JP2004067960A - 4-methyl-1-pentene polymer type insect-controlling resin composition and insect control molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a 4-methyl-1-pentene polymer type insect-controlling resin composition exerting, durably over a long period, excellent controlling effects without adverse effects upon bio-hormones by the use of an insect-controlling active ingredient in a low concentration, and a molding made from the composition. <P>SOLUTION: The composition is obtained by blending an insect-controlling active ingredient with a 4-methyl-1-pentene type polymer which is the lowest in density among polyolefin types. The molding made from the composition is also provided. <P>COPYRIGHT: (C)2004,JPO

Description

【００３１】
【表２】

【００３２】
（実施例２）
４−メチル−１−ペンテン共重合体、及びフェノトリンを９８／２の重量比率で二軸押出機にて押し出しながらホットカットを行いペレット化し、防虫樹脂組成物を得た。この防虫樹脂組成物を成形温度２７０℃で射出成形を行い、長さ３５ｃｍ、幅１ｃｍ、厚さ４ｍｍの首輪の形状に成形した。これにバックルを取り付け首輪とし、この首輪を装着した犬を床面が絨毯である飼育室で飼育した。経時と共に絨毯を切り出し、直径５ｃｍの円形に切り抜き、切り抜いた円の上にネコノミの卵約６０個をネコノミの餌と共に載せ、２５℃にて２０日間ノミ成虫の出現を観察し、成虫出現率を測定した。本実施例による首輪は、８週間に亘り防虫効果を示していた。結果を表３に示す。
【００３３】
（比較例３）
防虫活性成分を含まない４−メチル−１−ペンテン共重合体を用い、実施例２と同様に首輪を製造した。得られた首輪により、実施例２と同様の方法で、ノミ成虫の出現率を測定した。結果を表３に示す。
【００３４】
【表３】

【００３５】
【発明の効果】
本発明の防虫活性成分が４−メチル−１−ペンテン系重合体中に含有されてなる防虫樹脂組成物は、従来のポリ塩化ビニルや高密度ポリエチレン等の樹脂基材を用いたものに比べて、低濃度の防虫活性成分の使用で優れた防虫効果を示すとともに長期間安定した防虫効果を持続させることができ、大量の防虫活性成分を配合した場合にも、組成物の物性に影響を与えることなく、しかも一定の速度で防虫活性成分を分散させる効果を有する。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a 4-methyl-1-pentene polymer insect repellent resin composition and a molded article obtained by using the composition. More specifically, a 4-methyl-1-pentene polymer insect repellent resin composition having a low environmental load, exhibiting an excellent insect repellent effect by using a low concentration of an insect repellent active ingredient, and capable of maintaining the effect for a long period of time. And a molded article formed from the composition.
[0002]
[Prior art]
Conventionally, as a composition of insect repellent tools for animals such as pets, there has been known a resin composition comprising polyvinyl chloride or polyurethane as a base material and an insect repellent active ingredient added thereto (JP-A-52-9057). No., JP-A-57-96650). However, chlorine-based resins such as polyvinyl chloride resin are feared to affect the environment.In addition, a resin molded body made of polyvinyl chloride or polyurethane has a large amount to obtain a sufficient insect repellent effect. Insect repellent active ingredients had to be blended, and it was difficult to maintain efficacy over a long period of time.
JP-A-06-315332 discloses an insect repellent resin composition in which an insect repellent active component is contained in a linear low-density polyethylene, and the linear low-density polyethylene has excellent diffusibility of the insect repellent active component. It is described that an insect repellent active ingredient having a lower concentration than the conventional one exhibits an excellent insect repellent effect over a long period of time. However, even if linear low-density polyethylene is used, the balance between the immediate effect and the permanence of the insect repellent active ingredient is not yet at a sufficient level, and further improvement has been desired.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a 4-methyl-1-pentene polymer which exhibits an excellent insect repellent effect by using a low concentration of an insect repellent active ingredient without adversely affecting living hormones, and which has a long-lasting effect. An object is to provide an insect repellent resin composition and a molded article obtained from the composition.
[0004]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a resin composition obtained by blending an insect repellent active component with a 4-methyl-1-pentene polymer having the lowest density among polyolefins has an environmental impact. It was found that the insect repellent active ingredient volatilized from the surface of the molded article was quickly supplied to the surface from inside the molded article, and the present invention was completed.
[0005]
That is, the present invention provides an insect repellent resin composition comprising a 4-methyl-1-pentene polymer containing 0.01 to 50% by weight of an insect repellent active component, and a molded article comprising the composition.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
The 4-methyl-1-pentene polymer used in the present invention is, for example, a homopolymer of 4-methyl-1-pentene or a copolymer of 4-methyl-1-pentene and another α-olefin. Is mentioned. Other α-olefins include, for example, ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, Examples thereof include α-olefins having 2 to 20 carbon atoms such as 1-octadecene and 1-eicosene. These α-olefins may be used alone or in combination of two or more. Among the α-olefins preferred in the present invention, among them, α-olefins having 7 to 20 carbon atoms, and particularly preferred are α-olefins having 10 to 20 carbon atoms.
[0007]
The content of the α-olefin in the 4-methyl-1-pentene polymer used in the present invention is usually 0 to 7% by weight, preferably 3 to 5% by weight.
[0008]
The method for producing the 4-methyl-1-pentene polymer of the present invention is not particularly limited, and the polymer is produced by a known method using a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. be able to. In addition, a crystalline polymer can be preferably used, and both an isotactic structure and a syndiotactic structure can be used. Particularly, a polymer having an isotactic structure is preferable, and it is easily available. Furthermore, there are no particular restrictions on the stereoregularity and molecular weight as long as they satisfy the moldability and have a strength that can withstand use when formed into a molded article. A commercially available resin can be used as it is (for example, TPX manufactured by Mitsui Chemicals, Inc.).
[0009]
The 4-methyl-1-pentene polymer used in the present invention has an MFR measured under the conditions of a load of 5.0 kg and a temperature of 260 ° C. according to ASTM D1238, of 1 to 400 g / 10 min, preferably 10 to 300 g / min. It is desirable to be in the range of 10 minutes.
[0010]
Furthermore, in order to efficiently disperse the insect repellent active ingredient in the 4-methyl-1-pentene polymer, it is effective to blend a modified 4-methyl-1-pentene polymer obtained by polymerizing a polar group-containing monomer. It is. Examples of the polar group-containing monomer include an organic acid having a carboxylic acid residue or the like, an unsaturated hydrocarbon compound having a group such as an amide, an amine or an alkylene oxide, and grafting by a known graft polymerization method. To introduce a polar group. Among these, a 4-methyl-1-pentene polymer modified with an unsaturated carboxylic acid such as maleic anhydride can be preferably used.
[0011]
As a method for obtaining a polar group-containing modified 4-methyl-1-pentene polymer, a so-called graft polymerization method used for modifying a well-known polyolefin can be applied. Specifically, it can be produced by mixing a 4-methyl-1-pentene polymer before modification with a polymerizable polar group-containing monomer in the presence of a known radical polymerization initiator such as an organic peroxide. . It can be produced in either a solid phase such as in an extruder or a liquid phase dissolved in a solvent.
[0012]
Although the graft ratio of the obtained polar group-containing modified 4-methyl-1-pentene polymer is not particularly limited, it is preferably 0.01 to 50% by weight. Control of the graft ratio can be easily performed by appropriately selecting the graft conditions.
[0013]
The modified polymer is generally used by mixing with an unmodified polymer, and the amount of the polar group-containing modified 4-methyl-1-pentene-based polymer is determined by the type and composition of the insect-controlling active ingredient. Although it depends on the use of the product, it is usually preferably 0.1 to 10 wt%.
[0014]
The insect-controlling active ingredient used in the present invention is not particularly limited. Examples of the insect repellent active ingredient include active ingredient compounds such as various insecticidal active ingredients, insect growth controlling active ingredients, and repellent active ingredients.
[0015]
The amount of the insect repellent active ingredient in the insect repellent resin composition varies depending on the kind of the insect repellent active ingredient and the use of the composition, but is usually 0.01 to 50% by weight.
[0016]
Specific examples of the insecticidal active component include, for example, pyrethroid compounds, organic phosphorus compounds, carbamate compounds, and phenylpyrazole compounds. Examples of the pyrethroid compound include permethrin, allethrin, d-allethrin, dd-allethrin, pralesulin, cyphenothrin, d-phenothrin, d-resmethrin, empentrin, fenvalerate, fenproprasulin, cyhalothrin, cyfurthrin, etofenprox, Tralomethrin, esbiosulin, benfluthulin, teralesulin, and the like.Examples of organophosphorus compounds include fenitrothion, dichlorvos, naled, fenthion, siaphos, chloropyrifos, diazinon, carclophos, salithion, diazinon, and the like. Diazones, propoxur, fenobukab, carbaryl, etc., and phenylpyrazole compounds such as fipronil. It is below.
[0017]
Specific examples of the insect growth controlling active ingredient include, for example, pyriproxyfen, mesoprene, hydroprene, diflubenzuron, cyromazine, phenoxysilomazine, phenoxycarb, lufenuron (CGA184599) and the like. Specific examples of the repellent active component include, for example, diethyltriamide, dibutylphthalate and the like. These insect repellent active ingredients may be used alone or in combination of two or more.
[0018]
In the present invention, in particular, the insect-controlling active ingredient is absorbed and absorbed, and can be taken into the inner surface or the surface, and is used by supporting the insect-controlling active ingredient on a carrier that does not exert an action such as decomposing the insect-controlling active ingredient. It is also possible. Since a large amount of insect repellent active ingredients can be retained on the carrier surface, etc., it is possible to use a low concentration of insect repellent active ingredients to show an excellent insect repellent effect and maintain a long-term stable insect repellent effect. Also in this case, it has the effect of dispersing the insect-controlling active ingredient at a constant rate without affecting the physical properties of the composition.
[0019]
The carrier for supporting the insect repellent active ingredient is not particularly limited, but specific examples include inorganic compounds such as silica, alumina and zeolite, and organic compounds such as cross-linked styrene and cyclodextrin. Among these, silica gel can be preferably used.
[0020]
The silica gel to be used may be a powdered industrial material that is usually used as a filler, and the compounding ratio is preferably 1 to 5 silica gels with respect to the insect repellent active ingredient 1 by weight ratio, more preferably 1 to 5 insect repellent active ingredients. On the other hand, it is silica gel 2.
[0021]
In the present invention, a compound having a role of enhancing the effect of the insect repellent active ingredient may be used together. Examples of the compound that enhances the effect of the insect repellent active ingredient include piperonyl butoxide, MGK264, octachlorodipropyl ether, and the like.
[0022]
In the present invention, various known additives such as a heat stabilizer, a weather stabilizer, a rust inhibitor, a copper damage stabilizer, and an antistatic agent can be blended as long as the object is not impaired.
[0023]
The insect repellent resin composition of the present invention can be produced by various known methods utilized in producing ordinary thermoplastic resin compositions. In particular, it is common to heat and mix, and specifically, a kneading method using an extruder or the like, specifically, an insect repellent active ingredient (may be used in a state of being supported on a carrier as necessary), 4-methyl It can be obtained by melt-kneading a -1-pentene polymer and, if necessary, a modified 4-methyl-1-pentene polymer containing a polar group in combination.
[0024]
The insect-prevented molded article molded from the insect-resistant resin composition of the present invention is not particularly limited, and is a molded article having an arbitrary shape molded by a known molding method according to desired use conditions. . Specific examples include an injection molded article, a net, a nonwoven fabric, a fiber, a sheet, and a film of an arbitrary shape. Further, depending on the purpose, a molded article formed by a processing method used for ordinary thermoplastic resins such as multilayer extrusion molding, multicolor injection molding, composite spinning, and extrusion lamination molding may be used.
[0025]
Animal tools molded from the insect-controlling resin composition of the present invention are not particularly limited. Any tool may be used as long as it is aimed at controlling insects, and examples include a collar of a pet or livestock.
[0026]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited at all by these examples.
[0027]
(Example 1)
The 4-methyl-1-pentene copolymer and phenothrin were hot-cut while being extruded at a weight ratio of 98/2 with a twin-screw extruder and pelletized to obtain an insect-resistant resin composition. This insect repellent resin composition was formed into a sheet having a size of 16 cm square and a thickness of 1 mm at a pressing temperature of 270 ° C., and the knockdown rate with the passage of time was measured by the following method using the obtained molded body. The results are shown in Tables 1 and 2.
(Measurement of knockdown rate)
A glass ring having a diameter of 45 mm and a height of 2 cm was placed on the sheet, and ten termite termites were released in the ring. The number of knockdowns after lapse of time was observed, and the knockdown rate was calculated from the average value of the number of repetitions 4.
[0028]
(Comparative Example 1)
Polyvinyl chloride, DOP (dioctyl phthalate) as a plasticizer, barium stearate, and phenothrin as stabilizers are kneaded for 5 minutes by roll kneading at a weight ratio of 57.8 / 40 / 0.2 / 2. The obtained sheet was pelletized with a sheet pelletizer to obtain an insect repellent resin composition. This insect-controlling resin composition was formed into a sheet having a size of 16 cm square and a thickness of 1 mm at a pressing temperature of 270 ° C., and the knockdown rate was measured in the same manner as in Example 1 using the obtained molded body. The results are shown in Tables 1 and 2.
[0029]
(Comparative Example 2)
The high-density polyethylene and phenothrin were extruded at a weight ratio of 98/2 by a twin-screw extruder and hot-cut to pelletize, thereby obtaining an insect-resistant resin composition. This insect-controlling resin composition was formed into a sheet having a size of 16 cm square and a thickness of 1 mm at a pressing temperature of 270 ° C., and the knockdown rate was measured in the same manner as in Example 1 using the obtained molded body. The results are shown in Tables 1 and 2.
[0030]
[Table 1]

[0031]
[Table 2]

[0032]
(Example 2)
The 4-methyl-1-pentene copolymer and phenothrin were hot-cut while being extruded at a weight ratio of 98/2 with a twin-screw extruder, and pelletized to obtain an insect-resistant resin composition. This insect repellent resin composition was injection-molded at a molding temperature of 270 ° C. to form a collar having a length of 35 cm, a width of 1 cm and a thickness of 4 mm. A buckle was attached to the collar and used as a collar, and the dog wearing the collar was bred in a breeding room where the floor surface was a carpet. Over time, the carpet was cut out, cut out into a circular shape with a diameter of 5 cm, and about 60 cat flea eggs were placed on the cut circle together with the cat flea bait. It was measured. The collar according to the present example exhibited an insect repellent effect for 8 weeks. Table 3 shows the results.
[0033]
(Comparative Example 3)
A collar was produced in the same manner as in Example 2 using a 4-methyl-1-pentene copolymer containing no insect-controlling active ingredient. The appearance rate of adult flea was measured with the obtained collar in the same manner as in Example 2. Table 3 shows the results.
[0034]
[Table 3]

[0035]
【The invention's effect】
The insect repellent resin composition comprising the insect repellent active ingredient of the present invention in a 4-methyl-1-pentene polymer is more effective than a conventional resin repellent using a resin substrate such as polyvinyl chloride or high-density polyethylene. The use of a low concentration of insect repellent active ingredient shows excellent insect repellent effect and can maintain the stable insect repellent effect for a long time. Even when a large amount of insect repellent active ingredient is blended, it affects the physical properties of the composition Without dispersing the insect repellent active ingredient at a constant rate.

Claims (3)

A 4-methyl-1-pentene polymer composition comprising 0.01 to 50% by weight of an insect repellent active ingredient. An insect-proof molded article obtained by molding the composition according to claim 1. An animal tool obtained by molding the composition according to claim 1.