Resin composition, member containing said resin composition, laminate, and sustained release formulation of insect repellent

Abstract

The present invention provides a resin composition containing at least a resin (A) which is a copolymer of ethylene and a vinyl monomer containing an oxygen atom, a linear or branched carboxylic acid ester (B) having a molecular weight of 255-380 and a saturated vapor pressure of 1.0×10-4 Pa or more at 25ºC, and an insect repellent (C) having a saturated vapor pressure of 1.0×10-4 Pa or more at 25ºC, wherein the amount of the resin (A) is 10-87 mass%, the amount of the carboxylic acid ester (B) is 3-30 mass%, and the amount of the insect repellent (C) is 10-60 mass% relative to the total amount of the resin composition, and the mass ratio of the carboxylic acid ester (B) and the insect repellent (C) is 2:1 to 1:5 inclusive.

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a member containing the resin composition, a laminate, and an insect repellent sustained-release formulation. [Background technology]

[0002] Resin compositions containing an insect repellent and additives that are volatile at room temperature and molded articles thereof have been known. For example, Patent Document 1 describes a resin composition containing a pyrethroid compound, a synergist, and a thermoplastic resin. Patent Document 2 describes a resin composition comprising a resin, an active compound such as an insect repellent, a volatile plasticizer having a vapor pressure of 0.001 mmHg or more at 20°C, and a bleeding promoter. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-149000 [Patent Document 2] Japanese Patent Application Laid-Open No. 2005-320550 Summary of the Invention [Problem to be solved by the invention]

[0004] In resin compositions containing a volatile active ingredient, the active ingredient exerts its efficacy by volatilizing into the surrounding environment, but the concentration of the active ingredient in the resin composition gradually decreases over time. As the concentration decreases, the volatilization rate of the active ingredient also decreases over time, which causes problems such as insufficient efficacy of the active ingredient and a shortened effective period, even though the active ingredient remains in the resin composition. This decrease in volatilization rate over time occurs when the saturated vapor pressure of the active ingredient is 1.0 x 10 -4 This becomes a problem especially when the pressure is relatively large, such as Pa or more.

[0005] In addition, in order to increase the amount of volatilization of the active ingredient, it is conceivable to increase the concentration of the active ingredient in the resin composition, but simply increasing the concentration of the active ingredient not only fails to efficiently extend the effective period, but also tends to cause bleeding on the surface of the product, often resulting in poor appearance. Furthermore, when additives such as plasticizers are used in combination, bleeding of these additives may also occur, resulting in poor appearance. In the present invention, bleeding refers to a phenomenon in which components such as active ingredients and additives that exude from the resin composition do not volatilize from the surface of a molded product made of the resin composition, but remain on the surface as a liquid or solid.

[0006] Therefore, the present invention aims to provide a resin composition that is suitable for producing products that have a long effective period and are less likely to bleed onto the product surface by volatilizing the active ingredient at a high volatilization rate over a long period of time, as well as a component, laminate, and insect repellent sustained-release formulation that contain the resin composition. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to solve the above problems, and as a result, have discovered a resin (A) which is a copolymer of ethylene and a vinyl monomer containing an oxygen atom, has a molecular weight of 255 to 380, and has a saturated vapor pressure at 25°C of 1.0 × 10 -4 A linear or branched carboxylic acid ester (B) having a saturated vapor pressure of 1.0 x 10 Pa or more at 25°C. -4 The present inventors have found that the above-mentioned problems can be solved by a resin composition containing at least an insect repellent (C) having a viscosity of 100 Pa or more, wherein the amount of resin (A) is 10 to 87 mass %, the amount of carboxylic acid ester (B) is 3 to 30 mass %, and the amount of insect repellent (C) is 10 to 60 mass %, based on the total amount of the resin composition, and the mass ratio of carboxylic acid ester (B) to insect repellent (C) is 2:1 to 1:5, and have completed the present invention.

[0008] That is, the present invention includes the following preferred embodiments. [1] Resin (A) is a copolymer of ethylene and a vinyl monomer containing an oxygen atom; The molecular weight is 255 to 380, and the saturated vapor pressure at 25°C is 1.0 × 10 -4 A linear or branched carboxylic acid ester (B) having a viscosity of at least 100 Pa, and Saturated vapor pressure at 25°C is 1.0 x 10 -4 Insect repellent (C) with Pa or higher A resin composition comprising at least the above, wherein the amount of resin (A) is 10 to 87 mass%, the amount of carboxylic acid ester (B) is 3 to 30 mass%, and the amount of insect repellent (C) is 10 to 60 mass%, based on the total amount of the resin composition, and the mass ratio of the carboxylic acid ester (B) to the insect repellent (C) is 2:1 to 1:5. [2] The resin composition according to [1] above, wherein the resin (A) is a copolymer of ethylene and an organic carboxylic acid derivative having an ethylenically unsaturated bond. [3] The resin composition according to [1] or [2], wherein the carboxylic acid ester (B) is at least one component selected from the group consisting of esters of saturated fatty acids having 8 to 20 carbon atoms, esters of dicarboxylic acids having 2 to 8 carbon atoms, carbonate esters, citrate esters, and acetyl citrate esters. [4] The resin composition according to any one of the above [1] to [3], wherein the insect repellent (C) is a pyrethroid-based insect repellent. [5] The resin composition according to [4], wherein the insect repellent (C) is at least one component selected from the group consisting of transfluthrin, metofluthrin, empenthrin, profluthrin, meperfluthrin, and heptafluthrin. [6] The saturated vapor pressure (Pb) of the carboxylic acid ester (B) at 25°C and the saturated vapor pressure (Pc) of the insect repellent (C) at 25°C are calculated using the following formula (1): 0.2≦Pb / Pc≦500 (1) The resin composition according to any one of [1] to [5] above, which satisfies the above. [7] The resin composition according to any one of [1] to [6], wherein the solubility index (R1) of the resin (A) and the carboxylic acid ester (B), the solubility index (R2) of the resin (A) and the insect repellent (C), and the solubility index (R3) of the carboxylic acid ester (B) and the insect repellent (C) are all 5.0 or less. [8] A member for a sustained-release insect repellent formulation, comprising the resin composition according to any one of [1] to [7] above. [9] A laminate comprising a first layer (D) containing the resin composition according to any one of [1] to [7] above, and a second layer (E) having permeability to a carboxylic acid ester (B) and an insect repellent (C).

[10] The laminate according to [9] above, wherein the first layer (D) is a single layer, the second layer (E) is a single layer or a multilayer, one surface of the second layer (E) is in contact with the first layer (D), and the other surface of the second layer (E) is the outermost surface of the laminate.

[11] The laminate according to [9] or

[10] above, having at least a layer structure of Layer (E) / Layer (D) / Layer (E), wherein each Layer (E) may be the same as or different from each other.

[12] The laminate according to any one of the above [9] to

[11] , further comprising a third layer (F) different from the layer (E) and the layer (D).

[13] The laminate according to

[12] , wherein the third layer (F) is at least one layer selected from the group consisting of a pressure-sensitive adhesive layer, a surface protective layer, a colored layer, an insect repellent permeation barrier layer, a design layer, and an ultraviolet absorbing layer.

[14] A sustained-release insect repellent preparation comprising the member according to [8] above and / or the laminate according to any one of [9] to

[13] above. [Effects of the Invention]

[0009] According to the present invention, by volatilizing the active ingredient at a high volatilization rate over a long period of time, it is possible to provide a resin composition that has a long shelf life and is suitable for producing products that are less likely to bleed onto the product surface, as well as components, laminates, and insect repellent sustained-release formulations that contain the resin composition. [Brief explanation of the drawings]

[0010] [Figure 1] 1 is a graph showing the change over time in the active ingredient concentration retention rate for the laminates shown in Examples and Comparative Examples. [Figure 2] 1 is a graph showing the change over time in the sustained release amount of an active ingredient for the laminates shown in Examples and Comparative Examples. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments of the present invention will be described in detail. Note that the scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the spirit of the present invention.

[0012] The resin composition of the present invention comprises: Resin (A) is a copolymer of ethylene and a vinyl monomer containing an oxygen atom; The molecular weight is 255 to 380, and the saturated vapor pressure at 25°C is 1.0 × 10 -4 A linear or branched carboxylic acid ester (B) having a viscosity of at least 100 Pa, and Saturated vapor pressure at 25°C is 1.0 x 10 -4 Insect repellent (C) with Pa or higher The resin composition comprises at least the following: a resin (A) of 10 to 87 mass %, a carboxylic acid ester (B) of 3 to 30 mass %, and an insect repellent (C) of 10 to 60 mass % based on the total mass of the resin composition; and the mass ratio of the carboxylic acid ester (B) to the insect repellent (C) is 2:1 to 1:5. Here, the resin (A) is a matrix resin of the resin composition, the carboxylic acid ester (B) is a volatile plasticizer, and the insect repellent (C) is an active ingredient in the resin composition. In this specification, the "carboxylic acid ester (B)" is also referred to as the "plasticizer (B)."

[0013] The resin composition contains the above resin (A), carboxylic acid ester (B), and insect repellent (C) in such amounts that, based on the total amount of the resin composition, the amount of resin (A) is 10 to 87 mass%, the amount of carboxylic acid ester (B) is 3 to 30 mass%, and the amount of insect repellent (C) is 10 to 60 mass%, and the mass ratio of carboxylic acid ester (B) to insect repellent (C) is 2:1 to 1:5. This makes it possible to volatilize the insect repellent (C), which is the active ingredient, in a high amount over a long period of time, and to inhibit the carboxylic acid ester (B) and the insect repellent (C) from bleeding onto the surface of the product.

[0014] The resin (A), a copolymer of ethylene and an oxygen-containing vinyl monomer, and the carboxylic acid ester (B) are highly compatible with each other. A resin composition containing these components and an insect repellent (C) in the above-described ratio can retain a large amount of the carboxylic acid ester (B) and the insect repellent (C) in the resin (A), or can retain a large amount of the insect repellent (C) in a mixture of the resin (A) and the carboxylic acid ester (B). Furthermore, when the insect repellent (C) volatilizes, the carboxylic acid ester (B) is thought to simultaneously volatilize at a rate close to that of the insect repellent (C). As a result, the rate of decrease in the concentration of the insect repellent (C) in the resin composition due to its volatilization from the resin composition can be slowed, and the decrease in the amount of volatilization of the insect repellent (C) per unit surface area of ​​the product over time can be suppressed. Furthermore, it is thought that the insect repellent (C), which is the active ingredient, can be volatilized at a high volatilization rate over a long period of time, while bleeding of the carboxylic acid ester (B) and the insect repellent (C) onto the surface of the product can be suppressed.

[0015] The amount of resin (A) contained in the resin composition of the present invention is 10 to 87% by mass based on the total amount of the resin composition. If the amount of resin (A) is less than 10% by mass, the solubility of the carboxylic acid ester (B) and the insect repellent (C) is insufficient, making it difficult to retain these components in the resin composition, and bleeding cannot be suppressed. If the amount of resin (A) exceeds 87% by mass, the amounts of the carboxylic acid ester (B) and the insect repellent (C) contained in the resin composition are reduced, resulting in an insufficient effective period. From the viewpoint of easily suppressing bleeding and, if desired, easily improving shape retention, the amount of resin (A) is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more based on the total amount of the resin composition. On the other hand, from the viewpoint of easily increasing the contents of the carboxylic acid ester (B) and the insect repellent (C) in the resin composition and easily improving the effective period, the amount of resin (A) is preferably 85% by mass or less, more preferably 75% by mass or less, and even more preferably 60% by mass or less.

[0016] The amount of carboxylic acid ester (B) contained in the resin composition of the present invention is 3 to 30% by mass based on the total amount of the resin composition. If the amount of carboxylic acid ester (B) is less than 3% by mass, the rate of decrease in the concentration of the insect repellent (C) cannot be reduced, and the decrease over time in the amount of vaporization of the insect repellent (C) per unit surface area cannot be suppressed. On the other hand, if the amount of carboxylic acid ester (B) exceeds 30% by mass, the physical properties (e.g., dimensional stability) of the resin composition decrease, making it difficult to maintain its shape. The amount of carboxylic acid ester (B) is preferably 5% by mass or more, more preferably 10% by mass or more, from the viewpoint of easily suppressing the decrease over time in the amount of vaporization of the insect repellent (C). Furthermore, the amount of carboxylic acid ester (B) is preferably 25% by mass or less, more preferably 20% by mass or less, from the viewpoint of easily improving the physical properties of the resin composition.

[0017] The amount of insect repellent (C) contained in the resin composition of the present invention is 10 to 60% by mass based on the total amount of the resin composition. If the amount of insect repellent (C) is less than 10% by mass, the initial volatilization amount of the insect repellent (C) is insufficient, and the effective period is also insufficient. On the other hand, if the amount of insect repellent (C) exceeds 60% by mass, the insect repellent (C) significantly bleeds from the resin composition. From the viewpoint of easily improving the volatilization amount and effective period of the insect repellent (C), the amount of insect repellent (C) is preferably 15% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, and even more preferably 30% by mass or more. Furthermore, from the viewpoint of easily suppressing bleeding in the resin composition, the amount of insect repellent (C) is preferably 50% by mass or less, more preferably 40% by mass or less. From the viewpoint of easily increasing compatibility with the resin (A) and the carboxylic acid ester (B), the insect repellent (C) is preferably at least one selected from the group consisting of pyrethroid insect repellents, organophosphorus insect repellents, carbamate insect repellents, juvenile hormone-like insect repellents, p-menthane-3,8-diol, N,N-diethyl-m-toluamide (DEET), carane-3,4-diol, p-dichlorobenzene, and camphor, and more preferably at least one selected from the group consisting of pyrethroid insect repellents.

[0018] The mass ratio of the carboxylic acid ester (B) to the insecticide (C) contained in the resin composition of the present invention is 2:1 to 1:5 (carboxylic acid ester (B): insecticide (C)). If the amount of the carboxylic acid ester (B) is more than twice the amount of the insecticide (C), the amount of the insecticide evaporated in the early stages of evaporation will be insufficient, and the insecticide effect will not be obtained. On the other hand, if the amount of the insecticide (C) is more than five times the amount of the carboxylic acid ester (B), the effect of suppressing the decrease in the concentration of the insecticide (C) will not be obtained. The mass ratio of the carboxylic acid ester (B) to the insecticide (C) is preferably 3:2 to 1:5, more preferably 1:1 to 1:5, even more preferably 4:5 to 1:4, even more preferably 3:4 to 1:3, and particularly preferably 2:3 to 1:2.

[0019] The resin composition of the present invention may contain one or more resins (A), one or more carboxylic acid esters (B), and one or more insect repellents (C) in the above-mentioned mass ranges and mass ratios. The resin composition may contain components other than the resin (A), carboxylic acid ester (B), and insect repellent (C). To facilitate increased sustained release of the insect repellent (C) and to enhance the efficacy of the active ingredient, the total mass of the resin (A), carboxylic acid ester (B), and insect repellent (C) contained in the resin composition is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, even more preferably 60% by mass or more, particularly preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 90% by mass or more, based on the total amount of the resin composition. The total amount of the resin (A), carboxylic acid ester (B), and insect repellent (C) contained in the resin composition may be 100% by mass or less based on the total amount of the resin composition.

[0020] The resin composition of the present invention contains resin (A), which is a copolymer of ethylene and a vinyl monomer containing an oxygen atom. Resin (A) is a copolymer of ethylene and a vinyl monomer containing an oxygen atom, and can be appropriately selected depending on the compatibility with plasticizer (B) and insect repellent (C) and the physical properties required for the member, laminate, and product containing the resin composition of the present invention. Examples of resin (A) include copolymers of ethylene and an organic carboxylic acid derivative having an ethylenically unsaturated bond, such as ethylene-vinyl acetate copolymer and ethylene-(meth)acrylic acid ester copolymer (ethylene-methyl acrylate copolymer and / or ethylene-methyl methacrylate copolymer), and ethylene-vinyl alcohol copolymer. As resin (A), one type of resin may be used, or two or more types of resins may be used in combination. From the viewpoint of easily enhancing the effect of suppressing bleeding of the carboxylic acid ester (B) and the insect repellent (C), the amount of constituent units derived from a vinyl monomer containing an oxygen atom that constitutes the resin (A) is preferably 5 to 50 mass%, more preferably 10 to 50 mass%, even more preferably 20 to 50 mass%, still more preferably 30 to 50 mass%, and particularly preferably 30 to 40 mass%, based on the total mass of the resin (A).

[0021] From the viewpoint of easily increasing the volatilization rate of the insect repellent (C), the resin (A) is preferably a resin with high molecular chain mobility, a resin with a low glass transition temperature, or the like. From this viewpoint, the glass transition temperature of the resin (A) is preferably 30°C or lower, more preferably 0°C or lower. From the viewpoint of suppressing deactivation of the insect repellent (C), the resin (A) is preferably a resin that does not undergo chemical reactions with the insect repellent (C). From the viewpoint of easily controlling the solubility and diffusibility of the insect repellent (C) over a wide range, the resin (A) is preferably a thermoplastic resin, more preferably a thermoplastic resin that can be molded at a temperature lower than the decomposition temperature or boiling point of the insect repellent (C). When the resin (A) is a thermoplastic resin that can be molded at a temperature lower than the decomposition temperature or boiling point of the insect repellent (C), it is easy to suppress loss of the insect repellent (C) due to decomposition or volatilization during processing of the resin composition.

[0022] Resin (A) is preferably a copolymer of ethylene and an organic carboxylic acid derivative having an ethylenically unsaturated bond, from the viewpoint of easily increasing the volatilization rate of the insecticide (C) and easily suppressing bleeding of the carboxylic acid ester (B) and the insecticide (C). The organic carboxylic acid derivative having an ethylenically unsaturated bond is preferably selected from the group consisting of vinyl acetate, methacrylic acid esters, and acrylic acid esters, more preferably selected from methacrylic acid esters and / or acrylic acid esters, even more preferably selected from alkyl methacrylates and / or alkyl acrylates, and particularly preferably selected from methyl methacrylate and / or methyl acrylate. In this case, from the viewpoint of easily further enhancing the effect of suppressing bleeding of the carboxylic acid ester (B) and the insecticide (C), the amount of structural units derived from the organic carboxylic acid derivative having an ethylenically unsaturated bond that constitutes resin (A) is preferably 5 to 50 mass%, more preferably 10 to 50 mass%, even more preferably 20 to 50 mass%, and even more preferably 30 to 40 mass%, based on the total mass of resin (A).

[0023] The weight-average molecular weight of resin (A) is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, even more preferably 30,000 to 400,000, even more preferably 30,000 to 300,000, particularly preferably 30,000 to 150,000, even more particularly preferably 30,000 to 70,000, and most preferably 30,000 to 50,000, from the viewpoint of easily increasing the amount of volatilization of insecticide (C) per unit surface area of ​​the product. The weight-average molecular weight of resin (A) is measured by gel permeation chromatography (GPC). The measurement conditions may be those described in the Examples.

[0024] From the viewpoint of easily suppressing volatilization of the carboxylic acid ester (B) and the insecticide (C) during processing and easily maintaining the shape of the resin composition, the melting temperature of the resin (A) is preferably 0 to 180°C, more preferably 10 to 150°C, even more preferably 15 to 120°C, still more preferably 20 to 100°C, extremely preferably 20 to 80°C, and extremely more preferably 20 to 65°C. The melting temperature of the resin (A) is measured in accordance with JIS K7215-2012.

[0025] From the viewpoint of easily increasing the amount of volatilization of the insecticide (C) per unit surface area of ​​the product and easily maintaining the shape of the resin composition, the flexural rigidity of the resin (A) is preferably 0.001 to 4000 MPa, more preferably 0.001 to 2500 MPa, even more preferably 0.01 to 500 MPa, still more preferably 0.01 to 100 MPa, extremely preferably 0.01 to 20 MPa, extremely more preferably 0.01 to 15 MPa, and most preferably 0.01 to 10 MPa. The flexural rigidity of the resin (A) is measured in accordance with ASTM D747-70.

[0026] The durometer D hardness of the resin (A) is preferably 1 to 70 MPa, more preferably 1 to 40 MPa, even more preferably 2 to 35 MPa, still more preferably 5 to 30 MPa, extremely preferably 5 to 25 MPa, and extremely more preferably 10 to 20 MPa, from the viewpoint of easily increasing the amount of volatilization of the insect repellent (C) per unit surface area of ​​the product and easily maintaining the shape of the resin composition. The durometer D hardness of the resin (A) is measured in accordance with JIS K7215-1986.

[0027] The resin composition of the present invention has a molecular weight of 255 to 380 and a saturated vapor pressure at 25°C of 1.0 × 10 -4 The carboxylic acid ester (B) has a molecular weight of 255 to 380 and a saturated vapor pressure at 25°C of 1.0 x 10 Pa or more. -4 One type of linear or branched carboxylic acid ester having a viscosity of Pa or higher may be used, or two or more types of carboxylic acid esters may be used. The carboxylic acid ester (B) has a linear or branched structure and does not contain a cyclic structure. A linear or branched carboxylic acid ester refers to a carboxylic acid ester compound having a molecular structure in which the constituent atoms of the carboxylic acid ester do not contain a portion bonded in a ring, but rather these atoms are bonded in a chain.

[0028] The carboxylic acid ester (B) having the above saturated vapor pressure acts as a volatile plasticizer in the resin composition of the present invention. The inclusion of the carboxylic acid ester (B) facilitates increasing the mobility of the insect repellent (C) in the resin composition, thereby increasing the amount of volatilization of the insect repellent (C) per unit surface area of ​​the product and maintaining a high level of volatilization of the insect repellent (C) over a long period of time. If the molecular weight of the carboxylic acid ester (B) is less than 255, the volatility of the carboxylic acid ester (B) is too high relative to the volatility of the insect repellent (C), and thus the effect of suppressing the decrease in the concentration of the insect repellent (C) is not achieved. On the other hand, if the molecular weight is greater than 380, the volatility of the plasticizer (B) is too low relative to the volatility of the insect repellent (C), and thus the effect of suppressing the decrease in the concentration of the insect repellent (C) is not achieved. The molecular weight of the carboxylic acid ester (B) is preferably 260 or more, more preferably 270 or more, and even more preferably 280 or more. The molecular weight is preferably 370 or less, more preferably 360 or less, even more preferably 350 or less, and even more preferably 320 or less.

[0029] The saturated vapor pressure (P B ) is 1.0 × 10 -4 Pa or more, preferably 1.0 × 10 -3 Pa or higher. B ) is 1.0 × 10 -4 If the saturated vapor pressure is less than Pa, the volatilization rate of the carboxylic acid ester (B) is too slow compared to the volatilization rate of the insecticide (C), making it impossible to maintain a high volatilization rate of the insecticide (C) for a long period of time. If the saturated vapor pressure of the carboxylic acid ester (B) is equal to or higher than the above lower limit, the carboxylic acid ester (B) is easily volatilized at the same volatilization rate as the insecticide (C), and the carboxylic acid ester (B) is also easily volatilized as the insecticide (C) volatilizes from the resin composition. As a result, the gradient of the decrease in the concentration of the insecticide (C) in the resin composition due to the volatilization of the insecticide (C) from the resin composition can be made gentler, making it easier to suppress the decrease over time in the volatilization rate of the insecticide (C) per unit surface area of ​​the product. The saturated vapor pressure (P b) is not particularly limited, but from the viewpoint of molding processability of the resin composition, it is preferably 1.0 × 10 5 Pa or less, more preferably 1.0×10 3 From the above viewpoint, the saturated vapor pressure of the plasticizer (B) at 25°C is preferably 1.0 × 10 -4 Pa~1.0×10 5 Pa, more preferably 1.0 × 10 -4 Pa~1.0×10 3 Pa, more preferably 1.0 × 10 -3 Pa ~ 10 Pa.

[0030] The carboxylic acid ester (B) has a structure in which a carboxylic acid and an alcohol are ester-bonded. Examples of carboxylic acids constituting the carboxylic acid ester (B) include enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, oleic acid, linoleic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, citric acid, acetylcitric acid, and carbonic acid. From the viewpoint of easily increasing the stability of the carboxylic acid ester (B) itself, linear or branched carboxylic acids that do not contain a carbon-carbon double bond are preferred. From the viewpoint of preventing bleeding, the carboxylic acid constituting the carboxylic acid ester (B) is preferably selected from the group consisting of linear or branched saturated fatty acids having 8 to 20 carbon atoms, linear or branched dicarboxylic acids having 2 to 8 carbon atoms, carbonic acid, citric acid, and acetylcitric acid, more preferably selected from the group consisting of linear or branched saturated fatty acids having 8 to 16 carbon atoms, linear or branched dicarboxylic acids having 4 to 8 carbon atoms, citric acid, and acetylcitric acid, still more preferably selected from the group consisting of caprylic acid, isononanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, adipic acid, sebacic acid, citric acid, and acetylcitric acid, with lauric acid, myristic acid, adipic acid, sebacic acid, and acetylcitric acid being particularly preferred, and even more preferably selected from the group consisting of adipic acid, sebacic acid, and acetylcitric acid.

[0031] From the viewpoints of preventing bleeding and moisture absorption, the alcohol constituting the carboxylic acid ester (B) is preferably a monohydric alcohol, more preferably a monohydric alcohol having 1 to 12 carbon atoms, even more preferably a monohydric saturated alcohol having 1 to 12 carbon atoms, even more preferably an alcohol selected from the group consisting of ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, ethylhexyl alcohol, nonanol, isononanol, decanol, 2-propylhexyl alcohol, and dodecanol, even more preferably an alcohol selected from the group consisting of ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, and ethylhexyl alcohol, and even more preferably an alcohol selected from the group consisting of ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, and hexanol.

[0032] As the carboxylic acid ester (B), from the viewpoints of preventing bleeding, moisture absorption, and deterioration, at least one selected from the group consisting of esters of saturated fatty acids having 8 to 20 carbon atoms, esters of dicarboxylic acids having 2 to 8 carbon atoms, carbonate esters, citrate esters, and acetylcitric acid esters is preferred, and esters of carboxylic acids selected from linear or branched saturated fatty acids having 8 to 20 carbon atoms, linear or branched dicarboxylic acids having 2 to 8 carbon atoms, carbonic acid, citric acid, and acetylcitric acid with monohydric alcohols are more preferred, and linear or branched saturated fatty acids having 8 to 16 carbon atoms with monohydric alcohols are more preferred. Esters of a fatty acid, a linear or branched dicarboxylic acid having 4 to 8 carbon atoms, any one of citric acid and acetylcitric acid, and a monohydric saturated alcohol having 1 to 12 carbon atoms are more preferred, and examples thereof include octyl caprylate, ethylhexyl caprylate, nonyl caprylate, isononyl caprylate, decyl caprylate, 2-propylhexyl caprylate, dodecyl caprylate, heptyl isononanoate, octyl isononanoate, ethylhexyl isononanoate, nonyl isononanoate, isononyl isononanoate, decyl isononanoate, and 2-propylhexyl isononanoate. , Dodecyl Isononanoate, Hexyl Caprate, Heptyl Caprate, Octyl Caprate, Ethylhexyl Caprate, Nonyl Caprate, Isononyl Caprate, Decyl Caprate, 2-Propylhexyl Caprate, Dodecyl Caprate, Pentyl Laurate, Hexyl Laurate, Heptyl Laurate, Octyl Laurate, Ethylhexyl Laurate, Nonyl Laurate, Isononyl Laurate, Decyl Laurate, 2-Propylhexyl Laurate, Dodecyl Laurate, Propyl Myristate, Isopropyl Myristate, Myristate butyl myristate, isobutyl myristate, pentyl myristate, hexyl myristate, heptyl myristate, octyl myristate, ethylhexyl myristate, nonyl myristate, isononyl myristate, decyl myristate, 2-propylhexyl myristate, ethyl palmitate, propyl palmitate, isopropyl palmitate, butyl palmitate, isobutyl palmitate, pentyl palmitate, hexyl palmitate, heptyl palmitate, octyl palmitate, ethylhexyl palmitate, nonyl palmitate,Even more preferred are isononyl palmitate, dibutyl adipate, diisobutyl adipate, dipentyl adipate, dihexyl adipate, diheptyl adipate, dioctyl adipate, diethylhexyl adipate, diethyl sebacate, dipropyl sebacate, diisopropyl sebacate, dibutyl sebacate, diisobutyl sebacate, dipentyl sebacate, dihexyl sebacate, triethyl citrate, tripropyl citrate, triisopropyl citrate, tributyl citrate, triisobutyl citrate, triethyl acetyl citrate, tripropyl acetyl citrate, and triisopropyl acetyl citrate. Decyl caprylate, 2-propylhexyl caprylate, dodecyl caprylate, nonyl isononanoate, isononyl isononanoate, decyl isononanoate, 2-propylhexyl isononanoate, dodecyl isononanoate, octyl caprate, ethylhexyl caprate, nonyl caprate, isononyl caprate, decyl caprate, 2-propylhexyl caprate, dodecyl caprate, heptyl laurate, octyl laurate, ethylhexyl laurate, nonyl laurate, isononyl laurate, decyl laurate, 2-propylhexyl laurate, pentyl myristate, hexyl myristate, myristate Particularly preferred are heptyl myristate, octyl myristate, ethylhexyl myristate, nonyl myristate, isononyl myristate, propyl palmitate, isopropyl palmitate, butyl palmitate, isobutyl palmitate, pentyl palmitate, hexyl palmitate, heptyl palmitate, dipentyl adipate, dihexyl adipate, diheptyl adipate, dipropyl sebacate, diisopropyl sebacate, dibutyl sebacate, diisobutyl sebacate, dipentyl sebacate, triethyl citrate, tripropyl citrate, triisopropyl citrate, and triethyl acetylcitrate. Heptyl laurate, octyl laurate, ethylhexyl laurate, nonyl laurate, isononyl laurate, decyl laurate, 2-propylhexyl laurate, pentyl myristate, hexyl myristate, heptyl myristate, octyl myristate, ethylhexyl myristate, nonyl myristate, isononyl myristate,Dipentyl adipate, dihexyl adipate, diheptyl adipate, dipropyl sebacate, diisopropyl sebacate, dibutyl sebacate, diisobutyl sebacate, dipentyl sebacate, and triethyl acetylcitrate are particularly preferred. Pentyl myristate, hexyl myristate, heptyl myristate, octyl myristate, ethylhexyl myristate, dipentyl adipate, dihexyl adipate, diheptyl adipate, dipropyl sebacate, diisopropyl sebacate, dibutyl sebacate, diisobutyl sebacate, dipentyl sebacate, and triethyl acetylcitrate are even more particularly preferred. Dipentyl adipate, dipropyl sebacate, diisopropyl sebacate, dibutyl sebacate, diisobutyl sebacate, and / or triethyl acetylcitrate are even more preferred. The carboxylic acid ester (B) may contain one kind of these carboxylic acid esters or two or more kinds of them.

[0033] The resin composition of the present invention has a saturated vapor pressure of 1.0×10 at 25°C. -4 The present invention includes an insect repellent (C) having a viscosity of not less than 1 Pa. As the insect repellent (C), one type of insect repellent may be used, or two or more types of insect repellents may be used.

[0034] The saturated vapor pressure of insect repellent (C) at 25°C is 1.0 x 10 -4 The saturated vapor pressure of the insect repellent (C) is 1.0 × 10 Pa or more. -4 If the saturated vapor pressure is less than 1.0×10 Pa, sufficient volatility is not obtained, and the insect repellent effect in the space is not exhibited. -3 From the viewpoint of appropriately adjusting the volatility and easily extending the effective period, the saturated vapor pressure of the insect repellent (C) is preferably 1 Pa or less, more preferably 10 -1 Pa or less, more preferably 10 -2 Pa or less.

[0035] Examples of the insect repellent (C) include pyrethroid-based insect repellents, organophosphorus-based insect repellents, carbamate-based insect repellents, p-menthane-3,8-diol, N,N-diethyl-m-toluamide (DEET), carane-3,4-diol, p-dichlorobenzene, camphor, and the like. From the viewpoint of easily increasing compatibility with the resin (A) and the carboxylic acid ester (B), pyrethroid-based insect repellents are preferred.

[0036] Examples of pyrethroid insect repellents include transfluthrin, metofluthrin, profluthrin, empenthrin, allethrin, furamethrin, prallethrin, resmethrin, phthalthrin, fenothrin, momfluorothrin, heptafluthrin, meperfluthrin, and natural pyrethrins. Among these, from the viewpoint of volatilization rate, at least one insect repellent selected from the group consisting of transfluthrin, metofluthrin, empenthrin, profluthrin, meperfluthrin, and heptafluthrin is preferred, at least one insect repellent selected from the group consisting of transfluthrin, metofluthrin, empenthrin, profluthrin, and meperfluthrin is more preferred, at least one insect repellent selected from the group consisting of transfluthrin, metofluthrin, empenthrin, and profluthrin is even more preferred, and transfluthrin and / or metofluthrin are even more preferred.

[0037] Examples of organophosphorus insecticides include dichlorvos, trichlorfon, cyanophos, fenitrothion, chlorpyrifos, diazinon, fenthion, malathion, acephate, and isoxathion.

[0038] Examples of carbamate insect repellents include carbaryl and methomyl.

[0039] Other insect repellents include, for example, p-menthane-3,8-diol, N,N-diethyl-m-toluamide (DEET), carane-3,4-diol, p-dichlorobenzene, camphor, and the like.

[0040] The saturated vapor pressure (Pb) of the carboxylic acid ester (B) at 25°C and the saturated vapor pressure (Pc) of the insect repellent (C) at 25°C contained in the resin composition of the present invention are calculated by the following formula (1): 0.2≦Pb / Pc≦500 (1) When formula (1) is satisfied, the insect repellent (C) can be easily evaporated in a particularly high amount over a long period of time, and bleeding onto the product surface can be easily prevented.

[0041] The fact that the saturated vapor pressure (Pb) of the carboxylic acid ester (B) and the saturated vapor pressure (Pc) of the insect repellent (C) satisfy the relationship of formula (1) indicates that the volatilization behavior of these components is very similar to each other. Therefore, when the insect repellent (C) volatilizes, the carboxylic acid ester (B) is thought to volatilize simultaneously at a rate very close to the volatilization rate of the insect repellent (C). As a result, the gradient of the decrease in the concentration of the insect repellent (C) in the resin composition due to the volatilization of the insect repellent (C) from the resin composition can be made very gentle, further making it easier to suppress the decrease over time in the amount of volatilization of the insect repellent (C) per surface area of ​​the product.

[0042] From the viewpoints of facilitating the volatilization of the insect repellent (C) at a high volatilization rate over a long period of time and of easily suppressing bleeding onto the product surface, Pb / Pc in formula (1) is preferably 0.4 or more, more preferably 0.7 or more, and even more preferably 1.0 or more, and is preferably 100 or less, more preferably 50 or less, and even more preferably 15 or less. From the same viewpoint, the saturated vapor pressure (Pb) of the carboxylic acid ester (B) and the saturated vapor pressure (Pc) of the insect repellent (C) preferably satisfy formula (1-1), more preferably formula (1-2), and even more preferably formula (1-3). 0.4≦Pb / Pc≦100 (1-1) 0.7≦Pb / Pc≦50 (1-2) 1.0≦Pb / Pc≦15 (1-3)

[0043] When the insect repellent (C) and / or carboxylic acid ester (B) contained in the resin composition is a mixture of two or more substances, it is preferable that the Pb / Pc value of at least one combination of insect repellent (C) and carboxylic acid ester (B) contained in the mixture that has the closest saturated vapor pressure at 25°C satisfies formula (1). This is because, if a carboxylic acid ester (B) with a saturated vapor pressure that falls within the Pb / Pc range defined by formula (1) is present for any one of the insect repellents (C), it is possible to achieve the effects of volatilizing at least one insect repellent (C) at a high rate over a long period of time and reducing bleeding to the product surface. From the perspective of easily achieving high volatilization rates, long-term volatilization, and bleeding-suppression effects for all insect repellents (C) contained in the mixture, it is preferable that the mixture contain a carboxylic acid ester (B) with a saturated vapor pressure that satisfies the Pb / Pc relationship defined by formula (1) for all of the insect repellents (C).

[0044] From the viewpoint of facilitating stable retention of the resin (A), carboxylic acid ester (B), and insect repellent (C) in the resin composition of the present invention and suppressing bleeding, it is preferable that the compatibility of the resin (A), carboxylic acid ester (B), and insect repellent (C) be good. From the same viewpoint, the solubility index (R1) of the resin (A) and carboxylic acid ester (B) contained in the resin composition of the present invention, the solubility index (R2) of the resin (A) and the insect repellent (C), and the solubility index (R3) of the carboxylic acid ester (B) and the insect repellent (C) are each preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.0 or less, and even more preferably 2.0 or less. The solubility index (R1), solubility index (R2), and solubility index (R3) are each calculated using the formula described below.

[0045] As used herein, the Hansen solubility parameter is based on equation (2A): R1=((δp A -δp B ) 2 +(δh A -δh B ) 2 ) 1 / 2 (2A) [In formula (2A), δp A represents the polar term in the Hansen solubility parameter of resin (A), and δp B represents the polar term in the Hansen solubility parameter of the carboxylic acid ester (B), and δh A represents the hydrogen bond term in the Hansen solubility parameter of resin (A), and δh B represents the hydrogen bond term in the Hansen solubility parameter of the carboxylic acid ester (B). The solubility parameter distance of the resin (A) to the carboxylic acid ester (B), expressed as follows, is referred to as the solubility index (R1) between the resin (A) and the carboxylic acid ester (B). The closer the solubility index (R1) is to 0, the better the compatibility between the resin (A) and the carboxylic acid ester (B). When the solubility index (R1) between the resin (A) and the carboxylic acid ester (B) is not more than the above upper limit, the plasticizer (B) can be easily stably retained in the resin composition of the present invention, and bleeding can be easily suppressed.

[0046] As used herein, the Hansen solubility parameter is based on equation (2B): R2=((δp A -δp C ) 2 +(δh A -δh C ) 2 ) 1 / 2 (2B) [In formula (2B), δp A represents the polar term in the Hansen solubility parameter of resin (A), and δp C represents the polar term in the Hansen solubility parameter of the insect repellent (C), and δh A represents the hydrogen bond term in the Hansen solubility parameter of resin (A), and δh C represents the hydrogen bond term in the Hansen solubility parameters of the insect repellent (C). The distance between the solubility parameters of the resin (A) and the insect repellent (C), expressed as follows, is referred to as the solubility index (R2) between the resin (A) and the insect repellent (C). The closer the solubility index (R2) is to 0, the better the compatibility between the resin (A) and the insect repellent (C). When the solubility index (R2) between the resin (A) and the insect repellent (C) is not more than the above upper limit, the insect repellent (C) can be easily stably retained in the resin composition of the present invention, bleeding of the insect repellent (C) can be easily suppressed, and the amount of volatilization of the insect repellent (C) can be easily increased.

[0047] As used herein, the Hansen solubility parameter is based on equation (2C): R3=((δp C -δp B ) 2 +(δh C -δh B ) 2 ) 1 / 2 (2C) [δp in formula (2C) C , δp B , δh C and δh B is as defined above] The solubility parameter distance of the insect repellent (C) to the carboxylic acid ester (B), expressed as follows, is referred to as the solubility index (R3) between the carboxylic acid ester (B) and the insect repellent (C). The closer the solubility index (R3) is to 0, the better the compatibility between the carboxylic acid ester (B) and the insect repellent (C). When the solubility index (R3) between the carboxylic acid ester (B) and the insect repellent (C) is not more than the upper limit described above, bleeding is easily suppressed and a high volatilization rate of the insect repellent (C) can be easily maintained for a long period of time.

[0048] Therefore, the solubility index (R1), the solubility index (R2) and the solubility index (R3) are respectively: Equations (2A) to (2C) based on Hansen solubility parameters: R1=((δp A -δp B ) 2 +(δh A -δh B ) 2 ) 1 / 2 (2A) R2=((δpA -δp C ) 2 +(δh A -δh C ) 2 ) 1 / 2 (2B) R3=((δp C -δp B ) 2 +(δh C -δh B ) 2 ) 1 / 2 (2C) [In formulas (2A) to (2C), δp A and δh A represent the polar term and the hydrogen bonding term in the Hansen solubility parameter of the resin (A), respectively; δp B and δh B represent the polar term and the hydrogen bonding term in the Hansen solubility parameter of the carboxylic acid ester (B), respectively; δp C and δh C represent the polar term and hydrogen bonding term in the Hansen solubility parameters of the insect repellent (C), respectively. It is expressed as:

[0049] The Hansen solubility parameter divides the solubility of a substance into three components (dispersion term δd, polar term δp, and hydrogen bonding term δh) and represents them in three-dimensional space. The dispersion term δd represents the effect of dispersion forces, the polar term δp represents the effect of dipole-dipole forces, and the hydrogen bonding term δh represents the effect of hydrogen bonding forces. The definition and calculation of the Hansen solubility parameter are described in Charles M. Hansen, Hansen Solubility Parameters: A Users Handbook (CRC Press, 2007). Furthermore, by using the computer software Hansen Solubility Parameters in Practice (HSPiP), the Hansen solubility parameter can be easily estimated from the chemical structure of a substance even if literature values ​​are unknown. In the present invention, for compounds and monomers registered in the database included in HSPiP version 4.1, the values ​​are used. For compounds and monomers not registered, estimated values ​​using HSPiP version 4.1 are used to determine δd, δp, and δh.

[0050] The δp or δh of the resin (A) is determined as a numerical value obtained by multiplying the δp or δh of the monomer from which each structural unit contained in the resin (A) is derived by the content of the structural unit and adding up the results. When resin (A) is a mixture of two or more substances, the Δp of resin (A) is determined by multiplying the Δp of each substance contained in the mixture by the content of each substance and adding up the results. When resin (A) is a mixture of two or more substances, the δh of resin (A) is determined by multiplying the δh of each substance contained in the mixture by the content of each substance and adding up the results.

[0051] When the carboxylic acid ester (B) is a mixture of two or more substances, the δp of the carboxylic acid ester (B) is determined by multiplying the δp of each substance contained in the mixture by the content of each substance and adding up the results. When the carboxylic acid ester (B) is a mixture of two or more substances, the δh of the carboxylic acid ester (B) is determined by multiplying the δh of each substance contained in the mixture by the content of each substance and adding up the results.

[0052] When the insect repellent (C) is a mixture of two or more substances, the δp of the insect repellent (C) is determined by multiplying the δp of each substance contained in the mixture by the content of each substance and adding up the results. When the insect repellent (C) is a mixture of two or more substances, the δh of the insect repellent (C) is the value obtained by multiplying the δh of each substance contained in the mixture by the content of each substance and adding up the results.

[0053] The resin composition of the present invention may further contain other components in addition to the resin (A), the carboxylic acid ester (B), and the insect repellent (C). The other components may include a polymer other than the resin (A), a plasticizer that does not fall under the category of the carboxylic acid ester (B) (for example, a plasticizer that is not a carboxylic acid ester, a plasticizer having a saturated vapor pressure of 1.0 × 10 at 25°C, etc.). -4 Examples of known additives include plasticizers (e.g., plasticizers having a viscosity of less than 100 Pa), synergists, antioxidants, neutralizing agents, crosslinking agents, heat stabilizers, weather stabilizers, pigments, fillers, lubricants, and flame retardants. The resin composition of the present invention may contain one type of other component, or may contain two or more types of other components. The content of other components other than the resin (A), carboxylic acid ester (B), and insect repellent (C) may be set depending on the purpose and is not particularly limited, but is preferably less than 50 mass%, more preferably 30 mass% or less, and even more preferably 10 mass% or less, based on the total amount of the resin composition of the present invention.

[0054] The penetration of the resin composition of the present invention may be appropriately adjusted depending on the form of use of the resin composition, and is not particularly limited. From the viewpoints of easily increasing the amount of volatilization of the active ingredient per surface area of ​​the insect repellent (B) and easily improving the dimensional stability of members and laminates obtained from the resin composition, the molecular weight is preferably 1 to 600, more preferably 2 to 400, even more preferably 3 to 300, particularly preferably 5 to 250, even more particularly preferably 10 to 200, and most preferably 15 to 100. The penetration is measured in accordance with the penetration test method described in JIS K2207, using a cylindrical glass container 10 mm in diameter and 40 mm deep, instead of the test container and thermostatic water bath specified in JIS K2207, in room air maintained at a room temperature of 25°C, with a load of 50 g.

[0055] The method for producing the resin composition of the present invention is not particularly limited. For example, the resin composition can be obtained by mixing the raw materials, resin (A), carboxylic acid ester (B), and insect repellent (C), using a mixer such as a Banbury mixer, super mixer, kneader, extruder, planetary mixer, butterfly mixer, dissolver, roll mill, or mixing kettle. The obtained resin composition may be molded into powder, pellets, or blocks. A masterbatch in which at least some of the raw materials, resin (A), carboxylic acid ester (B), and insect repellent (C), are premixed may also be used. Alternatively, at least some of the raw materials for the resin (A), the carboxylic acid ester (B), and the insect repellent (C) (e.g., resin (A)) may be molded in advance into a powder, pellet, sheet, block, or other shape, and the resulting molded body may be brought into contact with a liquid or gas containing the remaining raw materials (e.g., carboxylic acid ester (B) and / or insect repellent (C)) to impregnate the remaining raw materials into the molded body, thereby producing a resin composition. Methods for contacting the molded body obtained as described above with the liquid include a method of immersing the molded body in the liquid, a method of adding the molded body to the liquid and optionally stirring, and a method of applying the liquid to the molded body.

[0056] For example, when the resin composition contains two or more types of resins (A), the resin (A), the carboxylic acid ester (B), and the insect repellent (C) may be mixed at once to obtain the resin composition, or one type of resin (A) may be mixed with the carboxylic acid ester (B) and / or the insect repellent (C), and the resulting mixture may be mixed with the remaining components to obtain the resin composition.

[0057] The resin composition of the present invention is used in an insect repellent sustained-release formulation. An insect repellent sustained-release formulation is a product that exerts an insect repellent effect on a space by volatilizing and diffusing an insect repellent into the space. The form of the formulation is not particularly limited, but examples include a formulation molded from the resin composition of the present invention alone, a formulation molded from a combination of the resin composition of the present invention with other materials, and a component using the resin composition of the present invention mounted on a container, frame, or insect repellent volatilization device. In order to maintain the mechanical properties required of a product or achieve a desirable appearance, an insect repellent sustained-release formulation using the resin composition of the present invention is preferably a formulation molded from a combination of the resin composition of the present invention with other materials, or a component using the resin composition of the present invention mounted on a container, frame, or insect repellent volatilization device. A component using the resin composition of the present invention mounted on a container, frame, or insect repellent volatilization device is particularly preferred. An insect repellent sustained-release formulation containing at least a portion of the resin composition of the present invention is also referred to as an insect repellent sustained-release resin formulation.

[0058] The present invention also provides a member for an insect repellent sustained-release formulation (insect repellent sustained-release resin formulation) containing the resin composition of the present invention described above. The member may be a molded product containing the resin composition of the present invention, for example, a molded article obtained by molding the resin composition of the present invention. The member of the present invention can be produced, for example, by molding the resin composition of the present invention using a known molding method such as injection molding, extrusion molding, press molding, or slush (powder) molding. The shape of the molded article may be appropriately determined depending on the conditions and purpose of use of the molded article and is not particularly limited. For example, the molded article may be rod-shaped, flat, mesh-shaped, round, spherical, fan-shaped, triangular, or the like, or may be processed into shapes such as nets, fibers, nonwoven fabrics, sheets, films, tubes, and pellets for use.

[0059] The member of the present invention may be a composite comprising the resin composition of the present invention and other materials. Such a member can be produced, for example, by compounding the resin composition of the present invention with a molded body that is incompatible with the resin composition of the present invention. When the member of the present invention is a composite as described above, the shape of the molded body constituting the composite may be appropriately selected depending on the conditions and purpose of use of the composite, and is not particularly limited. For example, it may be rod-shaped, flat, mesh-shaped, spherical, fan-shaped, triangular, etc., or may be in the form of a net, fiber, nonwoven fabric, sheet, film, tube, pellet, etc. Examples of materials for the molded body include resin, metal, ceramic, glass, plants and their derivatives, animal leather, and fur. Methods for compounding the resin composition of the present invention with the molded body include immersing the molded body in a liquid resin composition of the present invention, pressing the resin composition of the present invention into the molded body, adding the molded body to the liquid resin composition of the present invention and optionally stirring, applying the liquid resin composition of the present invention to the molded body, attaching a sheet-shaped resin composition of the present invention to the molded body, and knitting the molded body and a molded body of the resin composition of the present invention together.

[0060] The present invention also provides a laminate comprising a first layer (D) containing the resin composition of the present invention described above and a second layer (E) having permeability to the carboxylic acid ester (B) and the insect repellent (C). The first layer (D) may be a single layer containing the resin composition of the present invention, or a multilayer layer comprising two or more layers each containing the resin composition of the present invention. When the layer (D) is multilayered, the layers may be identical to each other or may be different from each other in terms of, for example, composition and / or thickness. The amount of the resin composition of the present invention contained in the first layer (D) may be appropriately determined depending on the application of the laminate, but is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total amount of the first layer (D). Furthermore, this amount need only be 100% by mass or less. Therefore, the first layer (D) may be a layer composed of the resin composition of the present invention. The first layer (D) may be a single layer or a multilayer, but from the viewpoint of ease of production of the laminate of the present invention, a single layer is preferred.

[0061] The second layer (E) in the present invention, which is permeable to the carboxylic acid ester (B) and the insect repellent (C), is a layer which satisfies the requirements defined by the following method. 3 g of carboxylic acid ester (B) is placed in a 60 mm diameter moisture-permeable cup for evaluating the moisture permeability of moisture-proof packaging materials as specified in JIS Z 0208, and the cup is sealed using layer (E) instead of packaging material. The cup is placed in a 40°C oven, and after 24 hours, the weight of the carboxylic acid ester (B) is measured. If the weight of the carboxylic acid ester (B) has decreased by 0.5 mg or more from the initial amount, the layer is defined as a layer permeable to the carboxylic acid ester (B). The same measurement is performed using an insect repellent (C) instead of the carboxylic acid ester (B). If the weight of the insect repellent (C) has decreased by 0.5 mg or more, the layer is defined as a layer permeable to the insect repellent (C). A layer that satisfies the above conditions for both the carboxylic acid ester (B) and the insect repellent (C) is the layer (E) of the present invention that is permeable to the carboxylic acid ester (B) and the insect repellent (C). The weight loss value measured as above is the permeability of the layer used for the measurement to each component. The transmittances described in the examples of this specification are transmittances measured by the above-mentioned method. When such a layer (E) is used to separate a space where the carboxylic acid ester (B) and the insect repellent (C) are present from a space where they are not present, the carboxylic acid ester (B) and the insect repellent (C) move to the space where the carboxylic acid ester (B) and the insect repellent (C) are not present, and the carboxylic acid ester (B) and the insect repellent (C) are present in both spaces.

[0062] The permeability of layer (E) to the carboxylic acid ester (B), measured as described above, is preferably 0.5 mg to 15 mg, more preferably 0.5 mg to 10 mg, even more preferably 1 mg to 6 mg, and even more preferably 2 mg to 5 mg, from the viewpoint of obtaining a formulation with a long shelf life. The permeability of layer (E) to the insecticide (C), measured as described above, is preferably 1 mg to 6 mg, more preferably 2 mg to 5 mg, from the viewpoint of fully exhibiting the efficacy of the insecticide (C). The ratio of the permeability of layer (E) to the carboxylic acid ester (B) (permeability B) (permeability C / permeability B) to the insecticide (C) (permeability C) is preferably 0.5 to 3, more preferably 0.8 to 2.5, and even more preferably 1 to 2, from the viewpoint of balancing efficacy and shelf life.

[0063] The material contained in layer (E) may be selected depending on the types of carboxylic acid ester (B) and insect repellent (C) used so as to achieve a desired level of permeability to the carboxylic acid ester (B) and the insect repellent (C), and is not particularly limited, and examples thereof include polyolefin resins such as polyethylene and polypropylene, ethylene copolymer resins such as ethylene-vinyl acetate copolymer, biodegradable resins such as polylactic acid, vinyl chloride, etc. From the viewpoint of easily achieving good permeability to the insect repellent (C), layer (E) preferably contains an ethylene copolymer resin and / or a polyolefin resin.

[0064] The layer (E) may have through-holes to adjust the permeability of the layer (E) to the carboxylic acid ester (B) and the insect repellent (C) and to appropriately change the amount of the carboxylic acid ester (B) and the insect repellent (C) vaporized through the layer (E). The diameter of the through-holes may be adjusted appropriately, but is preferably 0.1 to 500 μm. When the layer (E) has through-holes, the plasticizer (B) and the insect repellent (C) permeate the layer (E) through the through-holes and are vaporized, as described above. Therefore, the layer (E) does not need to be made of a material that is permeable to the plasticizer (B) and the insect repellent (C). The material constituting the layer (E) may be any material, including known resins, metals, glass, etc. From the viewpoint of processability, the material constituting the layer (E) is preferably a thermoplastic resin.

[0065] Layer (E) may be a fibrous material such as cloth or paper. Examples of the fibrous material include cellulose fibers, polyethylene fibers, polypropylene fibers, polyethylene terephthalate fibers, metal fibers, animal hair, and mixtures thereof. These materials may contain adhesives that bind the fibers together, fillers that fill the gaps between the fibers, dyes, pigments, paints, etc. to impart color or patterns.

[0066] The layer (E) may be a single layer or a multilayer. An example of a multilayer layer (E) is laminated paper in which a polyolefin resin is coated on paper. In this case, for example, in a laminate having at least a layer (E) / layer (D) layer structure, the polyolefin resin layer of the multilayer layer (E) may be the surface in contact with the layer (D), or the paper layer may be the surface in contact with the layer (D). Furthermore, a laminate in which the first layer (D) is a single layer and the second layer (E) is a single layer or a multilayer, one surface of the second layer (E) is in contact with the first layer (D), and the other surface of the second layer (E) is the outermost surface of the laminate, may be either a laminate in which the polyolefin resin layer of the multilayer layer (E) is the surface in contact with the layer (D) and the paper layer is the outermost surface of the laminate, or a laminate in which the paper layer is the surface in contact with the layer (D) and the polyolefin resin layer is the outermost surface. Preferably, the polyolefin resin layer is the surface in contact with layer (D), and the paper layer is the outermost surface of the laminate.

[0067] The laminate comprising a first layer (D) containing the resin composition of the present invention and a second layer (E) having permeability to the carboxylic acid ester (B) and the insect repellent (C) may further comprise a third layer (F) different from the layer (E) and the layer (D). Examples of the third layer (F) include at least one layer selected from the group consisting of a pressure-sensitive adhesive layer, a surface protective layer, a colored layer, an insect repellent permeation barrier layer, a design layer, and an ultraviolet absorbing layer.

[0068] One embodiment of the laminate of the present invention is a laminate comprising a first layer (D) containing the resin composition of the present invention and a second layer (E) permeable to the carboxylic acid ester (B) and the insect repellent (C). Examples of the laminate include a laminate in which layers (D) and (E) are laminated in this order, a laminate in which layers (E), (D), and (E) are laminated in this order, and a laminate in which layers (D), (E), and (D) are laminated in this order. A laminate in which layers (E), (D), and (E) are laminated in this order can volatilize the insect repellent (C) from both sides of the laminate, enabling the insect repellent to be supplied to the space at a high volatilization rate. Examples of such laminates include a laminate having at least a layer structure of layer (E) / layer (D), a laminate having at least a layer structure of layer (E) / layer (D) / layer (E), and a laminate having at least a layer structure of layer (E) / layer (D) / layer (E) / layer (D) / layer (E). In the layer structure such as Layer (E) / Layer (D) / Layer (E), Layer (E) / Layer (D) / Layer (E) / Layer (D) / Layer (E), each Layer (E) may be the same or different from each other, and each Layer (D) may be the same or different from each other. Furthermore, the above layer structure may further include Layer (F).

[0069] Another embodiment of the laminate of the present invention is a laminate comprising at least a first layer (D) made of the resin composition of the present invention, a second layer (E) permeable to the carboxylic acid ester (B) and the insect repellent (C), and a third layer (F) that may or may not be permeable to the insect repellent (C), with the layer structure being layered in the order of layer (E) / layer (D) / layer (F). A laminate laminated in this form can improve the value of the product by varying the volatilization rate of the insect repellent (C) from both sides of the laminate or by imparting a function other than insect control to layer (F). For example, layer (F) can be made of an impermeable material to exert an insect repellent effect only on one side of the space separated by the laminate, or layer (F) can be made of an adhesive material to allow the laminate to be attached to an appropriate surface. Furthermore, the above layer structure may further comprise layer (F).

[0070] Another embodiment of the laminate of the present invention is a laminate in which a first layer (D) made of the resin composition of the present invention and a second layer (E) permeable to the plasticizer (B) and the insect repellent (C) are laminated in the order of layer (D) / layer (E). A laminate laminated in this form can improve the mechanical properties of the laminate and avoid direct contact with the first layer (D) containing the insect repellent (C) while ensuring the volatility of the insect repellent (C). Furthermore, if the first layer (D) is adhesive, the laminate can be attached to an appropriate surface. Furthermore, the above layer configuration may further include layer (F).

[0071] In a preferred embodiment, the laminate of the present invention may be a laminate in which the first layer (D) is a single layer, the second layer (E) is a single layer or a multilayer, one surface of the second layer (E) is in contact with the first layer (D), and the other surface of the second layer (E) is the outermost surface of the laminate. Examples of such laminates include a laminate having a layer structure of a single layer (D) / a single layer or a multilayer layer (E), in which the surface of layer (E) that is not in contact with layer (D) is the outermost surface of the laminate, and a laminate having a layer structure of layer (E) / single layer (D) / layer (E), in which the surface of at least one of the two layers (E) that is not in contact with layer (D) is the outermost surface of the laminate. Examples of such a laminate include a laminate having a layer structure in the order of layer (E) / single layer (D), a laminate having a layer structure in the order of layer (E) / single layer (D) / layer (F), a laminate having a layer structure in the order of layer (E) / single layer (D) / layer (E), and a laminate having a layer structure in the order of layer (E) / single layer (D) / layer (E) / layer (F).

[0072] The method for producing the laminate of the present invention is not particularly limited. For example, a method of coating a layer (E) having a shape such as a sheet with the resin composition of the present invention liquefied by thermal melting or dissolving in an appropriate solvent; a method of coating a layer (D) having a shape such as a sheet with a composition to provide layer (E) liquefied by thermal melting or dissolving in an appropriate solvent; and, when both the composition to provide layer (D) and the composition to provide layer (E) are thermoplastic, a method of co-extrusion of these compositions, multilayer injection molding, composite spinning, and extrusion lamination are included. Here, if layer (E) needs to be processed at high temperatures, the high-temperature conditions for processing layer (E) may cause the insect repellent (B) contained in layer (D) to volatilize. From the viewpoint of easily preventing such volatilization of the insect repellent (B), it is preferable to produce the laminate of the present invention by a method of coating either layer (D) or layer (E) with the material of the other layer by thermal melting or dissolving in a solvent, or by extrusion laminating layer (D) to layer (E). [Example]

[0073] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the examples and comparative examples, "%" and "parts" mean "% by mass" and "parts by mass", respectively, unless otherwise specified. The materials used in the examples are as follows.

[0074] <Resin (A)> The following resins were used in the examples and comparative examples: Resin (X1) is a resin that does not fall under the category of resin (A) contained in the resin composition of the present invention. (A1): Ethylene-methyl acrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Acryft®, methyl acrylate comonomer content 35% by mass, weight-average molecular weight 4.0 × 10 4 ) (A2): Ethylene-methyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Acryft®, methyl methacrylate comonomer content 25% by mass, weight-average molecular weight 6.1 × 10 4 ) (A3): Ethylene-methyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Acryft®, methyl methacrylate comonomer content 18% by mass, weight average molecular weight 6.4 × 10 4 ) (A4): Ethylene-vinyl acetate copolymer (Sumitomo Chemical Co., Ltd., Sumitate, vinyl acetate comonomer content 28% by mass) (X1): Low-density polyethylene (Sumitomo Chemical Co., Ltd., Sumikathene (registered trademark) F101, weight-average molecular weight 6.1 × 10 4 )

[0075] <Plasticizer (Carboxylic Acid Ester (B)> The following carboxylic acid esters or plasticizers were used in the examples and comparative examples. Note that the carboxylic acid esters (Y1) and (Y2) do not fall under the category of the carboxylic acid ester (B) contained in the resin composition of the present invention. Furthermore, (Y3) is a plasticizer but is not a carboxylic acid ester. (B1): Diisopropyl sebacate (Wako Pure Chemical Industries, Ltd., special grade reagent, molecular weight 286.4, saturated vapor pressure at 25 °C: 6.5 × 10 -3 Pa) (B2): Acetyl triethyl citrate (Tokyo Chemical Industry Co., Ltd., molecular weight 318.3, saturated vapor pressure at 25°C 2.0 × 10 -2 Pa) (Y1): Diethyl adipate (Tokyo Chemical Industry Co., Ltd., molecular weight 202.5, saturated vapor pressure at 25°C: 1.2 Pa) (Y2): Acetyl tributyl citrate (Tokyo Chemical Industry Co., Ltd., molecular weight 402.5, saturated vapor pressure at 25°C: 1.7 x 10 -4 Pa) (Y3): Hexadecyl alcohol (GODREJ, GINOL16, purity 98%, molecular weight 242.4, saturated vapor pressure at 25°C: 8.0 × 10 -4Pa (Literature value, Daubert, TE, RP Danner. Physical and Thermodynamic Properties of Pure Chemicals Data Compilation. Washington, DC: Taylor and Francis, 1989.))

[0076] <Insect repellent> In the examples and comparative examples, the following insect repellents were used. (C1): Metofluthrin (manufactured by Sumitomo Chemical Co., Ltd., trade name: Eminence (registered trademark), saturated vapor pressure at 25°C: 1.7 × 10 -3 Pa) (C2): Transfluthrin (manufactured by Sumitomo Chemical Co., Ltd., trade name: Biothrin (registered trademark), saturated vapor pressure at 25°C: 3.7 × 10 -3 Pa)

[0077] <Layer(E)> In the examples and comparative examples, layers of materials having the following permeabilities were used: Table 1 shows the permeability of each layer to insect repellents and plasticizers. (E1): Linear low-density polyethylene film (Sumitomo Chemical Co., Ltd., linear low-density polyethylene Noblene, grade: FV203, blown film) (E2): Laminated kraft paper (kraft paper laminated with low-density polyethylene, basis weight 60 g / m 2 )

[0078] <Layer(F)> In the examples and comparative examples, layers made of the following materials were used: The permeability of layer (F) to insect repellents and plasticizers is shown in Table 1. (F1): Polyethylene terephthalate film (manufactured by PANAC Corporation, thickness: 100 μm)

[0079] In the examples and comparative examples, physical property measurements and performance evaluations were carried out according to the following methods. (1) Saturated vapor pressure The saturated vapor pressure was measured by temperature-programmed gas chromatography in accordance with the Donovan method (New method for estimating vapor pressure by the use of gas chromatography: Journal of Chromatography A. 749 (1996) 123-129). Although plasticizer (Y3) was not measured by the above method, literature values ​​or estimated values ​​are listed for reference.

[0080] (2) Penetration The penetration of each composition was measured according to the penetration test method specified in JIS K2207. Instead of using the test container and thermostatic water bath specified in JIS K2207, a sample was placed in a cylindrical glass container with a diameter of 10 mm and a depth of 40 mm. The sample was then measured under room air at a temperature of 25°C with a load of 50 g. The penetration was measured three times for each sample in the same container, and the average value was recorded as the penetration. Each measurement point was selected to be at least 3 mm away from the peripheral wall of the test container, and from the second measurement onwards, a point at least 3 mm away from each penetration point in the previous measurement was selected. If the sample was so flexible that the needle contacted the bottom of the glass container, the penetration was recorded as 400 from a depth (40 mm) of the glass container. A high penetration indicates a softer composition.

[0081] (3) Weight average molecular weight The polystyrene-equivalent weight-average molecular chain length (Aw) of resin (A) was measured using gel permeation chromatography (GPC) with a light scattering detector under the following conditions: The baseline on the chromatogram was defined as a straight line connecting the points in the stable, flat region with retention times sufficiently shorter than the appearance of the sample elution peak and the points in the stable, flat region with retention times sufficiently longer than the observed solvent elution peak. GPC equipment: Tosoh HLC-8121GPC / HT Light scattering detector: Precision Detectors PD2040 Differential pressure viscometer: Viscotek H502 GPC column: Tosoh GMHHR-H(S)HT x 3 Sample solution concentration: 2mg / mL Injection volume: 0.3mL Measurement temperature: 155℃ Melting conditions: 145℃ 2hr Mobile phase: orthodichlorobenzene (with BHT 0.5 mg / mL added) Flow rate during elution: 1mL / min Measurement time: Approximately 1 hour Calibration curve creation method: Use standard polystyrene The weight average molecular weight (Mw) of each polymer was calculated from the polystyrene-equivalent weight average molecular chain length (Aw) using the following formula: Molecular weight (Mw) = molecular chain length (Aw) x Q factor The Q factor is the molecular weight of the monomer unit of a polymer divided by the extended chain length of the monomer unit (molecular weight per 1 Å). For each resin (A), the average molecular weight of the monomers that make up the resin was used as the monomer unit molecular weight, and the ideal interval between every other carbon atom in a CC trans bond extended chain in polyethylene, 2.52 Å, was used as the extended chain length of the monomer unit.

[0082] (4) Preparation of resin composition and samples for measuring sustained release amount The resin (A), carboxylic acid ester (B), and insect repellent (C) were kneaded for 15 minutes in a Labo Plastomill (Toyo Seiki Seisakusho, Model 65C150) or a small tabletop kneader (DSM Xplore, 15 cc biaxial microcompounder) at a rotation speed of 80 rpm and a chamber temperature of 70°C to prepare a resin composition. The resulting resin composition was press-molded at 70°C under a pressure of 20 MPa to obtain a sheet-like molded product (layer (D)) measuring 50 mm in length, 150 mm in width, and 0.15 mm in thickness. Next, a layer (E) consisting of a linear low-density polyethylene film (E1) or laminated kraft paper (E2) whose resin surface had been corona-treated was attached to both sides of layer (D) so that the corona-treated surface was in contact with layer (D), thereby obtaining a laminate. The edges of the resulting laminate were heat-sealed so that layer (D) was not exposed, and a sample was obtained.

[0083] (5) Sustained release amount measurement method (5-1) Static conditions Five samples were prepared using the method described in (4). Each sample was left standing in a test room at 30°C and a wind speed of 0.5 m / s for 3, 7, 14, 21, and 42 days. (5-2) Sustained release ratio (Qb and Qc) and sustained release mass (Rb and Rc) The mass loss [g] of each sample was calculated from the difference in mass between the sample before and after standing. The mass loss thus calculated was defined as the total sustained-release mass Rt of the carboxylic acid ester (B) and the insect repellent (C). Next, after leaving the samples for the specified number of days, each sample was immersed in 50 mL of methanol at room temperature for 24 hours to obtain an extract solution containing components extracted from each sample with methanol. The obtained extract solution was separated and quantified using a gas chromatography-flame ionization detector (GC-FID) (Shimadzu Corporation GC2010), and the remaining amount of carboxylic acid ester (B) Mb [g] and the remaining amount of insect repellent (C) Mc [g] present in each sample after leaving the sample were measured. Then, the sustained release rate Qb of carboxylic acid ester (B) was calculated using the following formula (3A), and the sustained release rate Qc of insect repellent (C) was calculated using the formula (3B). In addition, the sustained release mass Rb of carboxylic acid ester (B) was calculated using the formula (4A), and the sustained release mass Rc of insect repellent (C) was calculated using the formula (4B). The sustained release rates (Qb and Qc) are the ratios of the amount of each sustained release component to the total amount of sustained release components. The sustained release masses (Rb and Rc) correspond to the masses of the sustainedly released components. Qb = (Wb - Mb) / (Wb - Mb + Wc - Mc) (3A) Qc = (Wc - Mc) / (Wb - Mb + Wc - Mc) (3B) (In formula (3A) and formula (3B), Wb represents the content [g] of carboxylic acid ester (B) in the sample before standing, Wc indicates the content [g] of insect repellent (C) in the sample before standing. Rb = Rt × Qb (4A) Rc = Rt × Qc (4B) (5-3) Sustained release amount Next, the ratio (Rb / Wb × 100) [mass%] of the sustained-release mass (Rb) of the carboxylic acid ester (B) to the content (Wb) of the carboxylic acid ester (B) contained in the sample before standing was calculated and defined as the sustained-release amount of the carboxylic acid ester (B). Similarly, the ratio (Rc / Wc × 100) [mass%] of the sustained-release mass (Rc) of the insect repellent (C) to the content (Wc) of the insect repellent (C) contained in the sample before standing was defined as the sustained-release amount of the insect repellent (C). (5-4) Amount of sustained release of insect repellent (C) other than during collection In addition, the total sustained release mass Rt' was measured at regular intervals other than the time of collection, and the sustained release mass Qc' of the insect repellent (C) was calculated using the following formula (5). The sustained release mass Rc' of the insect repellent (C) relative to the content of the insect repellent (C) contained in the sample before standing was defined as the sustained release amount of the insect repellent (C) other than the time of collection. Qc'=Rt'×(Qcc+(D-Dc) / (Da-Dc)×(Qca-Qcc))(5) (In formula (5), D indicates the number of days of standing when the total sustained release mass Rt' is measured, Dc indicates the number of days immediately before D when the sample was collected, Da indicates the number of days immediately after D when the sample was collected, Qcc represents the sustained release rate Qc of the insect repellent (C) in the sample collected immediately before D, Qca indicates the sustained release rate Qc of the insect repellent (C) in the sample collected immediately after D.

[0084] (6) Maximum sustained release rate ratio The daily release rate of the insect repellent [mg / day] was calculated for each of the following periods: from the start of measurement to the third day (Period I), from the fourth day to the seventh day (Period II), from the eighth day to the fourteenth day (Period III), and from the fifteenth day to the twenty-first day (Period IV). Specifically, for example, the daily release rate of the insect repellent in Period II was calculated using the formula (released mass of insect repellent on the seventh day - released mass of insect repellent on the fourth day) / (7-4). Furthermore, the ratio of the maximum release rate to the minimum release rate (maximum release rate / minimum release rate) among the daily release rates of the insect repellent in each period was defined as the maximum release rate ratio.

[0085] (7) Evaluation of sustained release The sustained release properties of each sample were evaluated based on the sustained release mass measured by the method described in (5) and the maximum sustained release rate ratio measured by the method described in (6) according to the following criteria. Evaluation results of A and B were considered to be acceptable. [Evaluation criteria for sustained release] A: A sample in which the daily sustained-release mass of the insect repellent (C) is 2 mg or more in each of the periods from the start of the test to the third day (Period I), from the fourth day to the seventh day (Period II), from the eighth day to the fourteenth day (Period III), and from the fifteenth day to the twenty-first day (Period IV), and the maximum sustained-release rate ratio is within a range of 0.6 to 1.7. In this case, it is considered that a uniform, high insect repellent effect is exhibited for at least 21 days, and further long-term efficacy is expected because the rate at which the concentration of the insect repellent (C) in the resin composition decreases is gradual. B: Among samples that do not meet the criteria of A, the daily sustained-release amount of the insect repellent (C) in each of the above periods is 1.5 mg or more, and the maximum sustained-release rate ratio is within a range of 0.4 to 2.3. In this case, it is considered that a uniform insect repellent effect is exhibited for at least 21 days, and the rate of decrease in the concentration of the insect repellent (C) in the resin composition is somewhat slow, so that although it does not reach A, it is expected that the effect will be exhibited for a sufficiently long period of time. C: Among samples that do not meet the standards of A and B, the sustained release amount of insect repellent (C) per day is 1.5 mg or more in any of the above periods. In this case, it is considered that the insect repellent effect is exhibited for a limited period of time, but the rate of decrease in the concentration of insect repellent (C) cannot be controlled, so it is considered that the effectiveness cannot be maintained for a long period of time. D: Samples that do not meet the standards of A, B, or C. The sustained release amount is small and the effectiveness as an insect repellent is low, or even if it is released, the period of release is short or unstable.

[0086] (8) Measurement method for retention of active ingredient concentration The concentration of the active ingredient (insect repellent) in the resin composition of each sample that had been left standing under the conditions described in (5) was calculated using the following formula (6). Active ingredient concentration [wt%]={(Wc-Rc) / (Wt-Rt)}×100 (6) (In formula (6), Wc represents the amount of insect repellent (C) added to the sample before standing [g], Rc represents the sustained release mass [g] of the insect repellent (C), Wt represents the mass [g] of the resin composition in the sample before standing, Rt represents the total sustained release amount of the carboxylic acid ester (B) and the insect repellent (C). In the above formula, (Wc-Rc) represents the mass of the active ingredient contained in the resin composition after a specific standing period, and (Wt-Rt) represents the mass of the resin composition after a specific standing period. From the active ingredient concentration calculated as above, the retention rate of the active ingredient concentration was calculated according to the following formula (7). Active ingredient concentration retention rate [%] = [(active ingredient concentration according to formula (6)) / {(Wc / Wt) × 100}] × 100 (7) In the above formula, (Wc / Wt)×100 represents the concentration of the active ingredient in the resin composition in the sample before standing.

[0087] (9) Bleed evaluation For the laminates containing the resin compositions of the Examples and Comparative Examples, the samples were visually observed before and after the evaluation of the sustained release amount measurement (standing period: 21 days), and the degree of bleeding was evaluated according to the following evaluation criteria. Evaluation results of A to C were considered to be acceptable. [Breed evaluation criteria] A: There was no bleeding from the laminate either before or after the evaluation, and the surface remained uniform in composition as before the evaluation. B: No bleeding was observed when touching the surface of the laminate both before and after evaluation, but discoloration due to the active ingredient etc. penetrating into the (E) layer was observed. C: There is no bleeding from the surface of the laminate before evaluation, but after evaluation, there is a slight bleeding that can be felt when touching the surface of the laminate, or the resin composition can be observed to have separated into two or more layers inside the laminate. D: There is no bleeding from the surface of the laminate before the evaluation, but bleeding such as droplets or crystals can be clearly confirmed visually after the evaluation. E: After sample preparation, bleeding was noticeable when touching the laminate surface or was visible before evaluation.

[0088] Example 1 According to the formulation shown in Table 2, (A1), (B1), and (C1) were kneaded by the method described in (4) to obtain a resin composition, which was then used to prepare a layer (D), and a layer (E1) was laminated on both sides of the layer (D) to prepare a sample (laminate).

[0089] Example 2 A resin composition was obtained by the method described in (4) in the same manner as in Example 1, except that the ratios of (A1), (B1), and (C1) were as shown in Table 2. A layer (D) was produced using the resin composition, and layers (E1) were laminated on both sides of layer (D) to produce a sample.

[0090] Example 3 According to the formulation shown in Table 2, (A1), (B1), and (C2) were kneaded by the method described in (4) to obtain a resin composition, which was then used to prepare a layer (D), and a layer (E1) was laminated on both sides of the layer (D) to prepare a sample.

[0091] Example 4 According to the formulation shown in Table 2, (A1), (B2), and (C1) were kneaded by the method described in (4) to obtain a resin composition, which was then used to prepare a layer (D), and a layer (E1) was laminated on both sides of the layer (D) to prepare a sample.

[0092] Example 5 According to the formulation shown in Table 2, (A4), (B1), and (C1) were kneaded in the same manner as in (4), except that the kneading temperature was 90°C, to obtain a resin composition. Layer (D) was prepared using the resin composition, and layers (E1) were laminated on both sides of layer (D) to prepare a sample.

[0093] Example 6 According to the formulation shown in Table 2, (A4), (B1), and (C2) were kneaded in the same manner as in (4), except that the kneading temperature was 90°C, to obtain a resin composition. Layer (D) was prepared using the resin composition, and layers (E1) were laminated on both sides of layer (D) to prepare a sample.

[0094] Example 7 According to the formulation shown in Table 2, (A3), (B1), and (C2) were kneaded in the same manner as in (4), except that the kneading temperature was 90°C, to obtain a resin composition. The resin composition was used to prepare a layer (D), and a layer (E1) was laminated on both sides of the layer (D) to prepare a sample.

[0095] Example 8 According to the formulation shown in Table 2, (A2), (X1), (B2), and (C1) were kneaded in the same manner as in (4), except that the kneading temperature was 130°C, to obtain a resin composition. The resin composition was used to prepare a layer (D), and a layer (E1) was laminated on both sides of the layer (D) to prepare a sample.

[0096] Example 9 According to the formulation shown in Table 2, (A1), (B1), and (C1) were kneaded by the method described in (4) to obtain a resin composition, which was then used to prepare a layer (D), and a layer (E2) was laminated on both sides of the layer (D) to prepare a sample.

[0097] (Comparative Example 1) According to the formulation shown in Table 2, (A2), (X1), and (C1) were kneaded in the same manner as described in (4) except that the kneading temperature was 130°C to obtain a resin composition. A layer (D) was prepared using the resin composition, and a layer (E1) was laminated on both sides of the layer (D) to prepare a sample.

[0098] (Comparative Example 2) According to the formulation shown in Table 2, (A3) and (C2) were kneaded in the same manner as in (4) except that the kneading temperature was 90°C to obtain a resin composition. Layer (D) was produced using the resin composition, and layers (E1) were laminated on both sides of layer (D) to prepare a sample.

[0099] (Comparative Example 3) According to the formulation shown in Table 2, (A1), (Y1), and (C1) were kneaded by the method described in (4) to obtain a resin composition, which was then used to prepare a layer (D), and a layer (E1) was laminated on both sides of the layer (D) to prepare a sample.

[0100] Comparative Example 4 According to the formulation shown in Table 2, (A1), (Y2), and (C1) were kneaded by the method described in (4) to obtain a resin composition, which was then used to prepare a layer (D), and a layer (E1) was laminated on both sides of the layer (D) to prepare a sample.

[0101] (Comparative Example 5) According to the formulation shown in Table 2, (A1), (Y3), and (C1) were kneaded by the method described in (4) to obtain a resin composition, which was then used to prepare a layer (D), and a layer (E1) was laminated on both sides of the layer (D) to prepare a sample.

[0102] (Comparative Example 6) According to the formulation shown in Table 2, (A1), (B1), and (C1) were kneaded by the method described in (4) to obtain a resin composition, which was then used to prepare a layer (D), and a layer (E1) was laminated on both sides of the layer (D) to prepare a sample.

[0103] (Comparative Example 7) According to the formulation shown in Table 2, (A1), (B1), and (C1) were kneaded by the method described in (4) to obtain a resin composition, which was then used to prepare a layer (D), and a layer (E1) was laminated on both sides of the layer (D) to prepare a sample.

[0104] The saturated vapor pressure (Pb) of the carboxylic acid ester or plasticizer used in the Examples and Comparative Examples at 25°C and the saturated vapor pressure (Pc) of the insect repellent (C) at 25°C were measured using the method described in (1) Saturated Vapor Pressure, and the ratio Pb / Pc was calculated. The inter-component solubility indexes R (R1 to R3) between the resin, carboxylic acid ester or plasticizer, and insect repellent used in the Examples and Comparative Examples were calculated using equations (2A) to (2C) based on the Hansen solubility parameters. The resin compositions obtained in the Examples and Comparative Examples were measured for penetration using the method described in (2) Penetration. The results are shown in Table 2.

[0105] For the samples (laminates) for measuring the amount of sustained release obtained in the examples and comparative examples, the sustained release was evaluated according to the method described in (5) Sustained Release Amount Measurement Method and the maximum sustained release rate ratio measured according to the method described in (6) Sustained Release Evaluation Method. Furthermore, bleeding was evaluated according to the method described in (9) Bleeding Evaluation Method. The results are shown in Table 3.

[0106] The samples (laminates) for measuring the amount of sustained release obtained in the examples and comparative examples were measured for the amount of sustained release (Rc) of the insect repellent (C) after standing for a predetermined period of time according to (5) the method for measuring the amount of sustained release. The results are shown in Table 3. The maximum release rate ratio of the insect repellent (C) was calculated according to the measurement method described in (6) Maximum release rate ratio. The results are shown in Table 3.

[0107] The active ingredient concentration retention rate was measured for the samples (laminates) obtained in Example 1 and Comparative Example 1 according to the method described in (8) Method for measuring active ingredient concentration retention rate. The results are shown in FIG.

[0108] For the samples (laminates) obtained in Example 1 and Comparative Example 1, the amount of the active ingredient released was measured according to the methods described in (5-3) Amount of Release and (5-4) Amount of Release of Insect Repellent (C) at Times Other Than Recovery, and the change over time was confirmed. The results are shown in Figure 2.

[0109] [Table 1]

[0110] [Table 2]

[0111] [Table 3]

[0112] The samples of Examples 1 to 9 were good in the evaluation of sustained release, and were capable of volatilizing the active ingredient at a high volatilization rate over a long period of time, and were also good in the evaluation of bleeding, showing little bleeding. In contrast, the samples of Comparative Examples 1 to 7 were not capable of volatilizing the active ingredient at a high volatilization rate over a long period of time, and showed insufficient evaluation results for sustained release, and / or were prone to bleeding.

[0113] The samples of Examples 1 to 3 (particularly the sample of Example 1) maintained the concentration of the insect repellent (C) in the resin composition for a long period of time, and stably released a large amount of the insect repellent (C) for a long period of time. The sample described in Example 4 tended to release a lower amount of plasticizer (B) than Examples 1 to 3, but it stably released a high amount of insect repellent (C). The samples described in Examples 5 and 6 maintained the concentration of the insect repellent (C) in the resin composition for a long period of time and stably released a high amount of the insect repellent (C) for a long period of time. When the sample surface was wiped after the evaluation of the sustained release amount, a small amount of liquid bleeding was observed, but it was at a level that was not problematic. The samples of Examples 7 and 8 stably released the insect repellent (C) at a high sustained release amount, although the sustained release amount was lower than that of Examples 1 to 3. When the sample surfaces were wiped after the sustained release amount evaluation, a slight amount of liquid bleeding was observed in the sample of Example 7, but this was at an acceptable level, and no bleeding was observed on the sample surface of Example 8. The sample of Example 9 stably released a high amount of the insect repellent (C) over a long period of time. Although discoloration due to liquid penetration was observed in the paper of layer (E), no bleeding was observed on the surface of the sample after the evaluation of the sustained release amount.

[0114] In the sample of Comparative Example 1, the concentration of the insect repellent (C) in the resin composition decreased over time, and the sustained release amount of the insect repellent (C) was small. Furthermore, after the evaluation of the sustained release amount was completed, droplet-like bleeding was visibly observed on the surface of the sample. The sustained release amount of the insect repellent (C) gradually decreased in the sample of Comparative Example 2. Furthermore, when the surface of the sample was wiped after the sustained release amount evaluation, a small amount of liquid bleeding was observed. In the sample of Comparative Example 3, the plasticizer (B) was completely released in the early stage, and then the sustained release amount of the insect repellent (C) gradually decreased. The sample of Comparative Example 4 hardly released any plasticizer (B), and then the sustained release amount of the insect repellent (C) gradually decreased. The sample of Comparative Example 5 had a small and unstable sustained release of the plasticizer (B). The insect repellent (C) was stably released. Furthermore, layer separation was observed in the resin composition before the sustained release evaluation, and solid bleeding was visibly observed on the sample surface after the evaluation. In the sample of Comparative Example 6, the sustained release amount of the plasticizer (B) was small and unstable, and the sustained release amount of the insect repellent (C) gradually decreased. In the sample of Comparative Example 7, the insect repellent (C) was initially released significantly, but the amount of release subsequently decreased slightly. In addition, even before the start of the evaluation of the amount of release, the liquid separated from the resin composition, making the surface of the sample sticky, and after the evaluation was completed, clear bleeding of the liquid droplets was observed.

Claims

1. Resin (A) is a copolymer of ethylene and a vinyl monomer containing an oxygen atom; The molecular weight is 255 to 380, and the saturated vapor pressure at 25°C is 1.0 x 10 －４ a linear or branched carboxylic acid ester (B) having a viscosity of 100 Pa or more, and Saturated vapor pressure at 25°C is 1.0 x 10 －４ Insect repellent (C) having a viscosity of 100 Pa or more The resin composition contains at least the above-mentioned compound, wherein the amount of resin (A) is 10 to 87 mass%, the amount of carboxylic acid ester (B) is 3 to 30 mass%, and the amount of insect repellent (C) is 10 to 60 mass%, based on the total amount of the resin composition, and the mass ratio of the carboxylic acid ester (B) to the insect repellent (C) is 2:1 to 1:

5.

2. 2. The resin composition according to claim 1, wherein the resin (A) is a copolymer of ethylene and an organic carboxylic acid derivative having an ethylenically unsaturated bond.

3. 3. The resin composition according to claim 1, wherein the carboxylic acid ester (B) is at least one component selected from the group consisting of esters of saturated fatty acids having 8 to 20 carbon atoms, esters of dicarboxylic acids having 2 to 8 carbon atoms, carbonate esters, citrate esters, and acetyl citrate esters.

4. The resin composition according to any one of claims 1 to 3, wherein the insect repellent (C) is a pyrethroid-based insect repellent.

5. The resin composition according to claim 4, wherein the insect repellent (C) is at least one component selected from the group consisting of transfluthrin, metofluthrin, empenthrin, profluthrin, meperfluthrin, and heptafluthrin.

6. The saturated vapor pressure (Pb) of the carboxylic acid ester (B) at 25°C and the saturated vapor pressure (Pc) of the insect repellent (C) at 25°C are calculated by the following formula (1): 0.2≦Pb / Pc≦500 (1) The resin composition according to any one of claims 1 to 5, which satisfies the above.

7. The solubility index (R １ ), the solubility index (R ２ ) and the solubility index (R ３ 7. The resin composition according to claim 1, wherein each of the above formulas is 5.0 or less.

8. A member for a sustained-release insect repellent formulation, comprising the resin composition according to any one of claims 1 to 7.

9. A laminate comprising a first layer (D) containing the resin composition according to any one of claims 1 to 7, and a second layer (E) having permeability to a carboxylic acid ester (B) and an insect repellent (C).

10. 10. The laminate according to claim 9, wherein the first layer (D) is a single layer, the second layer (E) is a single layer or a multilayer, one surface of the second layer (E) is in contact with the first layer (D), and the other surface of the second layer (E) is the outermost surface of the laminate.

11. 11. The laminate according to claim 9 or 10, having at least a layer structure of layer (E) / layer (D) / layer (E), wherein each layer (E) may be the same or different from each other.

12. The laminate according to any one of claims 9 to 11, further comprising a third layer (F) different from the layer (E) and the layer (D).

13. The laminate according to claim 12, wherein the third layer (F) is at least one layer selected from the group consisting of a pressure-sensitive adhesive layer, a surface protective layer, a colored layer, an insect repellent permeation barrier layer, a design layer, and an ultraviolet absorbing layer.

14. A sustained-release insect repellent preparation comprising the member according to claim 8 and / or the laminate according to any one of claims 9 to 13.

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