JP2013133405A - Insect repellent resin composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel insect repellent resin composition which is excellent in light resistance and retainability of pyrethroid compound, and a use thereof.SOLUTION: The resin composition includes a pyrethroid compound and an ultraviolet absorber which are contained in a thermoplastic resin including two or more resins, one of the resins being ethylene/methylene methacrylate copolymer resin. Relative to 100 pts.wt. of other resins, the content of the ethylene/methyl methacrylate copolymer is preferably 5 pts.wt. or more and 45 pts.wt. or less. The pyrethroid compound is preferably permethrin, and the ultraviolet absorber is preferably based on benzotriazole.

Description

  The present invention relates to a novel insect repellent resin composition excellent in light resistance and retention of a pyrethroid compound, and use thereof.

  Conventionally, as means for gradual release of an insect repellent active ingredient, a film or sheet using a resin composition obtained by kneading a thermoplastic resin and an insect repellent active ingredient, or a resin composition obtained by impregnating a thermoplastic resin with an insect repellent active ingredient A technique is known in which an insect repellent active ingredient is released from an obtained molded article after being molded into, for example.

  For example, Patent Document 1 describes an insect repellent resin composition containing high density polyethylene, low density polyethylene, and a pyrethroid insect repellent at a predetermined ratio.

  Patent Document 2 describes an insect repellent resin composition in which an insect repellent active ingredient is contained in linear low density polyethylene.

  In Patent Documents 1 and 2, other additives such as antibacterial / antifungal agents, deodorizers, fragrances, antioxidants, ultraviolet absorbers, light-resistant agents, anti-blocking agents are added as necessary. It describes that an insecticide resin composition contains an agent, a filler, a pigment and the like.

Patent No. 3535258 (issue date: June 7, 2004) Patent No. 3336714 (issue date: October 21, 2002)

  By the way, insect repellent active ingredients contained in the insect repellent resin composition, especially pyrethroid compounds such as allethrin and permethrin, are unstable to light, and there are cases where sustained release over a long period of time cannot be expected.

  Moreover, since a pyrethroid compound is unstable to light, depending on a use condition, it may have a bad influence on the thermoplastic resin which comprises an insect-control resin composition.

  However, in Patent Documents 1 and 2, a combination of a specific insect repellent active ingredient (for example, a pyrethroid compound), a thermoplastic resin, and other additives (for example, a light-resistant agent and / or a UV absorber) is included in the insect repellent resin composition. There is no description as to whether or not it contributes to the light resistance and the retention of insect repellent active ingredients.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a novel insect repellent resin composition excellent in light resistance and pyrethroid compound retention, and use thereof. .

  The inventors of the present application have made extensive studies to solve the above problems. As a result, the inventors have found that the above-mentioned problems can be solved by including a pyrethroid compound and an ultraviolet absorber in a predetermined thermoplastic resin, and have arrived at the present invention.

  That is, the insect repellent resin composition according to the present invention includes a pyrethroid compound and an ultraviolet absorber in a thermoplastic resin containing two or more kinds of resins, one of which is an ethylene / methyl methacrylate copolymer resin. Containing.

  In the insect repellent resin composition according to the present invention, in the above configuration, the ultraviolet absorber is preferably a benzotriazole ultraviolet absorber.

  In the insect repellent resin composition according to the present invention, in the above structure, the pyrethroid compound is preferably permethrin.

  In the insect repellent resin composition according to the present invention, in the above structure, the proportion of the ethylene / methyl methacrylate copolymer resin in the thermoplastic resin is 100 parts by weight of the resin excluding the ethylene / methyl methacrylate copolymer resin. On the other hand, it is preferably within the range of 2 parts by weight or more and 25 parts by weight or less.

  In the insect repellent resin composition according to the present invention, the weight ratio of the ethylene unit and the methyl methacrylate unit constituting the ethylene / methyl methacrylate copolymer resin in the above configuration is methyl methacrylate with respect to 100 parts by weight of the ethylene unit. The unit is preferably in the range of 5 to 45 parts by weight.

  The present invention also provides a filament obtained by molding any one of the above insect repellent resin compositions, and a net formed from the filament.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a novel insect repellent resin composition excellent in retention and light resistance of a pyrethroid compound, and use thereof.

It is a figure which shows the measurement result of the time-dependent change of the permethrin content in a thread | yarn in an Example and a comparative example. It is a figure which shows the measurement result of the time-dependent change of the breaking strength of a thread | yarn in an Example and a comparative example.

  Hereinafter, the present invention will be described in detail.

[1. Insect repellent resin composition]
The insect repellent resin composition according to the present invention comprises a pyrethroid compound and an ultraviolet absorber in a thermoplastic resin containing two or more kinds of resins, one of which is an ethylene / methyl methacrylate copolymer resin. It contains.

(Thermoplastic resin)
The thermoplastic resin used in the present invention includes an ethylene / methyl methacrylate copolymer resin, and one other thermoplastic resin that is not an ethylene / methyl methacrylate copolymer (hereinafter simply referred to as another thermoplastic resin). It is comprised including the above. The ethylene / methyl methacrylate copolymer resin and the other thermoplastic resin are in a mixed state in the insect repellent resin composition.

  The other thermoplastic resin is preferably a polyolefin-based resin. Examples of the polyolefin-based resin include resins obtained by polymerizing one or more monomers selected from the group consisting of ethylene, α-olefin, cycloolefin, polar vinyl monomer, and the like. The polyolefin resin may be further modified after polymerization. When the polyolefin resin is a resin obtained by copolymerizing two or more types of monomers, it may be a random copolymer or a block copolymer. More specifically, examples of the polyolefin resin include an ethylene resin and a propylene resin.

(Ethylene resin)
An ethylene-based resin is a resin mainly composed of ethylene-derived structural units (repeating units) and is generally crystalline. In addition to an ethylene homopolymer, a comonomer copolymerizable with ethylene and ethylene The copolymer may be used. Examples thereof include ethylene-α-olefin copolymers, high density polyethylene, high pressure method low density polyethylene, ethylene-ethylenically unsaturated carboxylic acid copolymers, and the like.

  The melt flow rate (MFR) of the ethylene-based resin is preferably in the range of 0.01 g / 10 min or more and 100 g / 10 min or less from the viewpoint of the balance between workability, mechanical strength of the molded body, and heat resistance. More preferably, it is within the range of 0.1 g / 10 min or more and 80 g / 10 min or less, and further preferably within the range of 0.5 g / 10 min or more and 70 g / 10 min or less.

  More specifically, the ethylene-α-olefin copolymer is obtained by copolymerizing ethylene and an α-olefin having 4 to 12 carbon atoms using a metallocene catalyst or a Ziegler-Natta catalyst. It is an α-olefin copolymer.

  An α-olefin having 4 to 12 carbon atoms is used in a broad sense, and is a concept that includes a cyclic α-olefin in addition to a chain α-olefin. Examples of the α-olefin having 4 to 12 carbon atoms include butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, dodecene-1, 4-methyl- Examples include pentene-1, 4-methyl-hexene-1, vinylcyclohexane, vinylcyclohexene, styrene, norbornene, butadiene, isoprene and the like, preferably hexene-1, 4-methyl-pentene-1 or octene-1. . Among the cyclic α-olefins, norbornene and domon are preferable. Said C4-C12 alpha olefin may be used independently and may use at least 2 type together.

  Examples of the ethylene-α-olefin copolymer include an ethylene-butene-1 copolymer, an ethylene-4-methyl-pentene-1 copolymer, an ethylene-hexene-1 copolymer, and an ethylene-octene-1 copolymer. Polymers, and the like, preferably ethylene-hexene-1 copolymer, ethylene-4-methyl-pentene-1, or ethylene-octene-1 copolymer, and more preferably ethylene-hexene-1 It is a copolymer.

The density of the ethylene-α-olefin copolymer is preferably in the range of 880 Kg / m ³ or more and 945 Kg / m ³ or less, from the viewpoint of the balance of heat resistance and impact strength and transparency of the molded product. More preferably, it is in the range of 890 Kg / m ³ or more and 930 Kg / m ³ or less, and more preferably in the range of 900 Kg / m ³ or more and 925 Kg / m ³ or less.

  The metallocene catalyst is preferably a catalyst system including a transition metal compound having a group having a cyclopentadiene type anion skeleton. The transition metal compound having a group having a cyclopentadiene type anion skeleton is a so-called metallocene compound, for example, a general formula MLaXn-a (where M is a group 4 or lanthanide series transition of the periodic table of elements) L is a group having a cyclopentadiene-type anion skeleton or a group containing a heteroatom, and at least one is a group having a cyclopentadiene-type anion skeleton. X is a halogen atom, hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, n is a valence of a transition metal atom, and a is an integer of 1 or more and n or less. Only one type of metallocene catalyst may be used, or at least two types may be used in combination.

  The metallocene catalyst is used in combination with, for example, an organoaluminum compound, an alumoxane compound, and / or an ionic compound. Here, examples of the organoaluminum compound include triethylaluminum and triisobutylaluminum. Examples of the alumoxane compound include methylalumoxane. Examples of the ionic compound include trityl tetrakis pentafluorophenyl borate, N, N-dimethylanilinium tetrakis pentafluorophenyl borate, and the like.

The metallocene catalyst is a catalyst in which the metallocene compound and an organoaluminum compound, an alumoxane compound, and / or an ionic compound are supported or impregnated on a fine particle inorganic carrier or a fine particle organic polymer carrier. There may be. Here, examples of the fine inorganic support include SiO ₂ and Al ₂ O ₃ . Examples of the fine particle organic polymer carrier include polyethylene and polystyrene.

  As an ethylene-alpha-olefin copolymer obtained by superposition | polymerization using said metallocene catalyst, the ethylene-alpha-olefin copolymer described in Unexamined-Japanese-Patent No. 9-183816 is mentioned, for example. As a newer method, for example, there is a method using a late transition metal complex catalyst as a homogeneous catalyst.

  Examples of the method for producing the ethylene-α-olefin copolymer used in the present invention include a polymerization method using a metallocene catalyst or a Ziegler-Natta catalyst. Examples of the polymerization method include a solution polymerization method, a slurry polymerization method, a high pressure ion polymerization method, a gas phase polymerization method, and the like, preferably a gas phase polymerization method, a solution polymerization method, and a high pressure ion polymerization method. A gas phase polymerization method is preferred.

The density of the high-density polyethylene used as the other thermoplastic resin is preferably in the range of 945 Kg / m ³ or more and 970 Kg / m ³ or less from the viewpoint of the balance between the heat-fusible property of the molded article and the impact strength. Preferably, it is in the range of 945 Kg / m ³ or more and 965 Kg / m ³ or less.

  As a manufacturing method of said high density polyethylene, the polymerization method using a polymerization catalyst is mentioned. Examples of the polymerization catalyst include a Ziegler-Natta catalyst, and examples of the polymerization method include the same polymerization method as that used in the above-described method for producing an ethylene-α-olefin copolymer. More specifically, examples of the method for producing high-density polyethylene include a slurry polymerization method using a Ziegler-Natta catalyst.

The density of the high-pressure method low-density polyethylene used as the other thermoplastic resin is preferably 915 Kg / m ³ or more and 935 Kg / m ³ or less from the viewpoint of the balance between the heat-fusible property of the molded article and the impact strength. in the range, more preferably in the range of 930 kg / m ³ at 915 kg / m ³ or more, more preferably in the range 918 kg / m ³ or more 930 kg / m ³ or less of.

  As a method for producing high-pressure low-density polyethylene, for example, using a tank reactor or a tubular reactor, in the presence of a radical generator, a polymerization pressure of 140 MPa or more and 300 MPa or less, a polymerization temperature of 200 ° C. or more and 300 ° C. A method for polymerizing ethylene under the following conditions can be mentioned, and a hydrocarbon such as methane or ethane, or hydrogen is used as a molecular weight regulator in order to regulate the melt flow rate.

  The ethylene-ethylenically unsaturated carboxylic acid copolymer used as the other thermoplastic resin is a copolymer of ethylene and an ethylenically unsaturated carboxylic acid. The ethylenically unsaturated carboxylic acids are carboxylic acids and are compounds having an ethylenically unsaturated bond which is a polymerizable carbon-carbon unsaturated bond such as a carbon-carbon double bond.

  Examples of the ethylenically unsaturated carboxylic acids include vinyl esters of saturated carboxylic acids, vinyl esters of unsaturated carboxylic acids, α, β-unsaturated carboxylic acid esters, and the like.

  The vinyl ester of saturated carboxylic acid is preferably an aliphatic carboxylic acid vinyl ester having about 2 to 4 carbon atoms, and examples thereof include vinyl acetate, vinyl propionate and vinyl butyrate. The vinyl ester of unsaturated carboxylic acid is preferably an aliphatic carboxylic acid vinyl ester having about 2 to 5 carbon atoms, and examples thereof include vinyl acrylate and vinyl methacrylate. The α, β-unsaturated carboxylic acid ester is preferably an ester of an unsaturated carboxylic acid having about 3 to 8 carbon atoms such as an alkyl ester of acrylic acid or an alkyl ester of methacrylic acid. Examples of alkyl esters of acrylic acid include methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-t-butyl, and the like. Examples of the alkyl ester of methacrylic acid include methyl methacrylate, ethyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and t-butyl methacrylate. Each of these ethylenically unsaturated carboxylic acids may be used alone or in combination of two or more.

  In addition, hydrolysates of these ethylenically unsaturated carboxylic acids, for example, saponified ethylene-vinyl acetate copolymers obtained by hydrolysis of ethylene-vinyl acetate copolymers are also used as ethylene-ethylenically unsaturated carboxylic acid copolymers. It is preferably used as a coalescence.

  Among the above ethylenically unsaturated carboxylic acids, vinyl acetate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate are preferable, and vinyl acetate is more preferable.

  In addition, said ethylene-ethylenically unsaturated carboxylic acid copolymer may have a structural unit derived from other monomers other than ethylene and ethylenically unsaturated carboxylic acids.

(Propylene resin)
A propylene-based resin is a resin composed mainly of propylene-derived structural units (repeating units) and is generally crystalline. In addition to a propylene homopolymer, a comonomer that is copolymerizable with propylene and propylene The copolymer may be used.

  Examples of the comonomer copolymerized with propylene include ethylene and α-olefins having 4 to 20 carbon atoms. Examples of the α-olefin in this case include 1-butene, 2-methyl-1-propene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene and 2-ethyl-1. -Butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene 2-methyl-1-hexene, 2,3-dimethyl-1-pentene, 2-ethyl-1-pentene, 2-methyl-3-ethyl-1-butene, 1-octene, 5-methyl-1-heptene 2-ethyl-1-hexene, 3,3-dimethyl-1-hexene, 2-methyl-3-ethyl-1-pentene, 2,3,4-trimethyl-1-pentene, 2-propyl-1-pentene 2,3-diethyl-1 Butene, 1-nonene, 1-undecene, 1-dodecene, 1-tetradecene, 1-pentadecene 1-hexadecene 1-heptadecene 1-octadecene, 1-nonadecene, and the like.

  The α-olefin is preferably an α-olefin having 4 to 12 carbon atoms, and more preferably 1-butene, 2-methyl-1-propene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl- 1-pentene, 3,3-dimethyl-1-butene, 1-heptene, 2-methyl-1-hexene, 2,3-dimethyl-1-pentene, 2-ethyl-1-pentene, 2-methyl-3- Ethyl-1-butene; 1-octene, 5-methyl-1-heptene, 2-ethyl-1-hexene, 3,3-dimethyl-1-hexene, 2-methyl-3-ethyl-1-pentene, 2, 3,4-trimethyl-1-pen Ten, 2-propyl-1-pentene, 2,3-diethyl-1-butene, 1-nonene, 1-decene, 1-undecene or 1-dodecene. From the viewpoint of copolymerizability, 1-butene, 1-pentene, 1-hexene or 1-octene is preferable, and 1-butene or 1-hexene is more preferable.

  Examples of preferable propylene-based resins include propylene / ethylene copolymers and propylene / 1-butene copolymers. In the propylene / ethylene copolymer and the propylene / 1-butene copolymer, the content of the structural unit derived from ethylene and the content of the structural unit derived from 1-butene are, for example, Reference: “Polymer Analysis Handbook” (1995). Infrared (IR) spectrum measurement can be carried out by the method described on page 616 of Kinokuniya Shoten.

  The propylene resin is, for example, a solution polymerization method using an inert solvent typified by a hydrocarbon compound such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, or a liquid monomer as a solvent. It can be produced by a bulk polymerization method or a gas phase polymerization method in which a gaseous monomer is polymerized as it is. Polymerization by these methods may be carried out batchwise or continuously.

  The structure of the propylene-based resin is described in the reference: “Polypropylene Handbook” (edited by Edward P. Moore, Jr., Industrial Research Committee (issued in 1998)), isotactic structure, syndiotactic structure, attack tic. Any structure may be used, or a mixture of these structures may be used. In the present invention, a syndiotactic or isotactic propylene resin is preferably used from the viewpoint of heat resistance.

As described above, the propylene-based resin may have a syndiotactic structure. The propylene resin having a syndiotactic structure is a peak intensity observed at 20.2 ppm based on tetramethylsilane in a ¹³ C-NMR spectrum measured with a 1,2,4-trichlorobenzene solution at 135 ° C. A value obtained by dividing the sum of peak intensities attributed to methyl groups of propylene units (syndiotactic pentad fraction [rrrr]) is usually 0.3 or more and 0.9 or less, preferably Is a propylene-based resin that is 0.5 or more and 0.9 or less, more preferably 0.7 or more and 0.9 or less. The necessary peaks can be assigned according to the reference: A. Zambelli et al, Macromolecules, 6, 925 (1973).

  A method for producing a propylene resin having a syndiotactic structure uses, for example, a metallocene catalyst having a homogeneous active species as described in JP-A-5-17589, JP-A-5-131558, and the like. And produced by polymerizing propylene.

  The metallocene-based catalyst is a catalyst having homogeneous active species, and the propylene-based resin having a syndiotactic structure produced using the metallocene-based catalyst has a characteristic that the molecular weight distribution and the composition distribution are narrow. In addition, the molecular weight can be adjusted and the regularity of the structure can be controlled by selecting a ligand for the metallocene catalyst.

The propylene resin having the syndiotactic structure has a melting point of 130 ° C. or higher and 150 ° C. or lower, a density of about 880 Kg / mm ³ , and a crystallinity of 30% or higher and 40% or lower. For this reason, the molded object excellent in transparency, glossiness, etc. can be obtained.

  From the viewpoint of moldability, the propylene-based resin used in the present invention has a melt flow rate (MFR) measured at a temperature of 230 ° C. and a load of 21.18 N in accordance with JIS K 7210 of 0.1 g / 10 min or more. Is preferably in the range of 200 g / 10 min or less, more preferably in the range of 0.5 g / 10 min or more and 50 g / 10 min or less.

  Moreover, the polyolefin resin represented by the above-mentioned ethylene resin and propylene resin may be modified. Moreover, only 1 type may be used for said other thermoplastic resin, and 2 or more types may be used for it.

  In addition, from the viewpoint of sustaining the insect repellent effect, it is preferable to use at least one of high-density polyethylene and low-density polyethylene as the other thermoplastic resin, and it is more preferable to use at least high-density polyethylene.

  The proportion of the ethylene / methyl methacrylate copolymer resin and other thermoplastic resin may be determined based on the use of the insect repellent resin composition, but the improvement of the bleedability of the pyrethroid compound and the processability of the insect repellent resin composition From the standpoint of balance, for example, the ethylene / methyl methacrylate copolymer resin is preferably in the range of 2 parts by weight to 25 parts by weight with respect to 100 parts by weight of the other thermoplastic resin. More preferably, it is in the range of 10 parts by weight or less. In particular, as a thermoplastic resin, when using a mixture of high-density polyethylene (another thermoplastic resin) and an ethylene / methyl methacrylate copolymer resin, the mixing ratio may be determined based on the application, The ethylene / methyl methacrylate copolymer resin is preferably in the range of 2 to 25 parts by weight, preferably in the range of 2 to 10 parts by weight with respect to 100 parts by weight of the high-density polyethylene. More preferably.

  Further, the weight ratio of the ethylene unit and the methyl methacrylate unit constituting the ethylene / methyl methacrylate copolymer resin is 5 methyl methacrylate units with respect to 100 parts by weight of ethylene units from the viewpoint of excellent supportability of the pyrethroid compound. The range is preferably not less than 45 parts by weight and more preferably not less than 45 parts by weight and more preferably not less than 10 parts by weight and not more than 30 parts by weight.

(Pyrethroid compound)
The pyrethroid compound used in the present invention is a general term for natural pyrethroids, synthetic pyrethroids, and derivatives thereof. Examples of pyrethroid compounds include permethrin (permethrin), cypermethrin, phenothrin, ciphenothrin, d-phenothrin, cyphenothrin, resmethrin, d-resmethrin, fenvalerate, esfenvalerate, esbiothrin, fenpropatoline, etofenprox, Tralomethrin, deltamethrin, silafluophene, cyfluthrin, bifenthrin, allethrin, d-arethrin, dd-alleslin, prareslin, pyrethrin, tetramethrin, transfluthrin, methfluthrin, dimethfluthrin, profluthrin, empentrin, cylatrithrin, teraretrin Among others, permethrin, deltamethrin or metov Trindade is preferable.

  The compounding amount of the pyrethroid compound in the insect repellent resin composition may be determined depending on the type of the compound and the like, but is preferably 0.1 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin. More preferably, it is in the range of 0.5 to 5 parts by weight.

  In addition, since a pyrethroid compound is comparatively low toxicity compared with another insect repellent active ingredient, there may be a comparatively large compounding quantity. In such a case, the light resistance of the insect repellent resin composition is particularly affected.

(UV absorber)
Examples of the ultraviolet absorber used in the present invention include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4. -N-dodecyloxybenzophenone, 2-hydroxy-4-n-octadecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-hydroxy-5-chlorobenzophenone 2,2-dihydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, etc. Benzophenone UV absorber; 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3,5-dimethylphenyl) Benzotriazole, 2- (2-methyl-4-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-3-methyl-5-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3,5- Di-t-amylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy-3-t-5-methylphenyl) -5 Benzotriazole purple, which is a hydroxyphenyl-substituted benzotriazole compound such as chloro-2H-benzotriazole Linear absorption agent; and the like. Of these ultraviolet absorbers, benzotriazole ultraviolet absorbers are preferred.

  The blending amount of the UV absorber in the insect repellent resin composition may be determined by the type of the UV absorber, the blending amount of the pyrethroid compound, etc., preferably 0.05 parts by weight with respect to 100 parts by weight of the thermoplastic resin. It is in the range of not less than 2 parts by weight and more preferably in the range of not less than 0.1 parts by weight and not more than 1 part by weight.

(Other additives)
The resin composition for insect repellent according to the present invention further includes other additives such as antibacterial / antifungal agents, deodorants, fragrances, antioxidants, anti-blocking agents within the range not impairing the object of the present invention. Agents, fillers, weathering agents, pigments and the like may be contained. The filler may be used for the purpose of supporting the pyrethroid compound. Specific examples include inorganic particles having fine pores such as silica and zeolite.

[2. Production of insect repellent resin composition]
The insect repellent resin composition according to the present invention is produced, for example, by melt-kneading the thermoplastic resin, the pyrethroid compound, the ultraviolet absorber, and other additives used as necessary. The melt kneading method is, for example, 1) A method in which a thermoplastic resin, a pyrethroid compound, and an ultraviolet absorber are mixed in advance, and the resulting mixture is melt kneaded using an extruder, a roll molding machine, a kneader, or the like. 2) A method in which a thermoplastic resin, a pyrethroid compound, and an ultraviolet absorber are separately fed to an extruder and melt-kneaded. Moreover, when melt-kneading with an extruder, you may add a pyrethroid compound and a ultraviolet absorber from the middle of an extruder using raw material addition apparatuses, such as a side extruder or a feeder.

  In the production of the above-described insecticidal resin composition, the pyrethroid compound may be used in a state of being held by a predetermined holding body (holding body for pyrethroid compound). A method for holding the pyrethroid compound in a predetermined holding body may be performed by, for example, treatment such as loading, impregnation, infiltration, injection, adsorption, absorption, and the like. A composition obtained by adding a holding body holding a pyrethroid compound to a base resin may be used as a master batch.

  The resin serving as the base of the masterbatch is preferably, for example, at least one of a resin constituting an insect repellent resin composition, that is, an ethylene / methyl methacrylate copolymer resin, and another thermoplastic resin. When using this thermoplastic resin, it is more preferable to use at least one of high-density polyethylene and low-density polyethylene. The master batch is blended so that the proportion of the obtained insect-repellent resin composition is less than 50% by weight, for example, and is preferably blended so as to be 30% by weight or less from the viewpoint of improving economy. More preferably, it is blended so as to be not more than% by weight.

  Further, as another example of the method for producing the insect-repellent resin composition according to the present invention, a resin composition obtained by melt-kneading the thermoplastic resin, the ultraviolet absorber, and other additives used as necessary A method of adding the pyrethroid compound later to a product (including a molded product of the resin composition) by a method such as impregnation is exemplified. However, the above-described method of melt-kneading the pyrethroid compound together with the thermoplastic resin is more preferable.

[3. Insect repellent resin composition, usage, etc.)
Since the insect-repellent resin composition according to the present invention contains a thermoplastic resin as a main component, it can be easily molded into a desired shape according to the application by melting and molding. In particular, since the resin composition for insect repellent has excellent melt spinnability and good melt extrudability, it is used by molding into filaments such as multifilaments and monofilaments, and preferably used by molding into monofilaments. . In addition, filaments made of an insect repellent resin composition containing high-density polyethylene as another thermoplastic resin are particularly excellent in heat stretchability and also have good mechanical strength. In this case, the blending amount of the high density polyethylene is preferably within a range of 50% by weight to 98% by weight, more preferably 75% by weight to 98% by weight in the thermoplastic resin. More preferably, it is in the range of 90 wt% or more and 98 wt% or less (the total weight of the thermoplastic resin is 100 wt%). Furthermore, when the insect repellent resin composition according to the present invention is formed into a filament, it can be spun by extruding the insect repellent resin composition with high discharge, and the obtained yarn is highly stretched by a one-stage stretching operation. Since it is possible, it is excellent also in the viewpoint of the manufacturing cost of a filament.

  Examples of the method for molding the insect-repellent resin composition according to the present invention into a filament include molding methods such as a melt spinning method and a (direct) spinning / stretching method. More specifically, for example, the insect repellent resin composition is melted by using an extruder or the like, and if necessary, the insect repellent is discharged from the die nozzle through a gear pump that discharges a predetermined amount by meshing the gears. The resin composition is melt extruded to form a strand. Next, the strand-shaped insect repellent resin composition that has been melt-extruded is taken out, and the insect repellent resin composition is spun while being cooled using a cooling medium such as water or air. Examples of the method include winding the obtained filament by performing a treatment such as heat treatment or oil coating.

  In the method for producing a filament by heating and stretching a spun resin composition for insects according to the present invention, the temperature for heating and stretching is preferably in the range of 70 ° C. or more and 120 ° C. or less. From the viewpoint of improving the heat stretchability, the temperature for heat stretching is more preferably in the range of 75 ° C. or higher and 115 ° C. or lower, more preferably in the range of 80 ° C. or higher and 110 ° C. or lower, and particularly preferably 90 ° C. It is in the range of 105 ° C. or higher.

  Examples of the use of the filament composed of the insect repellent resin composition according to the present invention include monofilaments such as nets such as mosquito nets, screen doors and insect nets; ropes; threads; filters; Moreover, the use as a multifilament includes a rope; a net; a carpet; a nonwoven fabric; a filter; a shoe; Among these applications, applications requiring insect repellent properties such as screen doors, insect nets, mosquito nets, filters, carpets, shoes, and clothing are particularly preferable.

  In addition, the resin composition for insect control according to the present invention is particularly effective for insecticidal and repelling insects that mediate unpleasant pests and infectious diseases. Examples of insects that can be used include the mosquitoes, Aedes aegypti, Anopheles, Flyfish, Seduce chironae, Butterfly flies, House flies, Fly flies, Tsetse flies, Cattle fly, Floatfish and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited only to the range of these Examples.

  First, the details of the measurement methods of “Change with time of permethrin content in yarn” and “Change with time of break strength of yarn” measured in Examples and Comparative Examples will be described.

<Change over time of permethrin content in yarn>
The yarn sample 45 cm obtained in the examples and comparative examples was held for 16 hours under a temperature condition of 50 ° C., and then the inside of the tank using a sunshine weather meter (model WEL-SUN-DCHB: manufactured by Suga Test Instruments Co., Ltd.) An irradiation test was conducted for a specified time under the conditions of temperature: 50 ° C., humidity in the tank: 50%, and spray: none.

Thereafter, the yarn sample after the irradiation test was finely cut, and about 100 mg was weighed. Next, 20 mL of heptane was added to the weighed yarn sample, and component extraction was performed for 90 minutes under a temperature condition of 90 ° C. Subsequently, the obtained extract was subjected to gas chromatography under the following conditions, and the permethrin content (μg) per 1 g of the yarn sample was measured. And the obtained result was evaluated by the relationship between the time (irradiation time (hr)) of the irradiation test and the permethrin content (μg / g) per 1 g of the yarn sample.
Gas chromatography conditions:
Column: DB-1 (0.25 mm ID × 30 m, film thickness 0.25 μm)
Column temperature: 240 ° C. (18 min)
Sample vaporization chamber temperature: 260 ° C
Detector temperature: 265 ° C
Carrier gas: helium, average linear velocity: 40.0 cm / s
Injection system: Split (split ratio 50.0)
Injection volume: 1 μL
Internal standard: Triphenyl phosphate <Change in break strength of yarn over time>
The yarn sample 45 cm obtained in the examples and comparative examples was held for 16 hours under a temperature condition of 50 ° C., and then the inside of the tank using a sunshine weather meter (model WEL-SUN-DCHB: manufactured by Suga Test Instruments Co., Ltd.) An irradiation test was conducted for a specified time under the conditions of temperature: 50 ° C., humidity in the tank: 50%, and spray: none.

  Subsequently, the yarn sample after the irradiation test was subjected to a tensile test using a Tensilon universal testing machine (ATR-1T type: manufactured by Orientec Co., Ltd.) under the conditions of a tensile speed: 200 mm / min and a distance between chucks: 200 mm. . Then, the obtained results were evaluated by the relationship between the irradiation test time (irradiation time (hr)) and the residual strength at break (%). The residual strength at break of 100% means that the material has not deteriorated at all. The residual strength at break of 50% means that the deterioration has progressed and the strength at break has become half (50%). Represents a state.

[Example 1]
Permethrin (trade name Horser: manufactured by Sumitomo Chemical Co., Ltd.) 1.14 parts by weight as a pyrethroid compound and 0.553 parts by weight of a benzotriazole-based ultraviolet absorbent (trade name Sumisorb 300: manufactured by Sumitomo Chemical) as a UV absorber are homogeneous. The mixture was mechanically mixed so as to be mixed with each other.

Subsequently, 1.893 parts by weight of the obtained mixture, 94.252 parts by weight of high-density polyethylene (trade name: Hazex 440M: manufactured by Mitsui Chemicals, Inc .: density 951 kg / m ³ ), and ethylene / methyl methacrylate copolymer (commodity) Name Acrylift WH303F (manufactured by Sumitomo Chemical Co., Ltd.) (4.055 parts by weight) was mixed with an intensive mixer so as to be mixed uniformly to obtain a resin composition for insect repellent according to the present invention. Acrylift WH303F is a copolymer having a weight ratio of structural units derived from ethylene: structural units derived from methyl methacrylate of 82:18.

  Subsequently, the obtained insect-repellent resin composition was used as a yarn using a spinning machine (trade name: Monofilament production apparatus: manufactured by Musashino Kikai Co., Ltd.) to obtain a 120 denier yarn sample (filament).

  The spinning conditions for obtaining the yarn sample are as follows. A strand extruded from a die hole (4 holes, orifice diameter 1.0 mm) at a cylinder temperature of 130 ° C. to 200 ° C., a die temperature of 200 ° C., and an extrusion rotation speed of 4.5 rpm of the extruder provided in the production apparatus is first drawn. After taking water at a take-up speed of 14 m / min and water-cooling (water temperature 30 ° C.), it is led to a stretched water tank and taken in a boiled (95 ° C. or higher) stretch water tank at a second take-up speed of 112 m / min. A 120 denier yarn sample (filament) was obtained.

  With respect to the obtained yarn sample, the change with time of the permethrin content in the yarn and the change with time of the breaking strength of the yarn were measured. The measurement result of the change with time of the permethrin content in the yarn is shown in FIG. 1, and the measurement result of the change with time of the breaking strength of the yarn is shown in FIG.

[Comparative Example 1]
Permethrin as a pyrethroid compound (trade name: Horser: manufactured by Sumitomo Chemical Co., Ltd.) 1.140 parts by weight; high-density polyethylene (trade name: Hazex 440M: manufactured by Mitsui Chemicals Co., Ltd.): 94.805 parts by weight; and ethylene / methyl methacrylate copolymer 4.05 parts by weight of coalescence (trade name: ACLIFT WH303F: manufactured by Sumitomo Chemical Co., Ltd.) was mixed with an intensive mixer so as to be uniformly mixed to obtain a resin composition according to a comparative example.

  Subsequently, the obtained resin composition was made into a yarn using a spinning machine (trade name: Monofilament manufacturing apparatus: manufactured by Musashinokikai Co., Ltd.), thereby obtaining a 120-denier comparative yarn sample.

  With respect to the obtained yarn sample, the change with time of the permethrin content in the yarn and the change with time of the breaking strength of the yarn were measured. The measurement result of the change with time of the permethrin content in the yarn is shown in FIG. 1, and the measurement result of the change with time of the breaking strength of the yarn is shown in FIG.

[Comparative Example 2]
Instead of 0.553 parts by weight of a benzotriazole UV absorber (trade name: Sumisorb 300: manufactured by Sumitomo Chemical Co., Ltd.), which is an ultraviolet absorber, a light stabilizer (trade name: KIMASORB 944: HALS antioxidant: Sumitomo Chemical Co., Ltd.) A resin composition according to a comparative example was obtained in the same manner as in Example 1, except that 0.553 parts by weight was used.

  Subsequently, the obtained resin composition was made into a yarn using a spinning machine (trade name: Monofilament manufacturing apparatus: manufactured by Musashinokikai Co., Ltd.), thereby obtaining a 120-denier comparative yarn sample.

  With respect to the obtained yarn sample, the change with time of the permethrin content in the yarn and the change with time of the breaking strength of the yarn were measured. The measurement result of the change with time of the permethrin content in the yarn is shown in FIG. 1, and the measurement result of the change with time of the breaking strength of the yarn is shown in FIG.

[Comparative Example 3]
Instead of 0.553 parts by weight of a benzotriazole ultraviolet absorber (trade name Sumisorb 300: manufactured by Sumitomo Chemical Co., Ltd.) which is an ultraviolet absorber, a light stabilizer (trade name: Tinuvin 622: HALS antioxidant: Sumitomo Chemical Co., Ltd.) The resin composition which concerns on a comparative example was obtained like Example 1 except having used 0.553 weight part.

  Subsequently, the obtained resin composition was made into a yarn using a spinning machine (trade name: Monofilament manufacturing apparatus: manufactured by Musashinokikai Co., Ltd.), thereby obtaining a 120-denier comparative yarn sample.

  With respect to the obtained yarn sample, the change with time of the permethrin content in the yarn and the change with time of the breaking strength of the yarn were measured. The measurement result of the change with time of the permethrin content in the yarn is shown in FIG. 1, and the measurement result of the change with time of the breaking strength of the yarn is shown in FIG.

[Comparative Example 4]
Resin for comparison in the same manner as in Example 1 except that 98.308 parts by weight of high-density polyethylene (trade name: Hi-Zex 440M: manufactured by Mitsui Chemicals, Inc.) was used without using an ethylene / methyl methacrylate copolymer. A composition was obtained.

  Next, the resulting resin composition was attempted to be made into a yarn using a spinning machine (trade name: Monofilament production apparatus: Musashinokikai Co., Ltd.), but there was much permethrin deposition on the surface of the resin composition. The thread (filament) was not reached.

  In addition, the kind etc. of resin used for the Example and the comparative example were put together in the following Table 1.

※ 表中で、HDPEは高密度ポリエチレンを、EMMAはエチレン／メチルメタクリレート共重合体を表す。

* In the table, HDPE represents high-density polyethylene and EMMA represents ethylene / methyl methacrylate copolymer.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a novel insect repellent resin composition excellent in light resistance and retention of a pyrethroid compound, and use thereof.

Claims (7)

  An insect repellent resin composition containing a pyrethroid compound and an ultraviolet absorber in a thermoplastic resin containing two or more kinds of resins, one of which is an ethylene / methyl methacrylate copolymer resin.   The insect-repellent resin composition according to claim 1, wherein the ultraviolet absorber is a benzotriazole-based ultraviolet absorber.   The resin composition for insect repellent according to claim 1, wherein the pyrethroid compound is permethrin.   The ratio of the ethylene / methyl methacrylate copolymer resin in the thermoplastic resin ranges from 2 parts by weight to 25 parts by weight with respect to 100 parts by weight of the resin excluding the ethylene / methyl methacrylate copolymer resin. The resin composition for insect repellent according to any one of claims 1 to 3.   The weight ratio of ethylene units and methyl methacrylate units constituting the ethylene / methyl methacrylate copolymer resin is within the range of 5 to 45 parts by weight of methyl methacrylate units with respect to 100 parts by weight of ethylene units. The resin composition for insect control according to any one of claims 1 to 4.   The filament obtained by shape | molding the insecticidal resin composition of any one of Claims 1-5.   A net formed from the filament according to claim 6.

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