以上を用いる防虫フィルム及び防虫カバーを用いた飛翔昆虫の誘因又は飛来防止方法。
28.合成樹脂に、一般式(1)で表されるトリアジン系化合物を0.001~20質量%(好ましくは0.01~10質量%、より好ましくは0.1~5質量%)を用いてなる前記27の飛翔昆虫の誘因又は飛来防止方法。
29.合成樹脂が、ポリエステル、アクリル系樹脂、ポリカーボネートである前記27又は28の飛翔昆虫の誘因又は飛来防止方法。
30.上記一般式(1)で表されるトリアジン系化合物として下記一般式(2)で表されるトリアジン系化合物を用いる前記27~29の何れかである飛翔昆虫の誘因又は飛来防止方法。
31.波長500nmの可視光線の透過率が80%以上100%以下であり、且つ、波長400nmの紫外線の透過率が0%以上5.0%以下である前記27~29の何れかである飛翔昆虫の誘因又は飛来防止方法。
ポリエチレンテレフタレート(固有粘度:0.8dL/g)100質量部に対して、紫外線吸収剤として化合物No.1を3質量部混合し、260~280℃で溶融させ、T-ダイ押出により厚さ70μmの防虫フィルムを作製した。得られた防虫フィルムについて、波長500nmの可視光線の透過率、波長400nmの紫外線の透過率を測定した。結果を表1に示す。
即ち、横1.8m、奥行き1.8m、高さ1.8mの木製の箱を用意し、箱の天井の中央に、40Wの白色蛍光灯を設置し、箱の前面中央に、80cm×80cmの開口部を設けた。そして40Wの白色蛍光灯の全体を得られた防虫フィルムで覆った。
その後、屋外に箱を設置し、8月の午後7時~午後7時30分の30分間(雨天を除く)、白色蛍光灯を点灯させた後、箱内に殺虫剤を噴霧し、開口部を閉じた。虫が死滅した後、箱内の虫の数を数えた。測定は日を変えて5日間行い、その平均値を表1に示した。
紫外線吸収剤を使用しない以外は、実施例1と同様にして防虫フィルムを作製した。得られた防虫フィルムについて、波長500nmの可視光線の透過率、波長400nmの紫外線の透過率を測定した。結果を表1に示す。
さらに得られた防虫フィルムの防虫効果を実施例1と同様にして測定した。結果を表1に示す。
紫外線吸収剤として、化合物No.1の代わりに、本願トリアジン系化合物と類似構造のモノヒドロキシフェニルトリアジン化合物である、下記、化合物No.6を用いた以外は、実施例1と同様にして防虫フィルムを作製した。得られた防虫フィルムについて、波長500nmの可視光線の透過率、波長400nmの紫外線の透過率を測定した。結果を表1に示す。
さらに得られた防虫フィルムの防虫効果を実施例1と同様にして測定した。結果を表1に示す。
紫外線吸収剤として、化合物No.1の代わりに、ベンゾトリアゾール系紫外線吸収剤である、下記、化合物No.7を用いた以外は、実施例1と同様にして防虫フィルムを作成した。得られた防虫フィルムについて、波長500nmの可視光線の透過率、波長400nmの紫外線の透過率を測定した。結果を表1に示す。
さらに得られた防虫フィルムの防虫効果を実施例1と同様にして測定した。結果を表1に示す。
紫外線吸収剤として、化合物No.1の代わりに、ベンゾトリアゾール系紫外線吸収剤である、下記、化合物No.8を用いた以外は、実施例1と同様にして防虫フィルムを作製した。得られた防虫フィルムについて、波長500nmの可視光線の透過率、波長400nmの紫外線の透過率を測定した。結果を表1に示す。
さらに得られた防虫フィルムの防虫効果を実施例1と同様にして測定した。結果を表1に示す。
紫外線吸収剤として、化合物No.1の代わりに、ベンゾフェノン系紫外線吸収剤である、下記、化合物No.9を用いた以外は、実施例1と同様にして防虫フィルムを作製した。得られた防虫フィルムについて、波長500nmの可視光線の透過率、波長400nmの紫外線の透過率を測定した。結果を表1に示す。
さらに得られた防虫フィルムの防虫効果を実施例1と同様にして測定した。結果を表1に示す。
Claims (3)
- 紫外線吸収剤として、下記一般式(1)で表されるトリアジン系化合物の一種以上を含有する防虫フィルム又は防虫カバー。
- 波長500nmの可視光線の透過率が80%以上100%以下であり、且つ、波長400nmの紫外線の透過率が0%以上5.0%以下である請求項1又は2記載の防虫フィルム又は防虫カバー。
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CN112206851B (zh) * | 2020-09-24 | 2022-03-18 | 海南能国米业有限公司 | 一种大米的精加工方法 |
KR20230141859A (ko) * | 2021-03-29 | 2023-10-10 | 미쓰이금속광업주식회사 | 조화 처리 구리박, 동장 적층판 및 프린트 배선판 |
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JPS5523921A (en) * | 1978-08-07 | 1980-02-20 | Nippon Carbide Kogyo Kk | Method and material for limiting movement of arthropod |
JP2000169767A (ja) * | 1998-12-10 | 2000-06-20 | Mitsubishi Rayon Co Ltd | 害虫誘引阻止アクリル樹脂フィルムおよび積層体 |
JP2013067811A (ja) * | 2012-12-06 | 2013-04-18 | Adeka Corp | 遮光フィルム |
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JP4070157B2 (ja) * | 1997-08-29 | 2008-04-02 | 株式会社Adeka | トリアジン系化合物および紫外線吸収剤 |
JP2003016824A (ja) | 2001-07-03 | 2003-01-17 | Fujikoo:Kk | 昆虫の可視領域を吸収する機能を有する蛍光灯管被覆用チューブ |
EP1746445B1 (en) * | 2004-05-12 | 2012-02-22 | Adeka Corporation | Optical film |
JP4799234B2 (ja) * | 2006-03-22 | 2011-10-26 | 株式会社Adeka | 合成樹脂組成物 |
CN1836898A (zh) * | 2006-04-25 | 2006-09-27 | 上海大智三花薄膜有限公司 | 一种温室用光反射多功能复合薄膜及其制备方法 |
JP5213825B2 (ja) * | 2009-09-28 | 2013-06-19 | 大日本印刷株式会社 | 低誘虫シート及びこれを用いた照明器具 |
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2016
- 2016-03-04 WO PCT/JP2016/056811 patent/WO2016147911A1/ja active Application Filing
- 2016-03-04 KR KR1020177022042A patent/KR20170129105A/ko not_active Application Discontinuation
- 2016-03-04 JP JP2017506453A patent/JPWO2016147911A1/ja active Pending
- 2016-03-04 CN CN201680008358.6A patent/CN107205370A/zh active Pending
- 2016-03-04 US US15/550,911 patent/US10517289B2/en active Active
- 2016-03-04 EP EP16764741.1A patent/EP3272216A4/en not_active Withdrawn
- 2016-03-14 TW TW105107804A patent/TWI723983B/zh active
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JPS5523921A (en) * | 1978-08-07 | 1980-02-20 | Nippon Carbide Kogyo Kk | Method and material for limiting movement of arthropod |
JP2000169767A (ja) * | 1998-12-10 | 2000-06-20 | Mitsubishi Rayon Co Ltd | 害虫誘引阻止アクリル樹脂フィルムおよび積層体 |
JP2013067811A (ja) * | 2012-12-06 | 2013-04-18 | Adeka Corp | 遮光フィルム |
Non-Patent Citations (1)
Title |
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See also references of EP3272216A4 * |
Also Published As
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US20180042217A1 (en) | 2018-02-15 |
JPWO2016147911A1 (ja) | 2017-12-28 |
EP3272216A4 (en) | 2018-12-05 |
TWI723983B (zh) | 2021-04-11 |
EP3272216A1 (en) | 2018-01-24 |
KR20170129105A (ko) | 2017-11-24 |
TW201639457A (zh) | 2016-11-16 |
US10517289B2 (en) | 2019-12-31 |
CN107205370A (zh) | 2017-09-26 |
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