JPWO2009069710A1 - Small animal control resin composition and small animal control resin molding - Google Patents

Abstract

Provided are a resin composition and a resin molded body that can maintain the repellent action of pests over a long period of time without being affected by the usage environment such as outdoors, high temperature environment, or exposure to water. This is the issue. A small animal control resin composition comprising a base resin, a plasticizer, a small animal control agent, and an inorganic filler, and further containing an additive capable of suppressing film formation on the resin surface. According to the featured small animal control resin composition. Further, the additive capable of suppressing the film formation on the resin surface is selected from the group consisting of a hindered phenol antioxidant, a phosphorus antioxidant, an ultraviolet absorbing light stabilizer, a hindered amine light stabilizer, and carbon. It is based on the small animal control resin composition characterized by being 1 type, or 2 or more types.

Description

  The present invention relates to a small animal control resin composition and a small animal control resin molded product, and more particularly to a small animal control resin composition and a small animal control resin molded product having excellent weather resistance against light, heat, water, and the like.

  Conventionally, it has been pointed out that harmful insects invade electric / communication equipment, transportation equipment, and the like, causing failure and trouble, and there is a demand for preventing the invasion of harmful insects into the equipment. In particular, since many of these devices have a relatively long product life, it is desired to prevent the invasion of pests as long as possible.

  Conventional insect repellent countermeasures were mainly performed by simply spraying medicines at entrances / routes and nesting sites. However, in consideration of the residual effects of drugs and environmental pollution, comprehensive control (IPM) is achieved by reducing the application of methods such as simply spraying the drugs as much as possible, combining them with environmental improvements such as structures that are difficult to enter and nest, and placement of natural enemies. : Integrated Pest Management) has become the current trend. In other words, it is considered that we have entered an era in which the control of reducing the amount of drugs and controlling the environmental load is selected by combining the control of multiple technologies such as drugs, environmental improvements and natural enemies.

In response to such a request, the following Patent Document 1 discloses a method in which an insect repellent is mixed in a moldable resin and a predetermined fibrous inorganic filler is added to obtain a resin molded body. According to such a method, a sustained release effect of the drug is obtained in which the insect repellent drug contained in the molded body of the resin composition gradually moves to the molded body surface through the fibrous inorganic filler. The effect that the repellent action can be maintained for a long time against pests is obtained.
In addition, since it is a resin molded body, the shape can be designed freely, and it has a shape that is difficult to enter and nest, combined with the effect of insect repellent components, it is possible to enter and enter the facility where insects tend to nest. Nesting can be prevented and device troubles can be prevented. Therefore, the amount of the insect repellent component can be reduced as much as the physical repellent repellent effect due to a shape that is difficult to enter, and the repellent repellent member that realizes IPM can be provided.
Further, according to the invention described in the cited reference 1, it is possible to increase the sustainability of the chemical repellent effect by the insect repellent component by 10 times or more as compared with the conventional plastic product for repelling insect repellent, and the shape. Since the physical effect of is semi-permanent, by providing a product to which the molded body is applied, it is possible to realize a product that is almost maintenance-free and can provide an insect repellent effect.

Japanese Unexamined Patent Publication No. 2000-21205

  However, according to the study by the present inventors, in the resin molded body described in Patent Document 1, the release action of the insect repellent agent is deteriorated depending on the environment in which the resin molded body is used, and the insect pest A problem has been found that the repellent effect may not be sustained for a sufficiently long time.

  The present invention provides a resin composition and a resin molded body that can maintain the repellent action of pests over a long period of time without being affected by the use environment of the resin molded body, in view of such problems of the prior art. One purpose.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive research.When the resin molded body is used outdoors, in a high-temperature environment, or exposed to water, the surface of the resin molded body A film that does not allow the penetration of the insect repellent agent is formed, and this film inhibits the migration of the insect repellent agent remaining inside the molded body to the surface, so that the drug inside the molded body is not fully utilized. The inventor has come up with the knowledge that the effective period has been shortened.

  That is, the present invention relates to a base resin (hereinafter sometimes simply referred to as “A component”), a plasticizer (hereinafter sometimes simply referred to as “B component”), a drug having a small animal control property (hereinafter simply referred to as “C”). A small animal control resin composition comprising an inorganic filler (hereinafter also simply referred to as “D component”), which can inhibit film formation on the resin surface. Provided is a small animal control resin composition comprising an agent (hereinafter sometimes simply referred to as “E component”).

  The present invention also provides a small animal control resin molded product obtained by molding the small animal control resin composition.

  Since the additive which can suppress the film formation on the resin surface is added as the E component to the small animal control resin composition according to the present invention, the small animal control resin formed by molding the small animal control resin composition Even when the molded body continues to be used in an outdoor environment, a high-temperature environment, or in a situation where it is exposed to water or the like, a film is hardly formed on the surface of the resin molded body. Therefore, since the transfer of the small animal control agent contained in the molded body to the surface of the molded body is difficult to be inhibited, the release action due to the synergistic effect of the compound as the B component and the inorganic filler as the D component is long-term. This is effective over a long period of time, and has the effect that the effect of controlling small animals is more easily maintained.

(A) And (b) is a cross-sectional photograph before the exposure of the molded article for test used in Comparative Example 1, and (c) and (d) are also cross-sectional photographs after an exposure time of 200 hours. (A) And (b) is a cross-sectional photograph before the exposure of the test molded product used in Example 3, and (c) and (d) are also cross-sectional photographs after an exposure time of 200 hours. The graph which showed the analysis result by the X ray electron spectroscopy (XPS) in the vicinity of the molded article surface before exposure and 200 hours after exposure time about the test molded article used in the comparative example 1. FIG. The graph which showed the analysis result by the X ray electron spectroscopy (XPS) in the vicinity of the molded article surface before exposure and 200 hours after exposure time about the test molded article used in Example 3. FIG.

  The base resin (component A) used in the present invention is not particularly limited. For example, polyamide resin, polyacetal resin, polyethylene resin, polypropylene resin, polystyrene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate Examples thereof include resins, polyarylate resins, polyphenylene ether resins, thermoplastic polyurethane resins, and liquid crystalline polyester resins.

  Specific examples of the polyamide resin include polyamide resins such as polyamide 6, polyamide 66, polyamide 11 and polyamide 12 resin, and aromatic polyamide resins such as polyamide MXD and polyamide 6T resin.

  Specific examples of the polyacetal resin include, in addition to a homopolymer consisting only of oxymethylene units, copolymers having oxymethylene units as main components and other copolymer units such as oxyethylene units as subcomponents thereof, these Examples thereof include a cross-linked polymer obtained by cross-linking and a graft copolymer formed by graft copolymerization.

  Specific examples of the polyethylene resin include high density polyethylene, low density polyethylene, ultra low density polyethylene, and linear low density polyethylene.

  Specific examples of the polypropylene resin include a polypropylene homopolymer, a random copolymer of ethylene and propylene, and a block copolymer.

Specific examples of polystyrene resins include styrene homopolymers, styrene-acrylic acid copolymers based on styrene, styrene-methyl acrylate copolymers, styrene-ethyl acrylate copolymers, styrene-methacrylic copolymers. Acid copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-maleic anhydride copolymer, styrene-polyphenylene ether copolymer, styrene-butadiene copolymer, styrene-acrylonitrile Examples of the copolymer include acrylonitrile-butadiene-styrene copolymer, styrene-methylstyrene copolymer, styrene-dimethylstyrene copolymer, styrene-ethylstyrene copolymer, and styrene-diethylstyrene copolymer.
The styrene component content in the styrene-based copolymer is preferably 50 mol% or more, particularly preferably 80 mol% or more.

  As the polyethylene terephthalate resin, a polymer obtained by polycondensation using terephthalic acid as an acid component and ethylene glycol as a glycol component can be used. In addition, as an acid component, isophthalic acid, naphthalenedicarboxylic acid, adipic acid, Sebacic acid, dodecanedioic acid, oxalic acid, etc. as propylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol , Cyclohexanediol or the like, or a long chain glycol having a molecular weight of 400 to 6000, that is, a copolymer of 20 mol% or less of polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. Rukoto can also.

The polybutylene terephthalate resin has a structure in which terephthalic acid units and 1,4-butanediol units are ester-bonded, 50 mol% or more of dicarboxylic acid units are composed of terephthalic acid units, and 50 mol% or more of diol components are A polymer composed of 1,4-butanediol units can be preferably used.
When there are too few terephthalic acid units or 1,4-butanediol units, for example, when there are less than 50 mol%, the crystallization rate of PBT resin will fall and the moldability of the polybutylene terephthalate resin obtained may fall. Therefore, the proportion of terephthalic acid units in all dicarboxylic acid units is usually 70 mol% or more, preferably 80 mol% or more, more preferably 95 mol% or more, and particularly preferably 98 mol% or more. The proportion of 1,4 butanediol units is usually 70 mol% or more, preferably 80 mol% or more, more preferably 95 mol% or more, and particularly preferably 98 mol% or more.
In the dicarboxylic acid component which is a raw material of the polybutylene terephthalate resin, there is no particular limitation on the dicarboxylic acid component other than terephthalic acid. Specifically, for example, phthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, Aromatic dicarboxylic acids such as 4,4′-diphenylsulfone dicarboxylic acid and 2,6-naphthalenedicarboxylic acid; fats such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid Cyclic dicarboxylic acids; aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid; These dicarboxylic acid components can be introduced into the polymer skeleton as a dicarboxylic acid or using a dicarboxylic acid derivative such as a dicarboxylic acid ester or a dicarboxylic acid halide as a raw material.
Moreover, in the diol component which is a raw material of this polybutylene terephthalate resin, there is no restriction | limiting in particular as diol components other than 1, 4- butanediol. Specifically, for example, ethylene glycol, diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, polypropylene glycol, polytetramethylene glycol, dibutylene glycol, 1,5-pentanediol, neopentyl glycol Aliphatic diols such as 1,6-hexanediol and 1,8-octanediol; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4-cyclohexanedimethylol Alicyclic diols such as xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, and the like; Cited The
Furthermore, the polybutylene terephthalate resin may be a copolymer of any conventionally known monomer unit. Specific examples of the monomer component include hydroxy such as lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, and p-β-hydroxyethoxybenzoic acid. Carboxylic acids; monofunctional components such as alkoxycarboxylic acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid, benzoylbenzoic acid; tricarbaric acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid And trifunctional or higher polyfunctional components such as acid, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, and the like.

Examples of the polycarbonate resin include polymers obtained by a phosgene method in which various dihydroxy diaryl compounds and phosgene are reacted or a transesterification method in which a dihydroxy diaryl compound and a carbonic ester such as diphenyl carbonate are reacted. A typical example is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A).
Examples of the dihydroxydiaryl compound include bisphenol 4-, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane 1,1-bis (4-hydroxy-3- Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4 Bis (hydroxyaryl) alkanes such as -hydroxy-3,5-dichlorophenyl) propane; (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3, Dihydroxy diaryl ethers such as 3′-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′- Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone, dihydroxy diaryl sulfones such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, etc. It is below.
These may be used alone or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, and the like may be used in combination.
Furthermore, the dihydroxyaryl compound and a trivalent or higher valent phenol compound as shown below may be used in combination.
Trihydric or higher phenols include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4′-dihydroxydiphenyl) -cyclohexyl] -propane and the like.
The viscosity average molecular weight of the polycarbonate resin is not particularly limited, but is usually 10,000 to 100,000, more preferably 15,000 to 30,000, and further preferably 17,000 to 26,000 from the viewpoints of moldability and strength. Moreover, when manufacturing this polycarbonate resin, a molecular weight modifier, a catalyst, etc. can be used as needed.

As the polyarylate resin, a resin having an aromatic dicarboxylic acid residue and a bisphenol residue as repeating units can be used.
Polyarylate raw materials for introducing bisphenol residues are bisphenols, and specific examples thereof include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5- Dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 4,4′-dihydroxydiphenylsulfone 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, etc. It is done. These compounds may be used alone or in combination of two or more. In particular, 2,2-bis (4-hydroxyphenyl) propane is economically preferable, and it is optimal to use the compound alone.
On the other hand, as a raw material for introducing an aromatic dicarboxylic acid residue into a polyarylate resin, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenic acid, Examples include 4,4′-dicarboxydiphenyl ether, bis (p-carboxyphenyl) alkane, 4,4′-dicarboxydiphenyl sulfone, and terephthalic acid and isophthalic acid are particularly preferable. In the present invention, a polyarylate resin composition obtained by mixing and using both is particularly preferable in terms of melt processability and mechanical properties. The mixing ratio (terephthalic acid / isophthalic acid) can be arbitrarily selected, but is preferably in the range of 90/10 to 10/90 in terms of molar fraction, more preferably 70/30 to 30/70, The optimum is 50/50. Even if the mixed mole fraction of terephthalic acid is less than 10 mol% or more than 90 mol%, it may be difficult to obtain a sufficient degree of polymerization by the interfacial polymerization method.
It is desirable that the polyarylate resin has an intrinsic viscosity of 0.4 to 1.0, preferably 0.4 to 0.8, more preferably 0.5 to 0.7, from the viewpoint of mechanical properties and fluidity. .

（Ｒ1、Ｒ4は、それぞれ独立して、水素、第一級若しくは第二級の低級アルキル、フェニル、アミノアルキル、炭化水素オキシを表わす。Ｒ2、Ｒ3は、それぞれ独立して、水素、第一級若しくは第二級の低級アルキル、フェニルを表わす。）
該ポリフェニレンエーテル樹脂の具体例としては、ポリ（２，６−ジメチル−１，４−フェニレンエーテル）、ポリ（２−メチル−６−エチル−１，４−フェニレンエーテル）、ポリ（２−メチル−６−フェニル−１，４−フェニレンエーテル）、ポリ（２，６−ジクロロ−１，４−フェニレンエーテル）等が挙げられ、さらに、２，６−ジメチルフェノールと他のフェノール類（例えば、２，３，６−トリメチルフェノールや２−メチル−６−ブチルフェノール）との共重合体のようなポリフェニレンエーテル共重合体も挙げられる。中でもポリ（２，６−ジメチル−１，４−フェニレンエーテル）、２，６−ジメチルフェノールと２，３，６−トリメチルフェノールとの共重合体が好ましく、さらにポリ（２，６−ジメチル−１，４−フェニレンエーテル）が好ましい。
該ポリフェニレンエーテル樹脂の製造方法の例としては、米国特許第３３０６８７４号明細書記載の第一銅塩とアミンのコンプレックスを触媒として用い、２，６−キシレノールを酸化重合する方法がある。
米国特許第３３０６８７５号、同第３２５７３５７号及び同第３２５７３５８号の各明細書、日本国特公昭５２−１７８８０号及び日本国特開昭５０−５１１９７号及び日本国特開昭６３−１５２６２８号の各公報等に記載された方法も、ポリフェニレンエーテル樹脂の製造方法として好ましい。
該ポリフェニレンエーテル樹脂は、重合工程後のパウダーのまま用いてもよいし、押出機などを用いて、窒素ガス雰囲気下あるいは非窒素ガス雰囲気下、脱揮下あるいは非脱揮下にて溶融混練することでペレット化して用いてもよい。
該ポリフェニレンエーテル樹脂には、種々のジエノフィル化合物により官能化されたポリフェニレンエーテルも含まれる。種々のジエノフィル化合物としては、例えば無水マレイン酸、マレイン酸、フマル酸、フェニルマレイミド、イタコン酸、アクリル酸、メタクリル酸、メチルアリレート、メチルメタクリレート、グリシジルアクリレート、グリシジルメタクリレート、ステアリルアクリレート及びスチレンが挙げられる。これらジエノフィル化合物によりポリフェニレンエーテルを官能化するには、ラジカル発生剤存在下あるいは非存在下で押出機などを用い、脱揮下あるいは非脱揮下において溶融状態で官能化してもよいし、ラジカル発生剤存在下あるいは非存在下で、非溶融状態、すなわち室温以上かつ融点以下の温度範囲で官能化してもよい。官能化されたポリフェニレンエーテルの融点は、示差熱走査型熱量計（ＤＳＣ）の測定において、２０℃／分で昇温するときに得られる温度−熱流量グラフで観測されるピークのピークトップ温度で定義され、ピークトップ温度が複数ある場合にはその内の最高の温度で定義される。
該ポリフェニレンエーテル樹脂は、芳香族ビニル系重合体等、ポリフェニレンエーテル以外の樹脂成分を含有しても良い。芳香族ビニル系重合体の例としてはアタクティックポリスチレン、ハイインパクトポリスチレン、シンジオタクティックポリスチレン及びアクリロニトリル−スチレン共重合体が挙げられる。ポリフェニレンエーテル系樹脂がポリフェニレンエーテル樹脂及び芳香族ビニル系重合体を含有する場合、ポリフェニレンエーテル樹脂と芳香族ビニル系重合体との合計量に対して、ポリフェニレンエーテル樹脂を７０ｗｔ％以上とし、好ましくは８０ｗｔ％以上とする。The polyphenylene ether resin has a repeating unit structure of the following formula (1), and has a reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) in the range of 0.15 to 1.0 dl / g. Polymers and / or copolymers can be used. A more preferred reduced viscosity is in the range of 0.20 to 0.70 dl / g, most preferably in the range of 0.40 to 0.60.

(R1 and R4 each independently represent hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl, or hydrocarbonoxy. R2 and R3 each independently represent hydrogen, primary or Or secondary lower alkyl, phenyl.)
Specific examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl- 6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), and the like. Furthermore, 2,6-dimethylphenol and other phenols (for example, 2, Polyphenylene ether copolymers such as copolymers with 3,6-trimethylphenol and 2-methyl-6-butylphenol are also included. Of these, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1 , 4-phenylene ether).
As an example of a method for producing the polyphenylene ether resin, there is a method of oxidative polymerization of 2,6-xylenol using a complex of cuprous salt and amine described in US Pat. No. 3,306,874 as a catalyst.
U.S. Pat. Nos. 3,306,875, 3,257,357 and 3,257,358, Japanese Patent Publication No. 52-17880, Japanese Unexamined Patent Publication No. 50-51197 and Japanese Unexamined Patent Publication No. 63-152628. The method described in the publication is also preferable as a method for producing a polyphenylene ether resin.
The polyphenylene ether resin may be used as it is after the polymerization step, or melt kneaded using an extruder or the like under a nitrogen gas atmosphere or a non-nitrogen gas atmosphere, devolatilization or non-devolatilization. It may be used as a pellet.
The polyphenylene ether resin also includes polyphenylene ether functionalized with various dienophile compounds. Examples of various dienophile compounds include maleic anhydride, maleic acid, fumaric acid, phenylmaleimide, itaconic acid, acrylic acid, methacrylic acid, methyl allylate, methyl methacrylate, glycidyl acrylate, glycidyl methacrylate, stearyl acrylate and styrene. In order to functionalize polyphenylene ether with these dienophile compounds, an extruder may be used in the presence or absence of a radical generator, which may be functionalized in a molten state under devolatilization or non-devolatilization. The functionalization may be performed in the non-molten state, that is, in the temperature range from room temperature to the melting point in the presence or absence of the agent. The melting point of the functionalized polyphenylene ether is the peak top temperature of the peak observed in the temperature-heat flow graph obtained when the temperature is raised at 20 ° C./min in the differential thermal scanning calorimeter (DSC) measurement. If there are multiple peak top temperatures, the highest temperature is defined.
The polyphenylene ether resin may contain a resin component other than polyphenylene ether, such as an aromatic vinyl polymer. Examples of the aromatic vinyl polymer include atactic polystyrene, high impact polystyrene, syndiotactic polystyrene, and acrylonitrile-styrene copolymer. When the polyphenylene ether resin contains a polyphenylene ether resin and an aromatic vinyl polymer, the polyphenylene ether resin is 70 wt% or more, preferably 80 wt%, based on the total amount of the polyphenylene ether resin and the aromatic vinyl polymer. % Or more.

  As the thermoplastic polyurethane resin, a thermoplastic polyurethane resin containing polyisocyanate and polyol as starting materials can be used. Among them, the content of oxyethylene groups in the thermoplastic polyurethane resin is 40% by mass or more and 65% by mass or less. A film having a softening temperature of 160 ° C. or higher by thermomechanical analysis (TMA) when a film having a thickness of 20 μm is suitable.

前記液晶ポリエステル樹脂は、分子鎖中に脂肪族基を有する半芳香族液晶ポリエステル樹脂、または分子鎖が全て芳香族基より構成される全芳香族液晶ポリエステル樹脂の何れを用いてもよい。これらの液晶ポリエステル樹脂の中では、難燃性や機械的物性が良好であることから全芳香族液晶ポリエステル樹脂を用いるのが好ましい。
前記液晶ポリエステル樹脂を構成する繰返し単位としては、芳香族オキシカルボニル繰返し単位、芳香族ジカルボニル繰返し単位、芳香族ジオキシ繰返し単位、芳香族オキシジカルボニル繰返し単位、および脂肪族ジオキシ繰返し単位などが挙げられる。
前記液晶ポリエステル樹脂は、これらの各繰返し単位の中でも、芳香族オキシカルボニル繰り返し単位として、式（２）で表される６−オキシ−２−ナフトイル繰り返し単位、および／または、式（３）で表されるパラオキシベンゾイル繰り返し単位を必須に含むものである。
前記液晶ポリエステル樹脂において、全繰り返し単位中での式（２）で表される繰り返し単位の量は、得られる液晶ポリエステル樹脂組成物が高い靭性（衝撃強度）を示すために、４０モル％未満であり、３５モル％以下であるのが好ましく、３０モル％以下であるのが特に好ましい。
前記液晶ポリエステル樹脂において、全繰り返し単位中での式（３）で表される繰り返し単位の量は、本発明の目的が達成され、式（２）で表される繰り返し単位の全繰り返し単位中の量が４０モル％未満である限り、特に制限されないが、８０モル％以下であるのが好ましく、７５モル％以下であるのが特に好ましい。
式（２）の繰り返し単位を与える単量体としては、６−ヒドロキシ−２−ナフトエ酸が挙げられ、式（３）の繰り返し単位を与える単量体としては、パラヒドロキシ安息香酸が挙げられる。これらの単量体はアシル化物、エステル誘導体、酸ハロゲン化物などのエステル形成性誘導体として用いてもよい。
前記液晶ポリエステル樹脂が、式（２）および式（３）で表される繰り返し単位のみから構成される場合には、液晶ポリエステル樹脂の全繰り返し単位中での式（２）で表される繰り返し単位の含有量は、１５〜３０モル％であるのが好ましく、２０〜３０モル％であるのが特に好ましい。
前記液晶ポリエステル樹脂は、式（２）および式（３）以外の芳香族オキシカルボニル繰り返し単位を含んでいても良い。
式（２）および式（３）以外の芳香族オキシカルボニル繰返し単位を与える単量体の具体例としては、たとえばメタヒドロキシ安息香酸、オルトヒドロキシ安息香酸、５−ヒドロキシ−２−ナフトエ酸、３−ヒドロキシ−２−ナフトエ酸、４’−ヒドロキシフェニル−４−安息香酸、３’−ヒドロキシフェニル−４−安息香酸、４’−ヒドロキシフェニル−３−安息香酸、これらのアルキル、アルコキシまたはハロゲン置換体、ならびに６−ヒドロキシ−２−ナフトエ酸およびパラヒドロキシ安息香酸のアルキル、アルコキシまたはハロゲン置換体が挙げられる。これらの単量体はアシル化物、エステル誘導体、酸ハロゲン化物などのエステル形成性誘導体として用いてもよい。
本発明において、好ましい全芳香族液晶ポリエステル樹脂は、式（２）で表される繰り返し単位、および／または、式（３）で表される繰り返し単位、並びに芳香族ジカルボニル繰り返し単位および芳香族ジオキシ繰り返し単位からなるものである。
さらに好ましい全芳香族液晶ポリエステル樹脂は、式（２）で表される繰り返し単位と式（３）で表される繰り返し単位の合計量が、全繰り返し単位中５０〜９０モル％であり、かつ、芳香族ジオキシ繰り返し単位および芳香族ジカルボニル繰り返し単位の含有量が実質的に等モルであるものである。
上記のように液晶ポリエステル樹脂が、芳香族ジカルボニル繰り返し単位および芳香族ジオキシ繰り返し単位を含むものである場合には、両繰り返し単位の、液晶ポリエステル樹脂の全繰り返し単位中での含有量は実質的に等モルであるのが好ましい。
ここで、芳香族ジカルボニル繰り返し単位と芳香族ジオキシ繰り返し単位の含有量が実質的に等モルであるとは、液晶ポリエステル樹脂中での両繰り返し単位の含有量（モル％)の比が９５／１００〜１００／９５であることを意味する。
前記液晶ポリエステル樹脂において、芳香族ジカルボニル繰返し単位を与える単量体の具体例としては、たとえばテレフタル酸、イソフタル酸、２,６−ナフタレンジカルボン酸、１,６−ナフタレンジカルボン酸、２,７−ナフタレンジカルボン酸、１，４−ナフタレンジカルボン酸、４,４’−ジカルボキシビフェニル等の芳香族ジカルボン酸、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのエステル誘導体、酸ハロゲン化物などのエステル形成性誘導体が挙げられる。これらの中ではテレフタル酸、および２,６−ナフタレンジカルボン酸が得られる液晶ポリエステルの機械物性、耐熱性、融点温度、成形性を適度なレベルに調整しやすいことから好ましい。
前記液晶ポリエステル樹脂において、芳香族ジオキシ繰返し単位を与える単量体の具体例としては、たとえばハイドロキノン、レゾルシン、２,６−ジヒドロキシナフタレン、２,７−ジヒドロキシナフタレン、１,６−ジヒドロキシナフタレン、１，４−ジヒドロキシナフタレン、４,４’−ジヒドロキシビフェニル、３,３’−ジヒドロキシビフェニル、３,４’−ジヒドロキシビフェニル、４,４’−ジヒドロキシビフェニルエ−テル等の芳香族ジオール、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのアシル化物などのエステル形成性誘導体が挙げられる。これらの中ではハイドロキノン、レゾルシン、および４,４’−ジヒドロキシビフェニルが重合時の反応性、得られる液晶ポリエステル樹脂の特性などの点から好ましい。
前記液晶ポリエステル樹脂において、芳香族オキシジカルボニル繰返し単位を与える単量体の具体例としては、たとえば３−ヒドロキシ−２，７−ナフタレンジカルボン酸、４−ヒドロキシイソフタル酸、および５−ヒドロキシイソフタル酸等のヒドロキシ芳香族ジカルボン酸、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのアシル化物、エステル誘導体、酸ハロゲン化物などのエステル形成性誘導体が挙げられる。
本発明に用いる液晶ポリエステル樹脂において、脂肪族ジオキシ繰返し単位を与える単量体の具体例としては、たとえばエチレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオールなどの脂肪族ジオール、ならびにそれらのアシル化物が挙げられる。また、ポリエチレンテレフタレートや、ポリブチレンテレフタレートなどの脂肪族ジオキシ繰返し単位を含有するポリエステルを、前記の芳香族オキシカルボン酸、芳香族ジカルボン酸、芳香族ジオールおよびそれらのアシル化物、エステル誘導体、酸ハロゲン化物などと反応させることによっても、脂肪族ジオキシ繰返し単位を含む液晶ポリエステル樹脂を得ることができる。
前記液晶ポリエステル樹脂は、本発明の目的を損なわない範囲で、アミド結合やチオエステル結合を含むものであってもよい。このような結合を与える単量体としては、ヒドロキシ芳香族アミン、芳香族ジアミン、芳香族アミノカルボン酸、メルカプト芳香族カルボン酸、および芳香族ジチオールおよびヒドロキシ芳香族チオールなどが挙げられる。これらの単量体の使用量は、芳香族オキシカルボニル繰返し単位、芳香族ジカルボニル繰返し単位、芳香族ジオキシ繰返し単位、芳香族オキシジカルボニル繰返し単位、および脂肪族ジオキシ繰返し単位を与える単量体の合計量に対して１０モル％以下であるのが好ましい。
これらの繰り返し単位を組み合わせた液晶ポリエステル樹脂は、 モノマーの構成や組成比、ポリマー中での各繰り返し単位のシークエンス分布によっては、異方性溶融相を形成するものとしないものが存在するが、本発明に用いる液晶ポリエステル樹脂は異方性溶融相を形成するものに限られる。
好ましい液晶ポリエステル樹脂の具体例としては、例えば下記のモノマー構成単位からなるものが挙げられる。
１）４−ヒドロキシ安息香酸／２−ヒドロキシ−６−ナフトエ酸共重合体
２）４−ヒドロキシ安息香酸／テレフタル酸／４,４'−ジヒドロキシビフェニル共重合体
３）４−ヒドロキシ安息香酸／テレフタル酸／イソフタル酸／４,４'−ジヒドロキシビフェニル共重合体
４）４−ヒドロキシ安息香酸／テレフタル酸／イソフタル酸／４,４'−ジヒドロキシビフェニル／ハイドロキノン共重合体
５）４−ヒドロキシ安息香酸／テレフタル酸／ハイドロキノン共重合体
６）２−ヒドロキシ−６−ナフトエ酸／テレフタル酸／ハイドロキノン共重合体
７）４−ヒドロキシ安息香酸／２−ヒドロキシ−６−ナフトエ酸／テレフタル酸／４,４'−ジヒドロキシビフェニル共重合体
８）２−ヒドロキシ−６−ナフトエ酸／テレフタル酸／４,４'−ジヒドロキシビフェニル共重合体
９）４−ヒドロキシ安息香酸／２−ヒドロキシ−６−ナフトエ酸／テレフタル酸／ハイドロキノン共重合体
１０）４−ヒドロキシ安息香酸／２,６−ナフタレンジカルボン酸／４,４'−ジヒドロキシビフェニル共重合体
１１）４−ヒドロキシ安息香酸／テレフタル酸／２,６−ナフタレンジカルボン酸／ハイドロキノン共重合体
１２）４−ヒドロキシ安息香酸／２,６−ナフタレンジカルボン酸／ハイドロキノン共重合体
１３）４−ヒドロキシ安息香酸／２−ヒドロキシ−６−ナフトエ酸／２,６−ナフタレンジカルボン酸／ハイドロキノン共重合体
１４）４−ヒドロキシ安息香酸／テレフタル酸／２,６−ナフタレンジカルボン酸／ハイドロキノン／４,４'−ジヒドロキシビフェニル共重合体
１５）４−ヒドロキシ安息香酸／テレフタル酸／エチレングリコール共重合体
１６）４−ヒドロキシ安息香酸／テレフタル酸／４,４'−ジヒドロキシビフェニル／エチレングリコール共重合体
１７）４−ヒドロキシ安息香酸／２−ヒドロキシ−６−ナフトエ酸／テレフタル酸／エチレングリコール共重合体
１８）４−ヒドロキシ安息香酸／２−ヒドロキシ−６−ナフトエ酸／テレフタル酸／４,４'−ジヒドロキシビフェニル／エチレングリコール共重合体
１９）４−ヒドロキシ安息香酸／テレフタル酸／２,６−ナフタレンジカルボン酸／４,４−ジヒドロキシビフェニル共重合体。
これらの中では、耐熱性および機械的性質に優れることなどから、上記１）、１３）、または１９）から選択される共重合体を、液晶ポリエステル樹脂として用いるのが好ましい。
前記液晶ポリエステル樹脂の、示差操作熱量計により測定される結晶融解温度（Ｔｍ）は特に限定されないが、耐熱性の点から、３２０〜３８０℃であるのが好ましく、３２５〜３８０℃であるのがより好ましく、３３０〜３８０℃であるのが最も好ましい。なお、結晶融解温度（Ｔｍ）は以下に記載する方法により測定されるものである。
〈結晶融解温度測定方法〉
示差走査熱量計としてセイコーインスツルメンツ株式会社製Ｅｘｓｔａｒ６０００を用いる。液晶ポリエステル樹脂の試料を、室温から２０℃／分の昇温条件で測定した際に観測される吸熱ピーク温度（Ｔｍ１）の測定後、Ｔｍ１より２０〜５０℃高い温度で１０分間保持する。ついで、２０℃／分の降温条件で室温まで試料を冷却し、さらに、再度２０℃／分の昇温条件で測定した際の吸熱ピークを観測し、そのピークトップを示す温度を液晶ポリエステル樹脂の結晶融解温度（Ｔｍ）とする。
また、本発明に用いる液晶ポリエステル樹脂の、ＡＳＴＭ Ｄ６４８に準拠し測定される荷重撓み温度は、２７０〜３４０℃であるのが好ましく、２８０〜３４０℃であるのがより好ましく、２９０〜３４０℃であるのが最も好ましい。
なお、荷重撓み温度は以下に記載する方法により測定されるものである。
〈荷重撓み温度測定方法〉
射出成形機（日精樹脂工業（株）製ＵＨ１０００−１１０）を用いて長さ１２７ｍｍ、幅１２．７ｍｍ、厚さ３．２ｍｍの短冊状試験片を成形し、これを用いてＡＳＴＭ Ｄ６４８に準拠し、荷重１．８２ＭＰａ、昇温速度２℃／分で測定する。
さらに、本発明に用いる液晶ポリエステル樹脂のキャピラリーレオメーターにより測定される溶融粘度は、１０〜１００Ｐａ・ｓであるのが好ましく、１０〜８０Ｐａ・ｓであるのがより好ましく、１０〜６０Ｐａ・ｓであるのが最も好ましい。
なお、溶融粘度は以下に記載する方法により測定されるものである。
〈溶融粘度測定方法〉
溶融粘度測定装置（東洋精機（株）製キャピログラフ１Ｄ）を用い、０．７ｍｍφ×１０ｍｍのキャピラリーで、結晶融解温度（Ｔｍ）＋３０℃の温度条件にて剪断速度１０^３ｓ^−１での粘度を測定し、溶融粘度とする。As the liquid crystalline polyester resin, a liquid crystalline polyester resin that forms an anisotropic molten phase called a thermotropic liquid crystalline polyester can be used.
The property of the anisotropic molten phase of the liquid crystal polyester resin can be confirmed by a normal deflection inspection method using an orthogonal deflector, that is, by observing a sample placed on a hot stage in a nitrogen atmosphere.
The liquid crystalline polyester resin used in the present invention includes a repeating unit represented by the formula (2) and / or a repeating unit represented by the formula (2) and a repeating unit represented by the formula (2). It is also possible to use a blend of two or more liquid crystal polyester resins whose amount is less than 40 mol% in all repeating units.

As the liquid crystal polyester resin, either a semi-aromatic liquid crystal polyester resin having an aliphatic group in the molecular chain or a wholly aromatic liquid crystal polyester resin in which the molecular chains are all composed of aromatic groups may be used. Among these liquid crystal polyester resins, it is preferable to use a wholly aromatic liquid crystal polyester resin because of its good flame retardancy and mechanical properties.
Examples of the repeating unit constituting the liquid crystal polyester resin include an aromatic oxycarbonyl repeating unit, an aromatic dicarbonyl repeating unit, an aromatic dioxy repeating unit, an aromatic oxydicarbonyl repeating unit, and an aliphatic dioxy repeating unit. .
Among these repeating units, the liquid crystalline polyester resin is a 6-oxy-2-naphthoyl repeating unit represented by the formula (2) and / or a formula (3) as an aromatic oxycarbonyl repeating unit. The paraoxybenzoyl repeating unit is essential.
In the liquid crystal polyester resin, the amount of the repeating unit represented by the formula (2) in all repeating units is less than 40 mol% in order that the obtained liquid crystal polyester resin composition exhibits high toughness (impact strength). Yes, it is preferably 35 mol% or less, and particularly preferably 30 mol% or less.
In the liquid crystal polyester resin, the amount of the repeating unit represented by the formula (3) in all the repeating units is achieved by the purpose of the present invention, and the repeating unit represented by the formula (2) in all the repeating units. As long as the amount is less than 40 mol%, it is not particularly limited, but it is preferably 80 mol% or less, and particularly preferably 75 mol% or less.
Examples of the monomer that gives the repeating unit of formula (2) include 6-hydroxy-2-naphthoic acid, and examples of the monomer that gives the repeating unit of formula (3) include parahydroxybenzoic acid. These monomers may be used as ester-forming derivatives such as acylated products, ester derivatives and acid halides.
When the liquid crystalline polyester resin is composed of only repeating units represented by the formulas (2) and (3), the repeating unit represented by the formula (2) in all repeating units of the liquid crystal polyester resin. The content of is preferably 15 to 30 mol%, particularly preferably 20 to 30 mol%.
The liquid crystal polyester resin may contain an aromatic oxycarbonyl repeating unit other than those represented by formulas (2) and (3).
Specific examples of monomers that give aromatic oxycarbonyl repeating units other than those represented by formulas (2) and (3) include, for example, metahydroxybenzoic acid, orthohydroxybenzoic acid, 5-hydroxy-2-naphthoic acid, 3- Hydroxy-2-naphthoic acid, 4′-hydroxyphenyl-4-benzoic acid, 3′-hydroxyphenyl-4-benzoic acid, 4′-hydroxyphenyl-3-benzoic acid, alkyl, alkoxy or halogen substituents thereof, And alkyl, alkoxy or halogen substitutions of 6-hydroxy-2-naphthoic acid and parahydroxybenzoic acid. These monomers may be used as ester-forming derivatives such as acylated products, ester derivatives and acid halides.
In the present invention, preferred wholly aromatic liquid crystal polyester resins include the repeating unit represented by the formula (2) and / or the repeating unit represented by the formula (3), the aromatic dicarbonyl repeating unit and the aromatic dioxy. It consists of repeating units.
Further preferred wholly aromatic liquid crystal polyester resin, the total amount of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) is 50 to 90 mol% in all repeating units, and The content of the aromatic dioxy repeating unit and the aromatic dicarbonyl repeating unit is substantially equimolar.
When the liquid crystal polyester resin includes an aromatic dicarbonyl repeating unit and an aromatic dioxy repeating unit as described above, the content of both repeating units in all the repeating units of the liquid crystal polyester resin is substantially equal. Mole is preferred.
Here, the content of the aromatic dicarbonyl repeating unit and the aromatic dioxy repeating unit is substantially equimolar means that the ratio (mol%) of both repeating units in the liquid crystal polyester resin is 95 /%. It means 100-100 / 95.
In the liquid crystal polyester resin, specific examples of the monomer giving an aromatic dicarbonyl repeating unit include, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7- Ester formation of aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, alkyl, alkoxy or halogen-substituted products thereof, and ester derivatives and acid halides thereof Sex derivatives. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable because the liquid crystal polyesters from which terephthalic acid and 2,6-naphthalenedicarboxylic acid are obtained can be easily adjusted to an appropriate level.
In the liquid crystal polyester resin, specific examples of the monomer giving an aromatic dioxy repeating unit include, for example, hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1, Aromatic diols such as 4-dihydroxynaphthalene, 4,4′-dihydroxybiphenyl, 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl ether, alkyls and alkoxys thereof Alternatively, halogen-substituted products, and ester-forming derivatives such as acylated products thereof can be mentioned. Among these, hydroquinone, resorcin, and 4,4′-dihydroxybiphenyl are preferable from the viewpoint of reactivity during polymerization, characteristics of the obtained liquid crystal polyester resin, and the like.
In the liquid crystal polyester resin, specific examples of the monomer that gives an aromatic oxydicarbonyl repeating unit include, for example, 3-hydroxy-2,7-naphthalenedicarboxylic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, and the like. Hydroxy aromatic dicarboxylic acids, their alkyl, alkoxy or halogen-substituted products, and ester-forming derivatives thereof such as acylated products, ester derivatives and acid halides.
In the liquid crystal polyester resin used in the present invention, specific examples of the monomer that gives an aliphatic dioxy repeating unit include aliphatic diols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Of the acylated product. In addition, polyesters containing aliphatic dioxy repeating units such as polyethylene terephthalate and polybutylene terephthalate are mixed with the above aromatic oxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols and acylated products, ester derivatives, acid halides thereof. A liquid crystal polyester resin containing an aliphatic dioxy repeating unit can also be obtained by reacting with the above.
The liquid crystal polyester resin may contain an amide bond or a thioester bond as long as the object of the present invention is not impaired. Monomers that give such bonds include hydroxy aromatic amines, aromatic diamines, aromatic amino carboxylic acids, mercapto aromatic carboxylic acids, and aromatic dithiols and hydroxy aromatic thiols. The amount of these monomers used is that of the monomer giving the aromatic oxycarbonyl repeat unit, aromatic dicarbonyl repeat unit, aromatic dioxy repeat unit, aromatic oxydicarbonyl repeat unit, and aliphatic dioxy repeat unit. It is preferable that it is 10 mol% or less with respect to the total amount.
Depending on the monomer composition and composition ratio, and the sequence distribution of each repeating unit in the polymer, some liquid crystal polyester resins that combine these repeating units may or may not form an anisotropic melt phase. The liquid crystalline polyester resin used in the invention is limited to those forming an anisotropic molten phase.
Specific examples of preferable liquid crystal polyester resins include those composed of the following monomer structural units.
1) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid copolymer 2) 4-hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer 3) 4-hydroxybenzoic acid / terephthalic acid / Isophthalic acid / 4,4'-dihydroxybiphenyl copolymer 4) 4-hydroxybenzoic acid / terephthalic acid / isophthalic acid / 4,4'-dihydroxybiphenyl / hydroquinone copolymer 5) 4-hydroxybenzoic acid / terephthalic acid / Hydroquinone copolymer 6) 2-hydroxy-6-naphthoic acid / terephthalic acid / hydroquinone copolymer 7) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl Copolymer 8) 2-hydroxy-6-naphthoic acid / terephthalic acid / 4,4'-dihydroxybi Phenyl copolymer 9) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / hydroquinone copolymer 10) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / 4,4'-dihydroxy Biphenyl copolymer 11) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer 12) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer 13) 4 -Hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer 14) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone / 4,4 '-Dihydroxybiphenyl copolymer 15) 4-hydroxybenzoic acid / tere Taric acid / ethylene glycol copolymer 16) 4-hydroxybenzoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl / ethylene glycol copolymer 17) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalate Acid / ethylene glycol copolymer 18) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / ethylene glycol copolymer 19) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / 4,4-dihydroxybiphenyl copolymer.
In these, since it is excellent in heat resistance and mechanical property etc., it is preferable to use the copolymer selected from said 1), 13), or 19) as liquid crystal polyester resin.
The crystal melting temperature (Tm) measured by the differential operation calorimeter of the liquid crystal polyester resin is not particularly limited, but is preferably 320 to 380 ° C., and preferably 325 to 380 ° C. from the viewpoint of heat resistance. More preferably, it is 330-380 degreeC. The crystal melting temperature (Tm) is measured by the method described below.
<Method for measuring crystal melting temperature>
Exstar 6000 manufactured by Seiko Instruments Inc. is used as a differential scanning calorimeter. After measuring the endothermic peak temperature (Tm1) observed when a sample of liquid crystal polyester resin is measured at room temperature to 20 ° C./min, the sample is held at a temperature 20 to 50 ° C. higher than Tm1 for 10 minutes. Next, the sample was cooled to room temperature under a temperature lowering condition of 20 ° C./min, and an endothermic peak when measured again under a temperature rising condition of 20 ° C./min was observed. The crystal melting temperature (Tm) is used.
Moreover, it is preferable that the load deflection temperature measured based on ASTM D648 of the liquid crystal polyester resin used for this invention is 270-340 degreeC, It is more preferable that it is 280-340 degreeC, It is 290-340 degreeC. Most preferably.
The load deflection temperature is measured by the method described below.
<Load deflection temperature measurement method>
A strip-shaped test piece having a length of 127 mm, a width of 12.7 mm, and a thickness of 3.2 mm was molded using an injection molding machine (UH1000-110 manufactured by Nissei Plastic Industry Co., Ltd.), and this was used to comply with ASTM D648. , Measured at a load of 1.82 MPa and a heating rate of 2 ° C./min.
Further, the melt viscosity of the liquid crystalline polyester resin used in the present invention, as measured by a capillary rheometer, is preferably 10 to 100 Pa · s, more preferably 10 to 80 Pa · s, and 10 to 60 Pa · s. Most preferably.
The melt viscosity is measured by the method described below.
<Measuring method of melt viscosity>
Using a melt viscosity measuring apparatus (Capillograph 1D manufactured by Toyo Seiki Co., Ltd.), the viscosity at a shear rate of 10 ³ s ⁻¹ with a 0.7 mmφ × 10 mm capillary under the temperature condition of crystal melting temperature (Tm) + 30 ° C. Measure and use as melt viscosity.

  As the component A, any one of the above-described resins can be used alone, or a mixture of two or more selected from these can be used.

Further, the plasticizer (component B) used in the present invention is not particularly limited as long as it can impart plastic performance to the base resin, and in particular, sulfonamide derivatives and sulfonic acid ester derivatives. At least one compound selected from carboxylic acid amide derivatives and carboxylic acid ester derivatives is preferred, and these are considered to have the action of dissolving and holding the C component and imparting sustained release properties.
Among such B components, examples of the carboxylic acid ester derivative include alkyl esters, aromatic esters, and the like of various carboxylic acids that may be substituted with a hydroxyl group, a nitro group, an amino group, an epoxy group, a halogen, and the like. Those having an epoxy group are preferred because of their good compatibility with polyamides.

  Specific examples of the carboxylic acid ester derivative include, for example, dimethyl phthalate, diethyl phthalate, di-n-octyl phthalate, diphenyl phthalate, benzyl phthalate, dimethoxyethyl phthalate, 4,5-epoxyhexahydrophthalic acid di (2-ethylhexyl), 4,5-epoxycyclohexahydrophthalic acid di (7,8-epoxy-2-octenyl), 4,5-epoxycyclohexahydrophthalic acid di (9,10-epoxyoctadecyl), 4,5-epoxycyclohexa Phthalic acid ester derivatives such as hydrophthalic acid di (10,11-epoxyundecyl), phthalic acid di (tetrahydroflufuroxyloxyethyl), various phthalic acid mixed esters and phthalic acid mixed esters ethylene oxide adducts, Trahydrophthalic acid ester derivatives, butoxyethyl parahydroxybenzoate, cyclohexyloxyethoxyethoxyethyl parahydroxybenzoate, 2-ethylhexyl parahydroxybenzoate, hydroxybenzoic acid ester of ω-alkyl oligoethylene oxide, parahydroxy of undecyl glycidyl ether Benzoic acid ester derivatives such as benzoic acid adducts, propionic acid ester derivatives such as thiodipropionic acid di (tetrahydrofurfuroxylethyl), adipic acid ester derivatives, azelaic acid ester derivatives, sebacic acid ester derivatives, dodecane-2-acid ester Derivatives, maleic acid ester derivatives, fumaric acid ester derivatives, trimetic acid ester derivatives, tri (butoxyethoxyethyl) citrate, di-n-octyl citrate Citric acid ester derivatives such as ru-mono (nonylphenoxyethyl), tri-n-octyl citrate, dioctyl citrate (tetrahydrofluroxyethyl citrate), trimyristyl citrate, triethyl citrate, itaconic acid ester derivative, tetrahydrofuric acid oleate Oleic acid ester derivatives such as furyl, ricinoleic acid ester derivatives, lactic acid (n-butyl), lactic acid (2-ethylhexyl), lactic acid (n-butoxyethoxyethyl), lactic acid (n-octoxyethoxyethyl), lactic acid (n- Lactic acid ester derivatives such as decyloxyethoxyethyl), tartrate derivatives such as di (octoxyethoxyethyl) tartrate, (n-octyl) (nonylphenoxyethyl) tartrate, di (octoxyethoxyethyl) tartrate, dibutoxy malate ethyl, Ngosanji (n- butoxyethoxyethyl), distearyl malate, malic acid ester derivatives such as malic acid octadecenyl isononyl, salicylic acid ester derivatives of salicylic acid adduct of benzyl glycidyl ether and the like. Examples of the phosphoric acid ester derivatives include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri- (2-ethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, isodecyl -Diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (chloroethyl) phosphate, xylenyl diphenyl phosphate, tetrakis (2,4-ditertiarybutylphenyl) 4,4'-biphenylene diphosphate .

Moreover, as a specific example of a phosphazene derivative, following General formula (4)

[In formula, m shows the integer of 3-25. R ¹ and R ² are the same or different and represent a phenyl group which may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms and / or an allyl group. A cyclic phosphazene compound represented by the following general formula (5)

[In formula, n shows the integer of 3-1000. R ³ and R ⁴ are the same or different and represent a phenyl group which may be substituted with an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms and / or an allyl group. X represents a group —N═P (OR ³ ) ₃ , a group —N═P (OR ⁴ ) ₃ , a group —N═P (O) (OR ³ ) or a group —N═P (O) (OR ⁴ ). Show. Y represents a group —P (OR ³ ) ₄ , a group —P (OR ⁴ ) ₄ , a group —P (O) (OR ³ ) ₂ or a group —P (O) (OR ⁴ ) ₂ . And at least one phosphazene compound selected from these phosphazene compounds is an o-, m- or p-phenylene group, a biphenylene group, and the following general formula (6):

[Wherein, r represents 0 or 1, and A represents a group —SO ₂ —, —S—, —O—, or —C (CH ₃ ) ₂ —. And at least one bridging group selected from the group consisting of the groups represented by the above formulas, the ^two oxygen atoms from which the alkyl group and the like are eliminated from the substituents R ¹ , R ² , R ³ and R ⁴ are bridged. Phosphazene compounds.

  Specific examples of the cyclic phosphazene compound represented by the general formula (4) include hexaphenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decaffenoxycyclopentaphosphazene, hexapropoxycyclotriphosphazene, octapropoxycyclotetraphosphazene, decapropoxy And cyclic phosphazene compounds such as cyclopentaphosphazene.

  Further, specific examples of the linear phosphazene compound represented by the general formula (5) include a linear phosphazene compound in which a propoxy group and / or a phenoxy group is substituted on a linear dichlorophosphazene.

  Specific examples of the crosslinked structure represented by the general formula (6) include, for example, 4,4′-sulfonyldiphenylene (bisphenol-S residue), 4,4′-oxydiphenylene group, 4,4′-thiol. A diphenylene group, a 4,4'-diphenylene group, etc. can be mentioned.

  These phosphazene derivatives may be substituted with an amino group and / or a phenylamino group at an arbitrary position. These phosphazene derivatives may be used alone or in a mixture of two or more. Further, it may be a mixture of cyclic phosphazene and linear phosphazene.

  Examples of the carboxylic acid amide derivative include N-cyclohexylbenzoic acid amide.

  Examples of the sulfonamide derivatives include N-methyl-benzenesulfonamide, N-ethyl-benzenesulfonamide, N-butyl-benzenesulfonamide, N-cyclohexyl-benzenesulfonamide, N-ethyl-P-toluenesulfoamide, Examples thereof include N-butyl-toluenesulfoamide and N-cyclohexyl-toluenesulfoamide.

Examples of the sulfonate ester derivative include ethyl benzenesulfonate.
As the component B, one kind selected from a sulfonamide derivative, a sulfonic acid ester derivative, a carboxylic acid amide derivative, and a carboxylic acid ester derivative can be used alone, or a mixture of two or more kinds selected from these can be used.

  The component C is a small animal-controlling agent, and is a compound having a small animal repellent activity, which is a chemical having a small animal control activity such as various agricultural pests, sanitary pests, other insects, mosses, mites, moths, etc. Examples thereof include compounds having small animal activity such as insecticidal activity, acaricidal activity, rodenticidal activity or killing activity, compounds having small animal feeding inhibitory activity, compounds having growth control activity of small animals, and the like.

Specific examples of such small animal control agents include chloronicotinyl insecticides such as imidacloprid, compounds composed of neophyll radicals having a silicon atom such as silafluophene, benfuracarb, alanicarb, methoxydiazone, carbosphane Carbamate compounds such as fenobucarb, carbaryl, mesomil, propoxer, phenoxycarb, pyrethrin, allethrin, dl, d-T80-arethrin, d-T80-resmethrin, bioareslin, d-T80-phthalthrin, phthalthrin, resmethrin, flamethrin, Pyrethros such as propraslin, permethrin, acrinatrin, etofenprox, tralomethrin, phenothrin, d-phenothrin, fenvalerate, empentrin, praretrin, tefluthrin, benfluthrin Id compounds, dichlorobos, fenitrothion, diazinon, marathon, promophos, fenthion, trichlorfone, nared, temefos, fenclofos, chlorpyrifos methyl, siaphos, calclofos, azamethiphos, pyridafenthion, propetanephos, chlorpyrifos and the isomers thereof , Derivatives, analogs and the like. Further, compounds having an activity of controlling the growth of small animals such as metoprene, pyriproxyfen, quinoprene, hydroprene, deoenolan, NC-170, flufenoxuron, diflubenzuron, lufenuron, chlorazuron, and the like can be mentioned. Kelsen, chlorfenavir, debufenpyradopyridaben, milbemectin, fenpyroximate as acaricides, silyloside, norbomide, zinc chloride, thallium sulfate, precious neighbors, antu, warfarin, endoside, coumarin, bear tetralin , Promadiolone, diffetialone and the like.
Furthermore, Hinoki thiol contained in Taiwan Hinoki, Asunaro, Hinoki Asunaro (Aomori Hiba), herbs, casinoal derivatives (α-Cabinal, T-Cabinal) contained in Cypress, perfume oil such as clove, nutmeg, coriander, cumin Naturally-derived drugs such as geraniol, pinene, caryophyllene, borneol, eugenol, etc., which are abundant in plants, as well as known perfume oils having small animal control properties such as cedar, can also be used as the small animal control agents in the present invention. it can.

As an inorganic filler which is D component, a particulate inorganic filler, a fibrous inorganic filler, or a scale-like inorganic filler can be used.
Examples of the particulate inorganic filler include potassium titanate particles, titania particles, monoclinic titania particles, silica particles, calcium phosphate and the like, and these can be used alone or in combination. Among the particulate inorganic fillers, potassium titanate particles are particularly preferable.
The fibrous inorganic filler has, for example, an average fiber diameter of 0.05 to 10 μm, an average fiber length of 3 to 150 μm, preferably an average fiber diameter of 0.1 to 7 μm and an average fiber length of 5 to 50 μm. A fibrous inorganic filler can be suitably used. Examples of the fibrous inorganic filler include potassium tetratitanate fiber, potassium 6 titanate fiber, potassium potassium titanate fiber, titania fiber, monoclinic system Examples thereof include titania fiber, silica fiber, wollastonite, and zonotlite, and these can be used alone or in combination. Of these fibrous inorganic fillers, 8 potassium titanate fibers are particularly preferred.
Examples of scale-like inorganic fillers include potassium titanate, lithium potassium titanate, potassium magnesium titanate, talc, synthetic mica, natural mica, sericite, plate-like alumina, boron nitride, and the like. Or it can be mixed and used. Among the scaly inorganic fillers, potassium titanate is particularly preferable.
When these inorganic fillers are blended, sustained release can be maintained over a long period of time. In addition, the blending of the inorganic filler can contribute to the improvement of mechanical properties.

  The inorganic filler can be used as it is, but in order to improve the interfacial adhesion with the resin and further improve the mechanical properties, a silane coupling agent such as aminosilane, epoxy silane, acrylic silane or titanate coupling agent, etc. You may surface-treat with a surface treating agent and use.

  The additive which can suppress the film formation on the resin surface as the E component includes a hindered phenol-based antioxidant, a phosphorus-based antioxidant, an ultraviolet-absorbing light stabilizer, a hindered amine-based light stabilizer, and carbon. 1 type or 2 types or more selected from more can be mentioned.

  Examples of hindered phenolic antioxidants include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamido)], bis- [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) -butanoic acid]- Glycol ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl- 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,3 ', 3``, 5,5', 5 ''-hexa-tert-butyl-a, a ', a ''-(Methylene-2,4,6-triyl) tri-p-cresol, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tet Hinders such as kiss [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate Mention may be made of dophenol antioxidants.

  Phosphorous antioxidants include tris (2,4-di-tert-butylphenyl) phosphite, tris [2-[[2,4,8,10-tetra-tert-butylbenzo [d, f] [1 , 3,2] Dioxaphosphine-6-yl] oxy] ethyl] amine, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphos Phonite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol phosphite, bis (2,6-di-tert-butyl-4-phenyl) pentaerythritol phosphite, Examples thereof include phosphorus antioxidants such as bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite.

  UV absorbers include 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -4 , 6-di-tert-pentylphenol, propanedioic acid, [(4-methoxyphenyl) -methylene] -dimethyl ester, and the like.

  As a hindered amine light stabilizer, N, N ', N' ', N' ''-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine- 4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, poly [(6- (1,1,3,3-tetramethylbutyl) amino-1,3, 5-Triazine-2,4-diyl) (2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)) Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-dispiro- [5.1.11.2] -heneicosane -21-one, propanedioic acid, [(4-methoxyphenyl) -methylene]-, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 1,3-benzenedicarboxamide, Hinder doors such as N, N-bis (2,2,6,6-tetramethyl-4-piperidinyl), 2-ethyl, 2'-ethoxy-oxalanilide It can be mentioned emission type light stabilizer.

These E components can be used alone or in combination.
Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′- from the viewpoint of compatibility with the base resin and excellent film formation inhibition Hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamido)], tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, Tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, bis ( 2,4-di-tert-butylphenyl) pentaerythritol phosphite, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2-ethyl, 2'-ethoxy-oxalanilide, N, N ', N'',N'''-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine-4 -Yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, poly [(6- (1,1,3,3-tetramethylbutyl) amino-1,3,5 -Triazine-2,4-diyl) (2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)), 1,3-benzenedicarboxamide and N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) can be preferably used.

  In the resin composition of this invention, inorganic fillers, such as a zeolite, can also be used together in the range which does not impair the objective of this invention.

  The blending ratio of each component in the resin composition of the present invention can be appropriately set depending on the specifically selected component. Usually, the B component is 0.05 to 100 parts by weight, preferably 100 parts by weight of the A component, preferably 2 to 50 parts by weight, C component 0.01 to 50 parts by weight, preferably 0.1 to 20 parts by weight, D component 2 to 60 parts by weight, preferably 2 to 20 parts by weight, E component 0.01 to 20 parts by weight Parts, preferably 0.1 to 5 parts by weight.

If the blending amount of component D exceeds 60 parts by weight, it is not preferable because molding becomes difficult, and if it is less than 2 parts by weight, the effect of blending the fibrous inorganic filler is hardly obtained.
Moreover, when the compounding quantity of E component exceeds 20 weight part, since shaping | molding will become difficult, it is unpreferable, and when less than 0.01 weight part, the effect of film formation suppression is hard to be acquired sufficiently.

  The small animal control resin composition of the present invention can be produced, for example, by blending each component and melt-kneading. Each component can be blended in advance by dry mixing using a tumbler, blender, mixer, or the like, or can be performed by supplying each component from the same or different hopper of the kneader. The obtained small animal control resin composition of the present invention may be directly molded into a desired shape and used as a small animal control member, or may be stored and distributed after being extruded and then pelletized by a pelletizer. . A pellet or the like can be molded by a known method.

  When molding the small animal control resin composition of the present invention, it can be molded by various known molding methods, such as injection molding, extrusion molding, press molding, blow molding, machining molding, etc. Can be illustrated. The shape of the small animal control member of the present invention is not particularly limited, and can be any shape such as a flat plate shape, a rod shape, a cylindrical shape, a comb shape, and a spherical shape. In addition, the small animal control resin composition of the present invention can be formed into a structural member or the like in which a desired portion has small animal control properties by molding in two colors or multiple colors together with a normal resin composition or metal.

  Using a 45 mmφ twin screw extruder, a resin composition having the material composition shown in Table 1 below was prepared. Specifically, in the twin-screw extruder, the resin temperature is set to 190 ° C., the component A is charged from the main hopper and melted, and from the side hopper of the twin-screw extruder, a plunge pump is used to A mixture of the B component, the C component, and the E component in the ratio shown in 1 was kneaded, and the D component was side-fed to produce pelletized resin compositions of Examples and Comparative Examples, respectively. As the components A to E, materials shown in Table 2 below were used.

  Then, using each of the obtained pellets, a flat test product (50 mm × 50 mm, thickness 1.2 mm) was prepared with an injection molding machine.

Exposure Using the obtained molded articles for test of Examples and Comparative Examples, exposure tests (200 hours, 400 hours, 600 hours with a sunshine weather tester (model SEL-SUN-D, manufactured by Suga Test Instruments Co., Ltd.)) (200 Time test was conducted for 1 year exposure to UV rays and rain outdoors).

Evaluation of pest repellency Shelter test was used to evaluate pest repellency. Specifically, in a bottomed acrylic container (300 mm x 230 mm x 250 mm) with an open top, food and water are installed, and a shelter (60 mm x 60 mm, height 10 mm) that can hide pests Two were installed. The test molded product was placed in one shelter A, and nothing was placed in the other shelter B. Next, 10 German cockroaches were introduced and allowed to stand, and after 10 hours, the two shelters were removed simultaneously, the number of German cockroaches in each shelter was counted, and the repelling rate was calculated according to the following formula.
Repelling rate [%] = {(number of insects in shelter B−number of insects in shelter A) / number of insects in shelter B} × 100
The results are shown in Table 3 below.

  As shown in Table 3, it can be seen that in the comparative resin composition to which no E component was added, the repelling rate was significantly reduced over time. On the other hand, the resin composition of the example obtained by adding the E component maintains a good repellent rate even when the exposure time is 600 hours, and exhibits a small animal control action for an extremely long period of time. It is recognized that it can.

Here, with respect to the molded article for test used in Example 3 and Comparative Example 1, a cross-sectional photograph of the molded article before exposure and after 200 hours of exposure was taken, and the surface of the molded article before exposure and after 200 hours of exposure. Analysis by X-ray electron spectroscopy (XPS) in the vicinity was performed. Specifically, the XPS analysis uses an X-ray electron spectrometer (S-probe ESCA, manufactured by SSI), puts each sample into the analytical instrument, measures the energy spectrum of the excited electrons, and determines the peak of the spectrum. From the energy value, the element present in the vicinity of the surface (about 10 nm) was found, and the element content was found from the peak height. Since Cl element is an element peculiar to permethrin in the sample, analysis was performed using Cl element as an index of the surface concentration of permethrin.
Cross-sectional photographs are shown in FIGS. 1 and 2, respectively, and the analysis results by XPS are shown in FIGS. 3 and 4, respectively.

  In the cross-sectional photograph of Comparative Example 1 shown in FIG. 1, it was observed that a film having a different hue from the inner side was formed in the vicinity of the surface of the molded body after the exposure, whereas the example shown in FIG. In the sectional photograph of 3, it was not recognized that such a film was formed.

  Further, according to the XPS analysis results shown in FIGS. 3 and 4, in Comparative Example 1, the amount of Cl element derived from the drug has a large peak before the exposure, but about 1 / of that after the exposure. It can be seen that it has dropped to about 3. On the other hand, in Example 3, it is recognized that the amount of Cl element derived from the drug hardly changes before and after the exposure.

  According to these cross-sectional photographs and XPS analysis results, in the molded body of Comparative Example 1, a film that inhibits the release of the drug is formed in the vicinity of the surface by exposure, and the film inhibits the release of the drug and reduces the repelling rate. It was confirmed that it was. On the other hand, it is confirmed that the molded body of Example 3 has such a characteristic that such a film is not formed even by exposure, and the drug can be stably released.

Claims (4)

  A small animal control resin composition comprising a base resin, a plasticizer, a small animal control agent, and an inorganic filler, and further containing an additive capable of suppressing film formation on the resin surface. A small animal control resin composition characterized by the above.   The additive capable of suppressing the film formation on the resin surface is selected from the group consisting of a hindered phenol-based antioxidant, a phosphorus-based antioxidant, a UV-absorbing light stabilizer, a hindered amine-based light stabilizer, and carbon. The small animal control resin composition according to claim 1, wherein the resin composition is one type or two or more types.   The amount of the additive capable of suppressing film formation on the resin surface is 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the base resin. Small animal control resin composition.   A small animal control resin molded product, wherein the small animal control resin composition according to any one of claims 1 to 3 is molded.

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