Resin composition, parts containing the same, laminates and insecticide slow-release preparations

Abstract

The present application provides a resin composition comprising at least a resin (A) which is a copolymer of ethylene and a vinyl monomer containing an oxygen atom, a carboxylic acid ester (B) having a linear or branched chain with a vapor pressure of 1.0 x 10 －4 Pa or more at 25°C, and an insect repellent (C) having a vapor pressure of 1.0 x 10 －4 Pa or more at 25°C, wherein the amount of the resin (A) is 10 to 87 mass%, the amount of the carboxylic acid ester (B) is 3 to 30 mass%, the amount of the insect repellent (C) is 10 to 60 mass%, and the mass ratio of the carboxylic acid ester (B) to the insect repellent (C) is 2:1 to 1:5, based on the total amount of the resin composition.

Description

Technical Field

[0001] This invention relates to resin compositions, components containing the resin compositions, laminates, and sustained-release formulations of insect repellents. Background Technology

[0002] Previously, resin compositions and molded articles containing volatile insect repellents and additives at room temperature were known. For example, Patent Document 1 describes a resin composition comprising a pyrethroid compound, a synergist, and a thermoplastic resin. Patent Document 2 describes a resin composition consisting of a resin, an active compound such as an insect repellent, a evaporative plasticizer with a vapor pressure of 0.001 mmHg or higher at 20°C, and an exudation accelerator.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2011-149000

[0006] Patent Document 2: Japanese Patent Application Publication No. 2005-320550 Summary of the Invention

[0007] In resin compositions containing volatile active ingredients, the active ingredients exert their effectiveness through volatilization into the surrounding environment. However, the concentration of the active ingredients in the resin composition gradually decreases over time. As the concentration decreases, the volatilization rate of the active ingredients also decreases over time. Therefore, although the active ingredients remain in the resin composition, there is a problem of insufficient effectiveness and shortened shelf life. This decrease in volatilization rate over time is particularly pronounced when the saturated vapor pressure of the active ingredient is 1.0 × 10⁻⁶. －4 When Pa is significantly higher than a certain value, it becomes a problem.

[0008] Furthermore, while increasing the concentration of active ingredients in the resin composition can improve the volatilization rate, simply increasing the concentration not only fails to effectively extend the shelf life but also easily leads to exudation on the product surface, often resulting in poor appearance. Additionally, when plasticizers and other additives are used in conjunction, these additives sometimes also exudate, causing poor appearance. It should be noted that in this invention, exudation refers to the phenomenon where active ingredients and additives that exudate from the resin composition do not volatilize from the surface of the molded body made of the resin composition but remain on the surface as liquid or solid substances.

[0009] Therefore, the object of the present invention is to provide a resin composition suitable for manufacturing a product that has a long effective time by causing the active ingredient to volatilize at a high rate over a long period of time and is not prone to exudation on the product surface, as well as components, laminates and insect repellent sustained-release formulations containing the resin composition.

[0010] The inventors conducted in-depth research to solve the aforementioned problems and discovered that the following resin composition can solve these problems, thus completing the present invention. The resin composition is a resin (A) comprising at least a copolymer of ethylene and an oxygen-containing vinyl monomer, having a molecular weight of 255–380 and a saturated vapor pressure of 1.0 × 10⁻⁶ at 25°C. －4 Straight-chain or branched carboxylic esters (B) with a pressure above Pa and a saturated vapor pressure of 1.0 × 10⁻⁶ at 25°C. －4 A resin composition of an insect repellent (C) of Pa or higher, wherein, based on the total amount of the resin composition, the amount of resin (A) is 10 to 87% by mass, the amount of carboxylic acid ester (B) is 3 to 30% by mass, the amount of insect repellent (C) is 10 to 60% by mass, and the mass ratio of carboxylic acid ester (B) to insect repellent (C) is 2:1 to 1:5.

[0011] That is, the present invention includes the following appropriate methods.

[0012] [1] A resin composition comprising at least:

[0013] Resin (A) is a copolymer of ethylene and a vinyl monomer containing oxygen atoms.

[0014] The molecular weight is 255–380, and the saturated vapor pressure at 25°C is 1.0 × 10⁻⁶. －4 Straight-chain or branched carboxylic esters (B) with a pH of 1 or higher, and

[0015] The saturated vapor pressure at 25℃ is 1.0 × 10⁻⁶. －4 Insecticides with a strength of Pa or higher (C),

[0016] Based on the total amount of the resin composition, the amount of resin (A) is 10-87% by mass, the amount of carboxylic acid ester (B) is 3-30% by mass, the amount of insect repellent (C) is 10-60% by mass, and the mass ratio of carboxylic acid ester (B) to insect repellent (C) is 2:1 to 1:5.

[0017] [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 olefinic unsaturated bond.

[0018] [3] The resin composition according to [1] or [2] above, wherein the carboxylic acid ester (B) is at least one component selected from esters of saturated fatty acids having 8 to 20 carbon atoms, esters of dicarboxylic acids having 2 to 8 carbon atoms, carbonates, citrates and acetylic acid esters.

[0019] [4] The resin composition according to any one of [1] to [3] above, wherein the insecticide (C) is a pyrethroid insecticide.

[0020] [5] According to the resin composition described in [4] above, wherein the insect repellent (C) is at least one component selected from Transfluthrin, Metofluthrin, Empenthrin, Profluthrin, Meperfluthrin and Heptafluthrin.

[0021] [6] The resin composition according to any one of [1] to [5] above, wherein 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 satisfy formula (1).

[0022] 0.2≤Pb / Pc≤500 (1)

[0023] [7] The resin composition according to any one of [1] to [6] above, wherein the solubility index (R1) of resin (A) and carboxylic acid ester (B), the solubility index (R2) of resin (A) and insect repellent (C) and the solubility index (R3) of carboxylic acid ester (B) and insect repellent (C) are all 5.0 or less.

[0024] [8] A component for a sustained-release formulation of an insect repellent, comprising the resin composition described in any one of [1] to [7] above.

[0025] [9] A laminate comprising: a first layer (D) containing a resin composition as described in any one of [1] to [7] above, and a second layer (E) permeable to a carboxylic acid ester (B) and an insect repellent (C).

[0026]

[10] According to the laminate described in [9] above, the first layer (D) is a single layer, the second layer (E) is a single layer or multiple layers, one side of the second layer (E) is in contact with the first layer (D), and the other side of the second layer (E) is the outermost surface of the laminate.

[0027]

[11] According to the laminate described in [9] or

[10] above, it has at least a layer structure of layer (E) / layer (D) / layer (E), where each layer (E) may be the same or different from the others.

[0028]

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

[11] above, wherein it further has a third layer (F) different from layer (E) and layer (D).

[0029]

[13] According to the laminate described in

[12] above, the third layer (F) is a layer selected from at least one of the following: an adhesive layer, a surface protective layer, a coloring layer, an insect repellent barrier layer, an appearance design layer, and an ultraviolet absorption layer.

[0030]

[14] An insect repellent slow-release formulation having the component described in [8] above and / or the laminate described in any one of [9] to

[13] above.

[0031] According to the present invention, it is possible to provide a resin composition suitable for manufacturing a product having a long effective time of resin composition by long-term volatile release of active ingredients at a high volatile amount and not easily exuding on the product surface, as well as components, laminates and insect repellent sustained-release formulations containing the resin composition. Attached Figure Description

[0032] Figure 1 This is a graph showing the change over time in the retention rate of the active ingredient concentration in the laminates shown in the examples and comparative examples.

[0033] Figure 2 This is a graph showing the change over time in the sustained-release amount of the active ingredient in the laminates shown in the examples and comparative examples. Detailed Implementation

[0034] The embodiments of the present invention will now be described in detail. It should be noted that the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the invention.

[0035] The resin composition of the present invention comprises at least a resin (A) that is a copolymer of ethylene and an oxygen-containing vinyl monomer, having a molecular weight of 255 to 380 and a saturated vapor pressure of 1.0 × 10⁻⁶ at 25°C. －4 Straight-chain or branched carboxylic esters (B) with a pressure above Pa and a saturated vapor pressure of 1.0 × 10⁻⁶ at 25°C. －4 The insect repellent (C) with a mass of Pa or higher, based on the total amount of the resin composition, comprises 10-87% resin (A) by mass, 3-30% carboxylic acid ester (B) by mass, and 10-60% insect repellent (C) by mass, with a mass ratio of carboxylic acid ester (B) to insect repellent (C) of 2:1 to 1:5. Here, resin (A) is the matrix resin of the resin composition, carboxylic acid ester (B) is a volatile plasticizer, and insect repellent (C) is the active ingredient in the resin composition. It should be noted that in this specification, "carboxylic acid ester (B)" is also referred to as "plasticizer (B)".

[0036] By comprising a resin composition containing the above-mentioned resin (A), carboxylic acid ester (B), and insect repellent (C) in the following amounts, it is possible to enable the insect repellent (C), as an active ingredient, to volatilize at a high rate over a long period of time, and to inhibit the exudation of carboxylic acid ester (B) and insect repellent (C) on the product surface. Specifically, based on the total amount of the resin composition, the amount of resin (A) is 10 to 87% by mass, the amount of carboxylic acid ester (B) is 3 to 30% by mass, the amount of insect repellent (C) is 10 to 60% by mass, and the mass ratio of carboxylic acid ester (B) to insect repellent (C) is 2:1 to 1:5.

[0037] The aforementioned copolymer of ethylene and an oxygen-containing vinyl monomer, namely resin (A) and carboxylic acid ester (B), are highly miscible components. A resin composition containing these components and insecticide (C) in the aforementioned proportions can retain a large amount of carboxylic acid ester (B) and insecticide (C) in resin (A), or a large amount of insecticide (C) in a mixture of resin (A) and carboxylic acid ester (B). Furthermore, it is believed that when insecticide (C) volatilizes, carboxylic acid ester (B) volatilizes simultaneously at a rate similar to that of insecticide (C). As a result, the rate at which the concentration of insecticide (C) in the resin composition decreases due to the volatilization of insecticide (C) from the resin composition can be slowed down, and the over-term decrease in the amount of insecticide (C) volatilized per unit surface area of ​​the product can be suppressed. Moreover, it is believed that insecticide (C), as an active ingredient, can volatilize at a high rate over a long period, and the exudation of carboxylic acid ester (B) and insecticide (C) on the product surface can be suppressed.

[0038] The amount of resin (A) in the resin composition of the present invention is 10 to 87% by mass, based on the total amount of the resin composition. When the amount of resin (A) is less than 10% by mass, the solubility of carboxylic acid ester (B) and insect repellent (C) is insufficient, making it difficult to retain these components in the resin composition and suppress exudation. Furthermore, when the amount of resin (A) exceeds 87% by mass, the amount of carboxylic acid ester (B) and insect repellent (C) in the resin composition decreases, resulting in insufficient shelf life. From the viewpoint of easily suppressing exudation and easily improving shape retention as needed, the amount of resin (A) based on the total amount of the resin composition is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. On the other hand, from the viewpoint of increasing the content of carboxylic acid ester (B) and insect repellent (C) in the resin composition and easily improving the shelf life, 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.

[0039] 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 insect repellent (C) cannot be reduced, and the time-dependent decrease in the amount of insect repellent (C) volatilized 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, and shape retention becomes difficult. From the viewpoint of easily suppressing the time-dependent decrease in the amount of insect repellent (C) volatilized, the amount of carboxylic acid ester (B) is preferably 5% by mass or more, more preferably 10% by mass or more. In addition, from the viewpoint of easily improving the physical properties of the resin composition, the amount of carboxylic acid ester (B) is preferably 25% by mass or less, more preferably 20% by mass or less.

[0040] The amount of insect repellent (C) included 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 of insect repellent (C) is insufficient, and consequently, the shelf life is insufficient. On the other hand, if the amount of insect repellent (C) exceeds 60% by mass, insect repellent (C) significantly leaches from the resin composition. From the viewpoint of easily increasing the volatilization and shelf life of insect repellent (C), the amount of insect repellent (C) is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and even more preferably 30% by mass or more. In addition, from the viewpoint of easily suppressing leachation from 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 improving the compatibility of the resin (A) and the carboxylic acid ester (B), the insecticide (C) is preferably selected from at least one of pyrethroid insecticides, organophosphate insecticides, carbamate insecticides, juvenile hormone-like insecticides, p-menthane-3,8-diol, N,N-diethyl-m-toluamide (DEET), carbamate-3,4-diol, p-dichlorobenzene, and camphor, and more preferably from at least one of pyrethroid insecticides.

[0041] The resin composition of the present invention contains a carboxylic acid ester (B) to an insect repellent (C) in a mass ratio of 2:1 to 1:5 (carboxylic acid ester (B): insect repellent (C)). If the amount of carboxylic acid ester (B) exceeds twice the amount of insect repellent (C), the amount of insect repellent volatilized in the initial stage of volatilization will be insufficient, and no insect repellent effect will be obtained. On the other hand, if the amount of insect repellent (C) exceeds five times the amount of carboxylic acid ester (B), the effect of inhibiting the decrease in the concentration of insect repellent (C) will not be obtained. The mass ratio of carboxylic acid ester (B) to insect repellent (C) is preferably 3:2 to 1:5, more preferably 1:1 to 1:5, further preferably 4:5 to 1:4, even more preferably 3:4 to 1:3, and particularly preferably 2:3 to 1:2.

[0042] 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) within the above-described mass range and mass ratio. This resin composition may contain other components besides resin (A), carboxylic acid esters (B), and insect repellents (C). From the viewpoint of easily improving the sustained-release quality of insect repellents (C) and easily improving the efficacy of insect repellents (C) as active ingredients, the total mass of resin (A), carboxylic acid esters (B), and insect repellents (C) contained in this resin composition, based on the total amount of this resin composition, is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, even more preferably 60% by mass or more, particularly preferably 70% by mass or more, particularly more preferably 80% by mass or more, and most preferably 90% by mass or more. Furthermore, the total amount of resin (A), carboxylic acid esters (B), and insect repellents (C) contained in this resin composition is only required to be 100% by mass or less based on the total amount of this resin composition.

[0043] The resin composition of the present invention comprises a resin (A) that is a copolymer of ethylene and a vinyl monomer containing oxygen atoms. Resin (A) is a copolymer of ethylene and a vinyl monomer containing oxygen atoms, and can be appropriately selected based on its compatibility with plasticizers (B) and insect repellents (C), as well as the physical properties required for components, laminates, and products containing the resin composition of the present invention. Examples of resin (A include, for example, ethylene-vinyl acetate copolymers, ethylene-(meth)acrylate copolymers (ethylene-methyl acrylate copolymers and / or ethylene-methyl methacrylate copolymers), copolymers of ethylene and organic carboxylic acid derivatives having olefinic unsaturated bonds, and ethylene-vinyl alcohol copolymers. One type of resin (A) can be used, or two or more resins can be used in combination. From the viewpoint of easily improving the exudation inhibition effect of carboxylic acid ester (B) and insect repellent (C), the amount of constituent units of the resin (A) from the vinyl monomer containing oxygen atoms is based on the total mass of the resin (A), preferably 5 to 50% by mass, more preferably 10 to 50% by mass, further preferably 20 to 50% by mass, even more preferably 30 to 50% by mass, and particularly preferably 30 to 40% by mass.

[0044] 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 and a low glass transition temperature. 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 the deactivation of the insect repellent (C), the resin (A) is preferably a resin that does not chemically react with the insect repellent (C). From the viewpoint of easily controlling the solubility and diffusion 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 and processed 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 and processed at a temperature lower than the decomposition temperature or boiling point of the insect repellent (C), it is easier to suppress the disappearance of the insect repellent (C) due to decomposition or volatilization during the processing of the resin composition.

[0045] From the viewpoint of easily increasing the volatilization rate of the insecticide (C) and easily controlling the exudation of the carboxylic acid ester (B) and the insecticide (C), the resin (A) is preferably a copolymer of ethylene and an organic carboxylic acid derivative having an olefinic unsaturated bond. It should be noted that the organic carboxylic acid derivative having an olefinic unsaturated bond is preferably selected from vinyl acetate, methacrylate, and acrylate, more preferably from methacrylate and / or acrylate, further preferably from alkyl methacrylate and / or alkyl acrylate, and particularly preferably from methyl methacrylate and / or methyl acrylate. In this case, from the viewpoint of easily further improving the effect of inhibiting the exudation of the carboxylic acid ester (B) and the insecticide (C), the amount of the constituent units of the resin (A) from the organic carboxylic acid derivative having an olefinic unsaturated bond, based on the total mass of the resin (A), is preferably 5 to 50% by mass, more preferably 10 to 50% by mass, further preferably 20 to 50% by mass, and even more preferably 30 to 40% by mass.

[0046] From the viewpoint of easily increasing the amount of insect repellent (C) volatilized per unit surface area of ​​the product, the weight-average molecular weight of the resin (A) is preferably 0.5 million to 1,000,000, more preferably 10,000 to 500,000, further preferably 30,000 to 400,000, even more preferably 30,000 to 300,000, particularly preferably 30,000 to 150,000, further particularly preferably 30,000 to 70,000, and most preferably 30,000 to 50,000. The weight-average molecular weight of the resin (A) is determined by gel permeation chromatography (GPC). The conditions described in the examples can be used as the determination conditions.

[0047] From the viewpoint of easily suppressing the volatilization of carboxylic acid ester (B) and pesticide (C) during processing, and from the viewpoint of easily maintaining the shape of the resin composition, the melting temperature of resin (A) is preferably 0–180°C, more preferably 10–150°C, even more preferably 15–120°C, even more preferably 20–100°C, extremely preferably 20–80°C, and extremely more preferably 20–65°C. The melting temperature of resin (A) is determined according to JIS K7215-2012.

[0048] From the viewpoint of easily increasing the amount of insect repellent (C) volatilized per unit surface area of ​​the product, and from the viewpoint of easily maintaining the shape of the resin composition, the flexural stiffness of the resin (A) is preferably 0.001 to 4000 MPa, more preferably 0.001 to 2500 MPa, further preferably 0.01 to 500 MPa, even 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 stiffness of the resin (A) is measured according to ASTM D747-70.

[0049] From the viewpoint of easily increasing the amount of insect repellent (C) volatilized per unit surface area of ​​the product, and from the viewpoint of easily maintaining the shape of the resin composition, the D-type hardness of the resin (A) is preferably 1 to 70 MPa, more preferably 1 to 40 MPa, further preferably 2 to 35 MPa, even more preferably 5 to 30 MPa, extremely preferably 5 to 25 MPa, and extremely more preferably 10 to 20 MPa. The D-type hardness of the resin (A) is measured according to JIS K7215-1986.

[0050] The resin composition of the present invention comprises a molecular weight of 255-380 and a saturated vapor pressure of 1.0 × 10⁻⁶ at 25°C. － 4 Straight-chain or branched carboxylic acid esters (B) with a pressure of Pa or higher can be used. As carboxylic acid esters (B), those with a molecular weight of 255–380 and a saturated vapor pressure of 1.0 × 10⁻⁶ at 25°C can be used. －4 One or more linear or branched carboxylic esters of type Pa or higher may be used, or two or more carboxylic esters may be used. Carboxylic esters (B) have a linear or branched structure and do not contain a cyclic structure. Linear or branched carboxylic esters refer to carboxylic ester compounds that do not contain the cyclic portion formed by the constituent atomic bonds of the carboxylic ester, but rather the chain portion formed by these atomic bonds.

[0051] The carboxylic acid ester (B) having the above-mentioned saturated vapor pressure functions as a volatile plasticizer in the resin composition of the present invention. By including the carboxylic acid ester (B), the mobility of the insecticide (C) in the resin composition is easily improved, the amount of insecticide (C) volatile per unit surface area of ​​the product is easily increased, and the high amount of insecticide (C) volatile is easily maintained for a long period. When 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 insecticide (C), and the effect of inhibiting the decrease in the concentration of the insecticide (C) is not obtained. On the other hand, when the molecular weight is greater than 380, the volatility of the plasticizer (B) is too low relative to the volatility of the insecticide (C), and therefore the effect of inhibiting the decrease in the concentration of the insecticide (C) is not obtained. 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. Furthermore, this 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.

[0052] The saturated vapor pressure (P) of carboxylic acid ester (B) at 25°C B ) is 1.0 × 10 －4 Pa or higher, preferably 1.0 × 10 Pa －3 Above Pa. If the saturated vapor pressure (P) B Less than 1.0 × 10 －4 If the saturated vapor pressure of carboxylic acid ester (B) is above the lower limit mentioned above, the carboxylic acid ester (B) will evaporate at a rate too slow relative to the evaporation rate of insecticide (C), thus failing to maintain a high evaporation rate of insecticide (C) over a long period. When the saturated vapor pressure of carboxylic acid ester (B) is above the lower limit mentioned above, it is easy for carboxylic acid ester (B) to evaporate at the same rate as insecticide (C), and carboxylic acid ester (B) also becomes easy to evaporate while insecticide (C) evaporates from the resin composition. As a result, the gradient of decrease in the concentration of insecticide (C) in the resin composition due to the evaporation of insecticide (C) from the resin composition is slowed down, making it easier to suppress the time-dependent decrease in the evaporation rate of insecticide (C) per unit surface area of ​​the product. The saturated vapor pressure (P) of carboxylic acid ester (B) at 25°C... b There is no particular upper limit for the content of ), but from the viewpoint of the molding and processability of the resin composition, 1.0 × 10⁻⁶ is preferred. 5 Pa or less, more preferably 1.0 × 10 Pa. 3 Pa or less, more preferably 10 Pa or less. From the above perspective, the saturated vapor pressure of the plasticizer (B) at 25°C is preferably 1.0 × 10⁻⁶ Pa. －4 Pa ~ 1.0 × 10 5 Pa, more preferably 1.0 × 10 Pa －4 Pa ~ 1.0 × 10 3 Pa, more preferably 1.0 × 10 Pa. －3 Pa ~ 10 Pa.

[0053] Carboxylic acid esters (B) have a structure formed by the formation of ester bonds between a carboxylic acid and an alcohol. Examples of carboxylic acids constituting carboxylic acid esters (B) include heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, oleic acid, linoleic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, citric acid, acetylic acid, and carbonic acid. From the viewpoint of easily improving the stability of the carboxylic acid ester (B) itself, straight-chain or branched carboxylic acids that do not contain carbon-carbon double bonds are preferred. From the viewpoint of preventing leakage, the carboxylic acid constituting the carboxylic acid ester (B) is preferably selected from straight-chain or branched saturated fatty acids with 8 to 20 carbon atoms, straight-chain or branched dicarboxylic acids with 2 to 8 carbon atoms, carbonic acid, citric acid, and acetylic acid. More preferably, it is selected from straight-chain or branched saturated fatty acids with 8 to 16 carbon atoms, straight-chain or branched dicarboxylic acids with 4 to 8 carbon atoms, citric acid, and acetylic acid. Further preferably, it is selected from caprylic acid, isononanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, adipic acid, sebacic acid, citric acid, and acetylic acid. Particularly preferred are lauric acid, myristic acid, adipic acid, sebacic acid, and acetylic acid. Even more preferably, it is selected from adipic acid, sebacic acid, and acetylic acid.

[0054] From the viewpoint of preventing leakage and moisture absorption, monohydric alcohols are preferred as the alcohol constituting the carboxylic acid ester (B). Monohydric alcohols with 1 to 12 carbon atoms are more preferred. Monohydric saturated alcohols with 1 to 12 carbon atoms are even more preferred. Alcohols selected from ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, ethylhexanol, nonanol, isononol, decanol, 2-propylhexanol, and dodecanol are even more preferred. Alcohols selected from ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, and ethylhexanol are extremely preferred. Alcohols selected from ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, and hexanol are even more preferred.

[0055] As for the carboxylic acid ester (B), from the viewpoint of preventing leakage, preventing moisture absorption, and preventing deterioration, it is preferable to select at least one of esters of saturated fatty acids having 8 to 20 carbon atoms, esters of dicarboxylic acids having 2 to 8 carbon atoms, carbonates, citrates, and acetylic acid esters. More preferably, it is an ester of any carboxylic acid and a monohydric alcohol selected from straight-chain or branched saturated fatty acids having 8 to 20 carbon atoms, straight-chain or branched dicarboxylic acids having 2 to 8 carbon atoms, carbonic acid, citric acid, and acetylic acid. Even more preferably, it is an ester of straight-chain or branched saturated fatty acids having 8 to 16 carbon atoms, straight-chain or branched dicarboxylic acids having 4 to 8 carbon atoms, citric acid, and acetylic acid esters. The ester of any carboxylic acid and a monohydric saturated alcohol having 1 to 12 carbon atoms is preferred, and more preferably, octyl octanoate, ethylhexyl octanoate, nonyl octanoate, isononyl octanoate, decyl octanoate, 2-propylhexyl octanoate, dodecyl octanoate, heptyl isononanoate, octyl isononanoate, ethylhexyl isononanoate, nonyl isononanoate, isonononanoate, decyl isononanoate, 2-propylhexyl isononanoate, dodecyl isononanoate, hexyl decanoate, heptyl decanoate, octyl decanoate, ethylhexyl decanoate, nonyl decanoate, isononyl decanoate, decyl decanoate, 2-propylhexyl decanoate, dodecyl decanoate, pentyl laurate, and hexyl laurate. Heptyl lauryl laurate, Octyl lauryl laurate, Ethylhexyl lauryl laurate, Nonyl lauryl laurate, Isononyl lauryl laurate, Decyl lauryl laurate, 2-propylhexyl lauryl laurate, Dodecyl lauryl laurate, Propyl myristate, Isopropyl myristate, Butyl myristate, Isobutyl myristate, Amyl 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, Amyl palmitate, Hexyl palmitate Esters, heptyl palmitate, octyl palmitate, ethylhexyl palmitate, nonyl palmitate, isononyl palmitate, dibutyl adipate, diisobutyl adipate, dipentyl adipate, dihexyl adipate, diheptyl adipate, diethylhexyl 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 citrate, tripropyl citrate, triisopropyl citrate.Preferred ingredients include decyl caprylate, 2-propylhexyl caprylate, dodecyl caprylate, nonyl isononanoate, isonononanoate, decyl isononanoate, 2-propylhexyl isononanoate, dodecyl isononanoate, octyl decanoate, ethylhexyl decanoate, nonyl decanoate, isononanoate, decyl decanoate, 2-propylhexyl decanoate, dodecyl decanoate, heptyl laurate, octyl laurate, ethylhexyl laurate, nonyl laurate, isononanoate, decyl laurate, 2-propylhexyl laurate, amyl myristate, and myristic acid. Hexyl myristate, 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, triethyl acetylated triethyl citrate. More particularly preferred are 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 acetylglucate. Further preferred are amyl myristate, hexyl myristate, heptayl myristate, octyl myristate, ethylhexyl myristate, dipentyl adipate, dihexyl adipate, diheptyl adipate, dipropyl sebacate, diisopropyl sebacate, dibutyl sebacate, diisobutyl sebacate, dipentyl sebacate, and triethyl acetyl citrate. Further preferred are dipentyl adipate, dipropyl sebacate, diisopropyl sebacate, dibutyl sebacate, and / or triethyl acetyl citrate. As the carboxylic acid ester (B), it may contain one or more of these carboxylic acid esters.

[0056] The resin composition of the present invention contains a saturated vapor pressure of 1.0 × 10⁻⁶ at 25°C. －4 Insecticide (C) with a strength of Pa or higher. One insecticide (C) may be used, or two or more insecticides may be used.

[0057] The saturated vapor pressure of insecticide (C) at 25°C is 1.0 × 10⁻⁶. －4 The saturated vapor pressure of the insecticide (C) is above 1.0 × 10⁻⁶ Pa. －4 At a pressure of 1 Pa, sufficient volatility is not achieved, and the insect-repellent effect for the specific space is not observed. The preferred saturated vapor pressure of the insect repellent (C) is 1.0 × 10⁻⁶ Pa. －3Pa or higher. From the viewpoint of appropriately adjusting volatility and easily extending shelf life, the saturated vapor pressure of the insecticide (C) is preferably 1 Pa or lower, more preferably 10 Pa. －1 Pa or less, more preferably 10 Pa －2 Below Pa.

[0058] Examples of insect repellents (C) include pyrethroid insect repellents, organophosphate insect repellents, carbamate insect repellents, p-menthane-3,8-diol, N,N-diethyl-m-toluamide (DEET), carbaane-3,4-diol, p-dichlorobenzene, and camphor. From the viewpoint of easily improving compatibility with resin (A) and carboxylic acid ester (B), pyrethroid insect repellents are preferred.

[0059] Examples of pyrethroid insecticides include transfluthrin, metofluthrin, profluthrin, empenthrin, allethrin, furamethrin, prallethrin, resmethrin, phthalthrin, phenothrin, momfluorothrin, heptafluthrin, meperfluthrin, and natural pyrethrin. From the viewpoint of volatilization rate, at least one insecticide selected from tetrafluoroethylene, methoxyfenozide, fenpyroxene, propofol, chlorfluazuron, and heptafluazuron is preferred; more preferably, at least one insecticide selected from tetrafluoroethylene, methoxyfenozide, fenpyroxene, propofol, and chlorfluazuron is preferred; even more preferably, at least one insecticide selected from tetrafluoroethylene, methoxyfenozide, fenpyroxene, and propofol is preferred; and even more preferably, tetrafluoroethylene and / or methoxyfenozide is preferred.

[0060] Examples of organophosphate insecticides include dichlorvos, trichlorfon, cyanophos, fenitrothion, chlorpyrifos, diazinon, fenthion, malathion, acephate, and isoxathion.

[0061] Examples of carbamate-based insect repellents include carbaryl and methomyl.

[0062] Other examples of insect repellents include p-menthane-3,8-diol, N,N-diethyl-m-toluamide (DEET), carbapenem-3,4-diol, p-dichlorobenzene, and camphor.

[0063] Preferably, the saturated vapor pressure (Pb) of the carboxylic acid ester (B) and the saturated vapor pressure (Pc) of the insect repellent (C) contained in the resin composition of the present invention at 25°C satisfy formula (1).

[0064] 0.2≤Pb / Pc≤500 (1)

[0065] When equation (1) is satisfied, the insecticide (C) is easily volatilized at a particularly high rate for a long time, and the exudation on the product surface is easily suppressed.

[0066] The saturated vapor pressure (Pb) of the carboxylic acid ester (B) and the saturated vapor pressure (Pc) of the insecticide (C) satisfy the relationship of Equation (1), indicating that the volatilization behaviors of these components are very similar to each other. Therefore, it is assumed that when the insecticide (C) volatilizes, the carboxylic acid ester (B) volatilizes at a rate very similar to that of the insecticide (C). As a result, the gradient of the decrease in the concentration of insecticide (C) in the resin composition due to the volatilization of insecticide (C) from the resin composition becomes very gentle, which easily further inhibits the time-dependent decrease in the amount of insecticide (C) volatilized per unit surface area of ​​the product.

[0067] From the viewpoint that the insect repellent (C) can easily volatilize at a high rate over a long period and that exudation on the product surface can be easily suppressed, the Pb / Pc ratio in formula (1) is preferably 0.4 or more, more preferably 0.7 or more, even more preferably 1.0 or more, 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 satisfy formula (1-2), and even more preferably satisfy formula (1-3).

[0068] 0.4≤Pb / Pc≤100 (1-1)

[0069] 0.7≤Pb / Pc≤50 (1-2)

[0070] 1.0≤Pb / Pc≤15 (1-3)

[0071] When the resin composition contains a mixture of two or more substances, including an insect repellent (C) and / or a carboxylic acid ester (B), it is preferable that the Pb / Pc value of the combination of the insect repellent (C) and the carboxylic acid ester (B) contained in the mixture is closest to that of the other two combinations, satisfying formula (1). This is because if a carboxylic acid ester (B) with a saturated vapor pressure reaching the range of Pb / Pc specified in formula (1) is present for any of the insect repellents (C), it is possible to obtain an effect of high volatility over a long period of time for at least one insect repellent (C), and minimal exudation on the product surface. From the viewpoint of easily obtaining the effects of high volatility, long-term volatility and exudation suppression for all insect repellents (C) contained in the mixture, it is preferable to include a carboxylic acid ester (B) with a saturated vapor pressure satisfying the Pb / Pc relationship specified in formula (1) for each insect repellent (C).

[0072] From the viewpoint of easily and stably maintaining the resin (A), carboxylic acid ester (B), and insecticide (C), and easily suppressing exudation, it is preferable that the resin composition of the present invention exhibits good compatibility among the resin (A), carboxylic acid ester (B), and insecticide (C). From the same viewpoint, the solubility index (R1) of the resin (A) and carboxylic acid ester (B), the solubility index (R2) of the resin (A) and insecticide (C), and the solubility index (R3) of the carboxylic acid ester (B) and insecticide (C) contained in the resin composition of the present invention are preferably 5.0 or less, more preferably 4.0 or less, further preferably 3.0 or less, and even more preferably 2.0 or less. It should be noted that the solubility index (R1), solubility index (R2), and solubility index (R3) are calculated using the formulas described later.

[0073] In this specification, the distance between the solubility parameters of resin (A) and carboxylic acid ester (B) represented by formula (2A) based on Hansen solubility parameters is referred to as the solubility index (R1) of resin (A) and carboxylic acid ester (B).

[0074] R1=((δp A -δp B ) 2 +(δh A -δh B ) 2 ) 1 / 2 (2A)

[0075] In equation (2A), δp A δp represents the polarity term in the Hansen solubility parameter of resin (A). B δh represents the polarity term in the Hansen solubility parameter for carboxylic acid esters (B). A δh represents the hydrogen bonding term in the Hansen solubility parameter of resin (A). B [The hydrogen bond term in the Hansen solubility parameter for carboxylic acid ester (B)]

[0076] The closer the solubility index (R1) is to 0, the better the compatibility between resin (A) and carboxylic acid ester (B). When the solubility index (R1) of resin (A) and carboxylic acid ester (B) is below the above-mentioned upper limit, it is easy to stably retain plasticizer (B) in the resin composition of the present invention and to easily suppress exudation.

[0077] In this specification, the distance between the solubility parameters of resin (A) and insect repellent (C) represented by formula (2B) based on Hansen solubility parameters is referred to as the solubility index (R2) of resin (A) and insect repellent (C).

[0078] R2=((δp A -δp C ) 2 +(δh A -δh C ) 2 ) 1 / 2 (2B)

[0079] In equation (2B), δp A δp represents the polarity term in the Hansen solubility parameter of resin (A). C The polarity term in the Hansen solubility parameter for insect repellent (C), δh A δh represents the hydrogen bonding term in the Hansen solubility parameter of resin (A). C [The hydrogen bond term in the Hansen solubility parameter for insect repellent (C)]

[0080] The closer the solubility index (R2) is to 0, the better the compatibility between resin (A) and insecticide (C). When the solubility index (R2) of resin (A) and insecticide (C) is below the above-mentioned upper limit, it is easy to stably retain insecticide (C) in the resin composition of the present invention, while it is easy to inhibit the exudation of insecticide (C) and to increase the volatilization of insecticide (C).

[0081] In this specification, the distance between the solubility parameters of the insect repellent (C) and the carboxylic acid ester (B) represented by formula (2C) based on the Hansen solubility parameter is referred to as the solubility index (R3) of the carboxylic acid ester (B) and the insect repellent (C).

[0082] R3=((δp C -δp B ) 2 +(δh C -δh B ) 2 ) 1 / 2 (2C)

[0083] [δp in equation (2C)] C δp B δhC and δh B As defined above]

[0084] The closer the solubility index (R3) is to 0, the better the compatibility between the carboxylic acid ester (B) and the insecticide (C). When the solubility index (R3) of the carboxylic acid ester (B) and the insecticide (C) is below the upper limit mentioned above, exudation is easily inhibited, and the high volatility of the insecticide (C) can be maintained for a long time.

[0085] Therefore, the solubility index (R1), solubility index (R2) and solubility index (R3) are represented by equations (2A) to (2C) based on the Hansen solubility parameter, respectively.

[0086] R1=((δp A -δp B ) 2 +(δh A -δh B ) 2 ) 1 / 2 (2A)

[0087] R2=((δp A -δp C ) 2 +(δh A -δh C ) 2 ) 1 / 2 (2B)

[0088] R3=((δp C -δp B ) 2 +(δh C -δh B ) 2 ) 1 / 2 (2C)

[0089] In equations (2A) to (2C),

[0090] δp A and δh A These represent the polar term and hydrogen bonding term in the Hansen solubility parameter of resin (A), respectively.

[0091] δp B and δh B These represent the polarity and hydrogen bonding terms in the Hansen solubility parameter of carboxylic acid ester (B), respectively.

[0092] δp C and δh C [These represent the polar term and hydrogen bond in the Hansen solubility parameter for insect repellent (C), respectively.]

[0093] The Hansen solubility parameter is derived by dividing the solubility of a substance into three components (dispersion term δd, polar term δp, and hydrogen bonding term δh) and representing them in three-dimensional space. The dispersion term δd represents the effect based on dispersion forces, the polar term δp represents the effect based on interpolar forces, and the hydrogen bonding term δh represents the effect based on hydrogen bonding forces. The definition and calculation of the Hansen solubility parameter are described in Charles M. Hansen's *Hansen Solubility Parameters: A Users' Handbook* (CRC published, 2007). Furthermore, by using the computer software *Hansen Solubility Parameters in Practice* (HSPiP), the Hansen solubility parameter can be easily calculated from the chemical structure of substances whose literature values ​​are unknown. In this invention, for compounds and monomers registered in the database included in HSP version 4.1, their values ​​are used; for unregistered compounds and monomers, δd, δp, and δh are calculated using the values ​​derived from HSP version 4.1.

[0094] The δp or δh of resin (A) is obtained by multiplying the δp or δh of the source monomers of each constituent unit contained in resin (A) by the content of that constituent unit.

[0095] When resin (A) is a mixture of two or more substances, the δp of resin (A) is obtained by multiplying the δp of each substance in the mixture by the content of each substance and summing the results.

[0096] When resin (A) is a mixture of two or more substances, the δh of resin (A) is obtained by multiplying the δh of each substance in the mixture by the content of each substance and summing the results.

[0097] When carboxylic acid ester (B) is a mixture of two or more substances, the δp of the mixture is multiplied by the content of each substance and the sum is taken as the δp of carboxylic acid ester (B).

[0098] When carboxylic acid ester (B) is a mixture of two or more substances, the δh of the mixture is multiplied by the content of each substance and summed to obtain the value of carboxylic acid ester (B).

[0099] When the insect repellent (C) is a mixture of two or more substances, the sum of the δp values ​​of each substance in the mixture and their respective contents is taken as the δp value of the insect repellent (C).

[0100] When the insect repellent (C) is a mixture of two or more substances, the sum of the δh values ​​of each substance in the mixture and their respective contents is taken as the δh value of the insect repellent (C).

[0101] The resin composition of the present invention may further contain other components besides resin (A), carboxylic acid ester (B), and insect repellent (C). Examples of other components include polymers other than resin (A) and plasticizers that are not equivalent to carboxylic acid ester (B) (e.g., plasticizers that are not carboxylic acid esters, with a saturated vapor pressure of less than 1.0 × 10⁻⁶ at 25°C). －4 The resin composition of the present invention may contain one or more other components, such as plasticizers (e.g., plasticizers), synergists, antioxidants, neutralizers, crosslinking agents, heat stabilizers, weather stabilizers, pigments, fillers, lubricants, or flame retardants. The resin composition of the present invention may contain one other component or two or more other components. The content of other components besides resin (A), carboxylic acid ester (B), and insect repellent (C) can be set as needed and is not particularly limited. Based on the total amount of the resin composition of the present invention, it is preferably less than 50% by mass, more preferably 30% by mass or less, and even more preferably 10% by mass or less.

[0102] The penetration of the resin composition of the present invention can be appropriately adjusted according to the intended use of the resin composition, and is not particularly limited thereto.

[0103] From the viewpoint of easily increasing the amount of active ingredient volatilized per unit surface area of ​​the insect repellent (B) and easily improving the dimensional stability of the parts and laminates obtained from the resin composition, the value is preferably 1 to 600, more preferably 2 to 400, even more preferably 3 to 300, particularly preferably 5 to 250, even more preferably 10 to 200, and most preferably 15 to 100.

[0104] The penetration test was performed according to the penetration test method described in JIS K2207. A cylindrical glass container with a diameter of 10 mm and a depth of 40 mm was used instead of the test container specified in JIS K2207. The constant temperature water bath was used and the test was performed in an air bath at a room temperature of 25°C with a load of 50 g.

[0105] The method for manufacturing the resin composition of the present invention is not particularly limited. For example, the resin composition can be obtained by mixing resin (A), carboxylic acid ester (B), and insect repellent (C) as raw materials using a mixer such as a Banbury mixer, super mixer, kneader, extruder, planetary mixer, disc mixer, disperser, roller mill, or mixing kettle. The obtained resin composition can be shaped into powder, granules, or blocks. A masterbatch prepared by pre-mixing at least a portion of the raw materials, namely resin (A), carboxylic acid ester (B), and insect repellent (C), can be used.

[0106] Alternatively, a resin composition can be manufactured by pre-molding at least a portion of the raw materials (e.g., resin (A)) of resin (A), carboxylic acid ester (B), and insect repellent (C) into a powder, granules, flakes, or block shape, and then contacting the resulting molded body with a liquid or gas containing the remaining raw materials (e.g., carboxylic acid ester (B) and / or insect repellent (C)) to impregnate the molded body with the remaining raw materials. Methods for contacting the resulting molded body with the liquid include immersing the molded body in the liquid, adding the molded body to the liquid and stirring as needed, and coating the molded body with the liquid.

[0107] For example, when the resin composition contains two or more resins (A), the resin (A), carboxylic acid ester (B) and insect repellent (C) can be mixed at one time to obtain the resin composition, or one resin (A) can be mixed with carboxylic acid ester (B) and / or insect repellent (C) and the resulting mixture can be mixed with the remaining components to obtain the resin composition.

[0108] The resin composition of the present invention is used in sustained-release formulations of insect repellents. Sustained-release formulations of insect repellents are products that provide an insect-repellent effect by causing the insect repellent to volatilize and diffuse in space. There are no particular limitations on the method of preparation; examples include molding the resin composition of the present invention alone, combining the resin composition of the present invention with other materials, and incorporating a component using the resin composition of the present invention into a container, frame, or insect repellent volatilization device. To maintain the required mechanical properties or achieve a suitable appearance, the sustained-release formulation of insect repellents using the resin composition of the present invention is preferably formed by combining the resin composition of the present invention with other materials, or by incorporating a component using the resin composition of the present invention into a container, frame, or insect repellent volatilization device; particularly preferred is incorporating a component using the resin composition of the present invention into a container, frame, or insect repellent volatilization device. Sustained-release formulations of insect repellents comprising at least a portion of the resin composition of the present invention are also referred to as sustained-release resin formulations of insect repellents.

[0109] The present invention further provides a component for an insect repellent sustained-release formulation (insect repellent sustained-release resin formulation) comprising the resin composition of the present invention described above. This component can be a molded article comprising the resin composition of the present invention, for example, a molded body obtained by molding the resin composition of the present invention. The component of the present invention can be manufactured, for example, by molding the resin composition of the present invention using known molding methods such as injection molding, extrusion molding, pressure molding, and slush molding (powder molding). The shape of the molded body can be appropriately determined according to the conditions and purpose of using the molded body, and is not particularly limited. For example, it can be rod-shaped, flat, mesh-like, pellet-shaped, spherical, fan-shaped, triangular, etc., and can be processed into shapes such as rope, fiber, non-woven fabric, sheet, film, tube, granules, etc.

[0110] The component of the present invention can be a composite made of the resin composition of the present invention and other materials. For example, this component can be manufactured by incorporating the resin composition of the present invention into a molded body that is incompatible with the resin composition of the present invention. When the component of the present invention is a composite as described above, the shape of the molded body constituting the composite can be appropriately selected according to the conditions and purpose of using the composite, and is not particularly limited. For example, it can be rod-shaped, flat, mesh-shaped, spherical, fan-shaped, triangular, etc., and can also be rope, fiber, non-woven fabric, sheet, film, tube, granule, etc. Examples of materials for the molded body include resin, metal, ceramic, glass, plant materials and their derivatives, animal leather, hair, etc. Examples of methods for incorporating the resin composition of the present invention into 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 a liquid resin composition of the present invention and stirring as needed; coating the molded body with a liquid resin composition of the present invention; attaching a sheet-like resin composition of the present invention to the molded body; and weaving the molded body together with the molded body containing the resin composition of the present invention.

[0111] The present invention further provides a laminate comprising a first layer (D) containing the resin composition of the present invention described above, and a second layer (E) permeable to carboxylic acid esters (B) and insect repellents (C). The first layer (D) can be a single layer containing the resin composition of the present invention, or it can be a multilayer layer composed of two or more layers containing the resin composition of the present invention. When the layer (D) is multilayered, each layer can be identical to the others, or it can be layers with different compositions and / or thicknesses, for example. The amount of the resin composition of the present invention contained in the first layer (D) can be appropriately set according to the intended use of the laminate. Based on the total amount of the first layer (D), it is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and even more preferably 80% by mass or more. Furthermore, this amount is acceptable as long as it is 100% by mass or less. Therefore, the first layer (D) can be a layer composed of the resin composition of the present invention. The first layer (D) can be a single layer or multiple layers; from the viewpoint of ease of manufacturing the laminate of the present invention, a single layer is preferred.

[0112] The second layer (E) in this invention, which is permeable to carboxylic esters (B) and insect repellents (C), refers to a layer that satisfies the requirements defined in the following methods.

[0113] 3g of carboxylic acid ester (B) was placed in a 60mm diameter permeability cup used for evaluating the moisture permeability of moisture-proof packaging materials as specified in JIS Z 0208, and the cup was sealed using layer (E) instead of the packaging material. The cup was placed in an oven at 40°C, and after 24 hours, the weight of the carboxylic acid ester (B) was measured. A layer was defined as permeable to the carboxylic acid ester (B) when the weight of the carboxylic acid ester (B) decreased by more than 0.5mg from its initial amount. The same method was used to measure the permeability using an insect repellent (C) instead of the carboxylic acid ester (B). A layer was defined as permeable to the insect repellent (C) when the weight of the insect repellent (C) decreased by more than 0.5mg. A layer that satisfies the above conditions for both carboxylic acid ester (B) and insect repellent (C) is the permeable layer (E) of this invention for both carboxylic acid ester (B) and insect repellent (C). Furthermore, the value of the weight reduction measured as described above is taken as the permeability of the layer used in the measurement to each component. It should be noted that the transmittance described in the embodiments of this specification is the transmittance measured using the method described above.

[0114] When such a layer (E) is used, and the space containing carboxylic acid ester (B) and insect repellent (C) is separated from the space where carboxylic acid ester (B) and insect repellent (C) do not exist, carboxylic acid ester (B) and insect repellent (C) move to the space where carboxylic acid ester (B) and insect repellent (C) do not exist, and carboxylic acid ester (B) and insect repellent (C) will exist in both spaces.

[0115] From the viewpoint of obtaining a formulation with a long shelf life, the permeability of layer (E) to carboxylic acid ester (B) is determined as described above, preferably 0.5 mg to 15 mg, more preferably 0.5 mg to 10 mg, further preferably 1 mg to 6 mg, and even more preferably 2 mg to 5 mg. From the viewpoint of fully realizing the efficacy of insect repellent (C), the permeability of layer (E) to insect repellent (C) is determined as described above, preferably 1 mg to 6 mg, more preferably 2 mg to 5 mg. From the viewpoint of balancing efficacy and shelf life, the ratio of the permeability of layer (E) to insect repellent (C) to the permeability of layer (E) to carboxylic acid ester (B) (permeability C / permeability B) is preferably 0.5 to 3, more preferably 0.8 to 2.5, and even more preferably 1 to 2.

[0116] The materials contained in layer (E) are selected in a manner that allows for a desired degree of permeability to the carboxylic acid ester (B) and the insect repellent (C) based on the types of carboxylic acid ester (B) and insect repellent (C) used. There are no particular limitations; examples include polyolefin resins such as polyethylene and polypropylene, ethylene copolymer resins such as ethylene-vinyl acetate copolymer, biodegradable resins such as polylactic acid, and vinyl chloride. From the viewpoint of easily achieving good permeability to the insect repellent (C), layer (E) preferably contains ethylene copolymer resin and / or polyolefin resin.

[0117] To adjust the permeability of layer (E) to carboxylic acid ester (B) and insect repellent (C) and thus appropriately change the amount of carboxylic acid ester (B) and insect repellent (C) volatilized through layer (E), layer (E) may have through-holes. The diameter of these through-holes can be appropriately adjusted, preferably from 0.1 to 500 μm. When layer (E) has through-holes, as described above, plasticizer (B) and insect repellent (C) permeate through layer (E) and volatilize. Therefore, layer (E) need not be composed of a material permeable to plasticizer (B) and insect repellent (C), and the material constituting layer (E) can be any material including known resins, metals, glass, etc. From a processability point of view, the material constituting layer (E) is preferably a thermoplastic resin.

[0118] Layer (E) can also be a material made of fibrous materials such as cloth or paper. Examples of such fibrous materials include, for example, cellulose fibers, polyethylene fibers, polypropylene fibers, polyethylene terephthalate fibers, metal fibers, animal hair, or mixtures thereof. These materials may contain adhesives that connect the fibers, fillers that fill the gaps between the fibers, dyes, pigments, coatings, etc., for imparting color and pattern.

[0119] Layer (E) can be a single layer or multiple layers. For example, a laminated paper obtained by coating paper with a polyolefin resin can be described as a multi-layered layer (E). In this case, for example, in a laminate consisting of at least layers (E) / layer (D), the polyolefin resin layer of the multi-layered layer (E) can be the surface in contact with layer (D), and the paper layer can also be the surface in contact with layer (D). Furthermore, a laminate consisting of a single layer (D), a single or multiple layers (E), one surface of the second layer (E) in contact with the first layer (D), and the other surface of the second layer (E) being the outermost surface of the laminate can be any of the following: a laminate consisting of a multi-layered layer (E) with the polyolefin resin layer in contact with layer (D) and the paper layer being the outermost surface of the laminate; or a laminate consisting of a paper layer in contact with layer (D) and the polyolefin resin layer being 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.

[0120] A laminate comprising a first layer (D) containing the resin composition of the present invention and a second layer (E) permeable to a carboxylic acid ester (B) and an insect repellent (C) may further comprise a third layer (F) different from layers (E) and (D). Examples of the third layer (F) include at least one layer selected from adhesive layers, surface protective layers, coloring layers, insect repellent barrier layers, appearance design layers, and ultraviolet absorbing layers.

[0121] 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 a carboxylic acid ester (B) and an insect repellent (C). For example, it can be a laminate in which layers (D) and (E) are sequentially stacked, a laminate in which layers (E), (D), and (E) are sequentially stacked, or a laminate in which layers (D), (E), and (D) are sequentially stacked. A laminate in which layers (E), (D), and (E) are sequentially stacked allows the insect repellent (C) to evaporate from both sides of the laminate, enabling the insect repellent to be supplied into space at a high evaporation rate. Examples include a laminate consisting of at least one layer (E) / layer (D), a laminate consisting of at least one layer (E) / layer (D) / layer (E), and a laminate consisting of at least one layer (E) / layer (D) / layer (E) / layer (D) / layer (E). Here, in the layer structure of layer (E) / layer (D) / layer (E), layer (E) / layer (D) / layer (E) / layer (D) / layer (E), etc., each layer (E) can be the same or different from each other, and each layer (D) can be the same or different from each other. In addition, the above layer structure can further include a layer (F).

[0122] Another embodiment of the laminate of the present invention is a laminate comprising: a first layer (D) composed of the resin composition of the present invention, a second layer (E) permeable to a carboxylic acid ester (B) and an insect repellent (C), and a third layer (F) which may or may not be permeable to the insect repellent (C), the laminate having at least a layer configuration consisting of layers (E) / layer (D) / layer (F) stacked sequentially. The laminate constructed in this manner can enhance the product's value by altering the evaporation rate of the insect repellent (C) from both sides of the laminate, allowing layer (F) to possess a function different from insect repellency. For example, by making layer (F) a non-permeable material, the insect repellency effect can be achieved only on one side of the space separated by the laminate, or by making layer (F) an adhesive material, the laminate can be attached to a suitable surface. Furthermore, the above-described layer configuration may further include layer (F).

[0123] Another embodiment of the laminate of the present invention is a laminate formed by laminating a first layer (D) composed of the resin composition of the present invention and a second layer (E) permeable to both the plasticizer (B) and the insect repellent (C) in a layer (D) / layer (E) sequence. The laminate formed in this manner can improve the mechanical properties of the laminate while ensuring the volatility of the insect repellent (C), or avoid direct contact between the insect repellent (C) and the first layer (D). Furthermore, when the first layer (D) has adhesive properties, the laminate can be adhered to a suitable surface. Additionally, the above-described layer configuration may further include a layer (F).

[0124] 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 multiple layers, one side of the second layer (E) is in contact with the first layer (D), and the other side of the second layer (E) is the outermost surface of the laminate. Examples of such a laminate include a laminate comprising a single layer (D) and a single or multiple layers (E) where the side of layer (E) not in contact with layer (D) is the outermost surface of the laminate; and a laminate comprising a layer (E) and a single layer (D) / layer (E) where at least one of the two layers (E) has a side not in contact with layer (D) as the outermost surface of the laminate. For example, examples include a laminated body composed of layers (E) / single layers (D) stacked sequentially, a laminated body composed of layers (E) / single layers (D) / F stacked sequentially, a laminated body composed of layers (E) / single layers (D) / E stacked sequentially, and a laminated body composed of layers (E) / single layers (D) / E / F stacked sequentially.

[0125] The method for manufacturing the laminate of the present invention is not particularly limited. Examples include: coating a layer (E) having a sheet-like or similar shape with a resin composition of the present invention that is liquefied by hot melting or dissolving in a suitable solvent; coating a layer (D) having a sheet-like or similar shape with a composition of a supply layer (E) that is liquefied by hot melting or dissolving in a suitable solvent; co-extruding these compositions when both the composition of the supply layer (D) and the composition of the supply layer (E) are thermoplastic; performing multilayer injection molding; performing composite spinning; and performing extrusion lamination. Here, when it is necessary to process the layer (E) at high temperatures, the insect repellent (B) contained in the layer (D) may sometimes volatilize depending on the high temperature conditions used to process the layer (E). From the viewpoint of easily preventing such volatilization of the insect repellent (B), it is preferable to manufacture the laminate of the present invention by coating either the layer (D) or the layer (E) by hot melting or dissolving the material of the other layer in a solvent, or by extruding and laminating the layer (D) onto the layer (E).

[0126] Example

[0127] The present invention will now be described in more detail through examples and comparative examples, but the present invention is not limited to the above examples. It should be noted that, unless otherwise specified, "%" and "parts" in the examples and comparative examples refer to "% by mass" and "parts by mass," respectively. The materials used in the examples are as follows.

[0128] <Resin (A)>

[0129] The resins described below were used in the examples and comparative examples. It should be noted that resin (X1) is a resin that is not included in resin (A) of the resin compositions of the present invention.

[0130] (A1): Ethylene-methyl acrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Acryft (registered trademark), methyl acrylate comonomer content 35% by mass, weight average molecular weight 4.0 × 10⁻⁶ 4 )

[0131] (A2): Ethylene-methyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Acryft (registered trademark), methyl methacrylate comonomer content 25% by mass, weight average molecular weight 6.1×10⁻⁶ 4 )

[0132] (A3): Ethylene-methyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Acryft (registered trademark), methyl methacrylate comonomer content 18% by mass, weight average molecular weight 6.4 × 10⁻⁶ 4 )

[0133] (A4): Ethylene-vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., content of vinyl acetate comonomer 28% by mass)

[0134] (X1): Low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., Sumicasen (registered trademark) F101, weight average molecular weight 6.1×10⁻⁶). 4 )

[0135] <Plasticizer (Carboxylic Acid Ester (B))>

[0136] In the examples and comparative examples, the following carboxylic esters or plasticizers were used. It should be noted that carboxylic esters (Y1) and (Y2) are not the carboxylic esters (B) contained in the resin compositions of the present invention. Additionally, (Y3) is a plasticizer, but not a carboxylic ester.

[0137] (B1): Diisopropyl sebacate (manufactured by Wako Pure Chemical Industries, Ltd., premium reagent grade, molecular weight 286.4, saturated vapor pressure at 25°C: 6.5 × 10⁻⁶). －3 Pa)

[0138] (B2): Triethyl acetylcitrate (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 318.3, saturated vapor pressure at 25°C 2.0 × 10⁻⁶). －2 Pa)

[0139] (Y1): Diethyl adipate (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 202.5, saturated vapor pressure at 25°C: 1.2 Pa)

[0140] (Y2): Tributyl acetyl citrate (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 402.5, saturated vapor pressure at 25°C: 1.7 × 10⁻⁶) －4 Pa)

[0141] (Y3): Hexadecyl alcohol (Goldrej, Ginol 16, purity 98%, molecular weight 242.4, saturated vapor pressure at 25°C: 8.0 × 10⁻⁶). －4 Pa (literature value, Daubert, TE, RPDanner. Physical and Thermodynamic Properties of Pure Chemicals Data Compilation. Washington, DC: Taylor and Francis, 1989.))

[0142] <Insecticide>

[0143] In the examples and comparative examples, the following insect repellents were used.

[0144] (C1): Methoxybenzylfluoromethyl (manufactured by Sumitomo Chemical Co., Ltd., trade name: Eminence (registered trademark), saturated vapor pressure at 25°C: 1.7 × 10⁻⁶ －3 Pa)

[0145] (C2): Tetrafluoroethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Biothrin (registered trademark), saturated vapor pressure at 25°C: 3.7 × 10⁻⁶ －3 Pa)

[0146] <Layer(E)>

[0147] In the examples and comparative examples, layers of the following permeable materials were used. Furthermore, the permeability of each layer to insect repellents and plasticizers is shown in Table 1.

[0148] (E1): Linear low-density polyethylene film (manufactured by Sumitomo Chemical Co., Ltd., linear low-density polyethylene NOBLEN, grade: blow-molded from FV203)

[0149] (E2): Laminated kraft paper (paper obtained by laminating low-density polyethylene onto kraft paper, with a unit area weight of 60g / m²). 2 )

[0150] <Layer (F)>

[0151] In the examples and comparative examples, layers of the following materials were used. Furthermore, the permeability of layer (F) to insect repellents and plasticizers is shown in Table 1.

[0152] (F1): Polyethylene terephthalate film (manufactured by Panac Co., Ltd., thickness: 100μm)

[0153] The physical property determination and performance evaluation were carried out in the examples and comparative examples according to the following methods.

[0154] (1) Saturated vapor pressure

[0155] Saturated vapor pressure was determined using temperature-programmed gas chromatography according to the Donovan method (New method for estimating vapor pressure by the use of gas chromatography: Journal of Chromatography A.749 (1996) 123-129). It should be noted that although the plasticizer (Y3) was not determined using the above method, literature values ​​or estimated values ​​were recorded for reference.

[0156] (2) Penetration

[0157] The penetration of each composition was determined according to the penetration test method described in JIS K2207. Instead of using the test container and constant temperature water bath specified in JIS K2207, the sample was placed in a cylindrical glass container with a diameter of 10 mm and a depth of 40 mm. The penetration was measured under air at a room temperature of 25°C with a load of 50 g. The penetration of the sample in the same container was measured three times, and the average value was taken as the penetration. For each measurement, a point at least 3 mm from the circumference of the test container was selected. For subsequent measurements, points at least 3 mm from the previous penetration location were selected. If the sample is highly flexible and the needle contacts the bottom of the glass container, the penetration is set to 400 based on the container depth (40 mm). A high penetration indicates a flexible composition.

[0158] (3) Weight-average molecular weight

[0159] The equivalent weight-average molecular chain length (Aw) of polystyrene in resin (A) was determined using gel permeation chromatography (GPC) with a device equipped with a light scattering detector, under the following conditions. The baseline on the chromatogram is a straight line connecting points in a stable horizontal region with sufficiently short retention times relative to the observed sample elution peaks to points in a stable horizontal region with sufficiently long retention times relative to the observed solvent elution peaks.

[0160] GPC Unit: Tosoh HLC-8121GPC / HT

[0161] Precision Detectors PD2040 (Light Scattering Detector)

[0162] Differential pressure viscometer: Viscotek H502

[0163] GPC column: 3 columns from Tosoh GMHHR-H(S)HT

[0164] Sample solution concentration: 2 mg / mL

[0165] Injection volume: 0.3 mL

[0166] Measurement temperature: 155℃

[0167] Dissolution conditions: 145℃ for 2 hours

[0168] Mobile phase: o-dichlorobenzene (with added BHT 0.5 mg / mL)

[0169] Flow rate during elution: 1 mL / min

[0170] Measurement time: approximately 1 hour

[0171] Method for creating calibration curves: using standard polystyrene.

[0172] The weight-average molecular weight (Mw) of each polymer is calculated from the weight-average molecular chain length (Aw) of polystyrene using the following formula.

[0173] Molecular weight (Mw) = Chain length (Aw) × Q factor

[0174] The Q factor is a value obtained by dividing the molecular weight of the monomer unit of the polymer by the extended chain length of the monomer unit (per... (Molecular weight). For each resin (A), the average molecular weight of the monomers constituting the resin is taken as the monomer unit molecular weight, and the ideal carbon interval between each C-C trans bond in polyethylene is taken as the molecular weight. The calculation is performed as an extension of the chain length of a single unit.

[0175] (4) Preparation of resin composition and test sample for sustained release determination

[0176] A resin composition was prepared by mixing resin (A), carboxylic acid ester (B), and insect repellent (C) using a Labo Plastomill (Toyo Seiki Co., Ltd., model 65C150) or a benchtop small mixer (DSM Xplore, 15cc twin-shaft micro mixer) at 80 rpm and 70°C for 15 minutes.

[0177] The obtained resin composition was pressurized at 70°C and 20 MPa to obtain a sheet-like molded body (layer (D)) with a length of 50 mm, a width of 150 mm, and a thickness of 0.15 mm. Next, a layer (layer (E)) consisting of a linear low-density polyethylene film (E1) with a corona-treated resin surface or laminated kraft paper (E2) was attached to both sides of layer (D) with the corona-treated surface in contact to obtain a laminate. To prevent layer (D) from being exposed, the end faces of the obtained laminate were heat-sealed to obtain a sample.

[0178] (5) Method for determining sustained-release content

[0179] (5-1)Standing conditions

[0180] Five samples were prepared according to the method described in (4). Each sample was placed in the laboratory for 3, 7, 14, 21 and 42 days at 30°C and wind speed of 0.5 m / s.

[0181] (5-2) Sustained-release ratio (Qb and Qc) and sustained-release mass (Rb and Rc)

[0182] The mass reduction [g] of each sample was determined by the mass difference between the sample before and after standing. This mass reduction was then taken as the total sustained-release mass Rt of the carboxylic acid ester (B) and the insecticide (C).

[0183] Next, each sample, after standing for a specified number of days, was immersed in 50 mL of methanol at room temperature for 24 hours to obtain an extract solution containing the components extracted from each sample using methanol. The obtained extract solution was then separated and quantified using gas chromatography-flame ionization detector (GC-FID) (Shimadzu Corporation GC2010) to determine the residual amounts Mb[g] of carboxylic acid ester (B) and Mc[g] of insect repellent (C) in each sample after standing. The sustained-release ratio Qb of carboxylic acid ester (B) was then calculated using formula (3A), and the sustained-release ratio Qc of insect repellent (C) was calculated using formula (3B). Furthermore, the sustained-release mass Rb of carboxylic acid ester (B) was calculated using formula (4A), and the sustained-release mass Rc of insect repellent (C) was calculated using formula (4B). It should be noted that the sustained-release ratios (Qb and Qc) are the proportions of each sustained-release component to the total amount of all sustained-release components. In addition, the sustained-release mass (Rb and Rc) is equivalent to the mass of each component released in the sustained-release form.

[0184] Qb=(Wb-Mb) / (Wb-Mb+Wc-Mc)(3A)

[0185] Qc=(Wc-Mc) / (Wb-Mb+Wc-Mc)(3B)

[0186] (In equations (3A) and (3B),

[0187] Wb represents the content [g] of carboxylic acid ester (B) in the sample before standing.

[0188] Wc represents the content [g] of insecticide (C) in the sample before standing.

[0189] Rb=Rt×Qb(4A)

[0190] Rc = Rt × Qc (4B)

[0191] (5-3) Sustained-release dose

[0192] Next, the ratio (Rb / Wb×100) [mass%) of the sustained-release mass of carboxylic acid ester (B) to the content (Wb) of carboxylic acid ester (B) in the sample before standing is calculated as the sustained-release amount of carboxylic acid ester (B). Similarly, the ratio (Rc / Wc×100) [mass%) of the sustained-release mass (Rc) of insect repellent (C) to the content (Wc) of insect repellent (C) in the sample before standing is calculated as the sustained-release amount of insect repellent (C).

[0193] (5-4) Slow-release amount of insecticide (C) other than during recycling

[0194] In addition, the total sustained-release mass Rt' of each fixed period other than the above-mentioned recovery time is measured, and the sustained-release mass Qc' of the insecticide (C) is calculated by the following formula (5). Then, the sustained-release mass Rc' of the insecticide (C) relative to the content of insecticide (C) contained in the sample before standing is taken as the sustained-release amount of insecticide (C) other than the recovery time.

[0195] Qc'=Rt'×(Qcc+(D-Dc) / (Da-Dc)×(Qca-Qcc))(5)

[0196] (in equation (5),)

[0197] D represents the number of days of settling when measuring the total sustained-release mass Rt'.

[0198] Dc indicates the number of days before D when the sample was recovered.

[0199] Da represents the number of days after D when the sample was recovered.

[0200] Qcc represents the sustained-release ratio of insect repellent (C) in the sample recovered before D, Qc.

[0201] Qca represents the sustained-release ratio (Qc) of the insecticide (C) in the sample recovered after D.

[0202] (6) Maximum sustained-release rate ratio

[0203] Calculate the daily release rate of the insecticide [mg / day] for each period from the start of the measurement to day 3 (period I), from day 4 to day 7 (period II), from day 8 to day 14 (period III), and from day 15 to day 21 (period IV). Specifically, for example, the daily release rate of the insecticide in period II is calculated using the formula (released mass of the insecticide on day 7 - released mass of the insecticide on day 4) / (7 - 4). Furthermore, for each period, the ratio of the maximum release rate to the minimum release rate (maximum release rate / minimum release rate) is used as the maximum release rate ratio.

[0204] (7) Evaluation of sustained-release properties

[0205] The sustained-release properties of each sample were evaluated according to the following criteria, based on the ratio of the sustained-release mass determined by the method described in (5) to the maximum sustained-release rate determined by the method described in (6). It should be noted that if the evaluation results are A and B, the sample is considered acceptable.

[0206] [Evaluation Criteria for Slow-Release Properties]

[0207] A: Samples with a sustained-release mass of insect repellent (C) of 2 mg or more per day for each period from the start of the test to day 3 (period I), day 4 to day 7 (period II), day 8 to day 14 (period III), and day 15 to day 21 (period IV), and a maximum sustained-release rate ratio of 0.6 to 1.7 times. In this case, it is considered that a uniformly high insect repellent effect is observed for at least 21 days, and the concentration of insect repellent (C) in the resin composition decreases slowly; therefore, further long-term efficacy is anticipated.

[0208] B: In samples that do not meet the benchmark of A, the sustained-release mass of insect repellent (C) for each day during the above periods is 1.5 mg or more, and the maximum sustained-release rate ratio is within 0.4 to 2.3 times. In this case, it is considered that a uniform insect repellent effect is observed for at least 21 days, and the rate of decrease in the concentration of insect repellent (C) in the resin composition is relatively slow. Therefore, although it is not as good as A, a sufficiently long-term efficacy can be expected.

[0209] C: In samples that do not meet the benchmarks of A and B, the sustained-release mass 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 insect repellent effect is shown during a certain limited period, but the rate of decrease in the concentration of insect repellent (C) cannot be suppressed, and therefore it is considered that the efficacy cannot be maintained for a long period of time.

[0210] D: Samples that do not meet the standards of A, B, and C. These are considered to have low sustained-release mass, low efficacy as an insect repellent, or even if they exhibit efficacy, the duration of efficacy may be short or unstable.

[0211] (8) Determination of the concentration retention rate of active ingredients

[0212] The concentration of the active ingredient (insect repellent) in the resin composition of each sample placed under the conditions described in (5) is determined by the following formula (6).

[0213] Active ingredient concentration [wt%] = {(Wc-Rc) / (Wt-Rt)}×100(6)

[0214] (In formula (6),)

[0215] Wc represents the amount of insecticide (C) added to the sample before standing [g].

[0216] Rc represents the sustained-release mass [g] of the insecticide (C).

[0217] Wt represents the mass [g] of the resin composition in the sample before settling.

[0218] Rt represents the total sustained-release mass of the carboxylic acid ester (B) and the insecticide (C).

[0219] In the above formula, (Wc-Rc) represents the mass of the active ingredient contained in the resin composition after a specific settling period, and (Wt-Rt) represents the mass of the resin composition after a specific settling period.

[0220] The retention rate of the active ingredient concentration is determined according to the following formula (7) based on the active ingredient concentration calculated as above.

[0221] Active ingredient concentration retention rate [%)

[0222] = [(Concentration of active ingredient based on equation (6)) / {(Wc / Wt)×100}]×100(7)

[0223] In the above formula, (Wc / Wt)×100 represents the concentration of active ingredients in the resin composition of the sample before standing.

[0224] (9) Evaluation of Leakage

[0225] For laminates containing the resin compositions of the examples and comparative examples, samples before and after the evaluation of the sustained-release content (within a 21-day standing period) were visually observed, and the degree of exudation was evaluated according to the following evaluation criteria. It should be noted that an evaluation result of A to C is considered acceptable.

[0226] [Evaluation Criteria for Leakage]

[0227] A: No leakage occurred from the laminate before and after the evaluation, maintaining the same state of composition as before the evaluation.

[0228] B: Before and after evaluation, even touching the surface of the laminate could not confirm the exudate, but discoloration was observed due to the penetration of active ingredients into the (E) layer.

[0229] C: Although there was no exudation from the surface of the laminate before evaluation, when the surface of the laminate after evaluation was touched, there was a noticeable degree of slight exudation, or it was observed that the resin composition inside the laminate separated into more than two layers.

[0230] D: Although no seepage was observed from the surface of the laminate before evaluation, droplets, crystals, etc., could be clearly seen visually after evaluation.

[0231] E: After sample preparation, identifiable or visual exudation can be confirmed from the surface of the laminate before evaluation.

[0232] (Example 1)

[0233] According to the prescription shown in Table 2, (A1), (B1) and (C1) are mixed by the method described in (4) to obtain a resin composition. A layer (D) is made using the resin composition, and a sample (laminated body) is made by laminating (E1) on both sides of the layer (D).

[0234] (Example 2)

[0235] The ratio of (A1), (B1) and (C1) is as shown in Table 2. Otherwise, the resin composition is obtained by the same method as described in (4) as in Example 1. Layer (D) is made using the resin composition, and a sample is made by laminating (E1) on both sides of layer (D).

[0236] (Example 3)

[0237] According to the prescription shown in Table 2, (A1), (B1) and (C2) are mixed using the method described in (4) to obtain a resin composition. A layer (D) is made using the resin composition, and a sample is made by laminating (E1) on both sides of the layer (D).

[0238] (Example 4)

[0239] According to the prescription shown in Table 2, (A1), (B2) and (C1) are mixed using the method described in (4) to obtain a resin composition. A layer (D) is made using the resin composition, and a sample is made by laminating (E1) on both sides of the layer (D).

[0240] (Example 5)

[0241] According to the formula shown in Table 2, (A4), (B1) and (C1) are mixed in the same way as described in (4) except that the mixing temperature is 90°C to obtain a resin composition. A layer (D) is made using the resin composition, and a sample is made by laminating (E1) on both sides of the layer (D).

[0242] (Example 6)

[0243] According to the formula shown in Table 2, (A4), (B1) and (C2) were mixed in the same way as described in (4) except that the mixing temperature was set to 90°C to obtain a resin composition. A layer (D) was made using the resin composition, and a sample was made by laminating (E1) on both sides of the layer (D).

[0244] (Example 7)

[0245] According to the formula shown in Table 2, (A3), (B1) and (C2) were mixed in the same way as described in (4) except that the mixing temperature was set to 90°C to obtain a resin composition. A layer (D) was made using the resin composition, and a sample was made by laminating (E1) on both sides of the layer (D).

[0246] (Example 8)

[0247] According to the prescription shown in Table 2, (A2), (X1), (B2) and (C1) were mixed in the same way as described in (4) except that the mixing temperature was set to 130°C to obtain a resin composition. A layer (D) was made using the resin composition, and a sample was made by laminating (E1) on both sides of the layer (D).

[0248] (Example 9)

[0249] According to the prescription shown in Table 2, (A1), (B1) and (C1) are mixed using the method described in (4) to obtain a resin composition. A layer (D) is made using the resin composition, and a sample is made by laminating (E2) on both sides of the layer (D).

[0250] (Comparative Example 1)

[0251] According to the prescription shown in Table 2, (A2), (X1) and (C1) are mixed in the same way as described in (4) except that the mixing temperature is 130°C to obtain a resin composition. A layer (D) is made using the resin composition, and a sample is made by laminating (E1) on both sides of the layer (D).

[0252] (Comparative Example 2)

[0253] According to the prescription shown in Table 2, (A3) and (C2) are mixed in the same way as described in (4) except that the mixing temperature is 90°C to obtain a resin composition. A layer (D) is made using the resin composition, and a sample is made by laminating (E1) on both sides of the layer (D).

[0254] (Comparative Example 3)

[0255] According to the prescription shown in Table 2, (A1), (Y1) and (C1) are mixed using the method described in (4) to obtain a resin composition. A layer (D) is made using the resin composition, and a sample is made by laminating (E1) on both sides of the layer (D).

[0256] (Comparative Example 4)

[0257] According to the prescription shown in Table 2, (A1), (Y2) and (C1) are mixed using the method described in (4) to obtain a resin composition. A layer (D) is made using the resin composition, and a sample is made by laminating (E1) on both sides of the layer (D).

[0258] (Comparative Example 5)

[0259] According to the prescription shown in Table 2, (A1), (Y3) and (C1) are mixed using the method described in (4) to obtain a resin composition. A layer (D) is made using the resin composition, and a sample is made by laminating (E1) on both sides of the layer (D).

[0260] (Comparative Example 6)

[0261] According to the prescription shown in Table 2, (A1), (B1) and (C1) are mixed using the method described in (4) to obtain a resin composition. A layer (D) is made using the resin composition, and a sample is made by laminating (E1) on both sides of the layer (D).

[0262] (Comparative Example 7)

[0263] According to the prescription shown in Table 2, (A1), (B1) and (C1) are mixed using the method described in (4) to obtain a resin composition. A layer (D) is made using the resin composition, and a sample is made by laminating (E1) on both sides of the layer (D).

[0264] 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. Furthermore, the intercomponent solubility index R (R1-R3) between the resin and the carboxylic acid ester or plasticizer and the insect repellent used in the examples and comparative examples was calculated using formulas (2A) to (2C) based on the Hansen solubility parameter. Additionally, the penetration of the resin compositions obtained in the examples and comparative examples was measured using the method described in (2) Penetration. The results are shown in Table 2.

[0265] For the sustained-release samples (laminated bodies) obtained in the examples and comparative examples, the sustained-release properties were evaluated according to the method described in (7) Evaluation of Sustained-Release Properties, based on the ratio of the sustained-release mass determined according to the method described in (5) and the maximum sustained-release rate determined according to the method described in (6). Furthermore, exudation was evaluated according to the method described in (9) Evaluation of Exudation. The results are shown in Table 3.

[0266] For the test samples (laminated bodies) obtained in the examples and comparative examples for determining the sustained-release amount, the sustained-release mass (Rc) of the insect repellent (C) after a specified standing period was determined according to the sustained-release amount determination method (5). The results are shown in Table 3.

[0267] In addition, the maximum sustained-release rate ratio of the insecticide (C) was calculated according to the determination method described in (6) Maximum sustained-release rate ratio. The results are shown in Table 3.

[0268] For the samples (laminated bodies) obtained in Example 1 and Comparative Example 1, the concentration retention rate of the active ingredient was determined according to the method described in (8) Method for Determining the Concentration Retention Rate of Active Ingredient. The results are shown below. Figure 1 .

[0269] For the samples (laminated bodies) obtained in Example 1 and Comparative Example 1, the sustained-release amount of the active ingredient was determined according to the methods described in (5-3) sustained-release amount and (5-4) sustained-release amount of insecticide (C) other than at recovery time, to confirm the change over time. The results are shown below. Figure 2 .

[0270] [Table 1]

[0271]

[0272] [Table 2]

[0273]

[0274] [Table 3]

[0275]

[0276] The sustained-release properties of the samples in Examples 1-9 were good, allowing the active ingredient to volatilize at a high rate over a long period, and the exudation properties were also good, with little exudation. In contrast, the samples described in Comparative Examples 1-7 could not allow the active ingredient to volatilize at a high rate over a long period, the sustained-release properties were not adequate, and / or exudation was likely to occur.

[0277] The samples of Examples 1 to 3 (especially the sample of Example 1) maintained the concentration of insect repellent (C) in the resin composition for a long period of time, and the insect repellent (C) was released stably at a high sustained-release amount for a long period of time.

[0278] Although the sample described in Example 4 showed a trend of decreasing sustained-release amount of plasticizer (B) compared to Examples 1-3, it enabled the insect repellent (C) to be released stably at a high sustained-release amount.

[0279] The samples described in Examples 5 and 6 maintained a high concentration of insect repellent (C) within the resin composition for an extended period, and the insect repellent (C) was released stably at a high sustained-release level over a long period. When the surface of the sample after the sustained-release level was evaluated by wiping, slight liquid exudate was observed, but it was at a level that was not problematic.

[0280] Although the samples of Examples 7 and 8 had a lower sustained-release amount compared to Examples 1-3, they enabled the insect repellent (C) to be released stably at a high sustained-release amount. When the surface of the sample was wiped after the sustained-release amount was evaluated, the sample of Example 7 showed a slight liquid exudate, but it was at a level that was not problematic, while no exudate was seen on the surface of the sample of Example 8.

[0281] The sample of Example 9 allowed the insect repellent (C) to be released stably at a high sustained-release level over a long period. Although discoloration was observed on the paper of layer (E) due to liquid immersion, no exudate was observed on the surface of the sample after the sustained-release level was evaluated.

[0282] In Comparative Example 1, the concentration of insect repellent (C) in the resin composition decreased over time, resulting in a low amount of sustained-release insect repellent (C). Furthermore, after the sustained-release evaluation was completed, visible exudation of droplets was observed on the sample surface.

[0283] The amount of insect repellent (C) released from the sample in Comparative Example 2 decreased slowly. Additionally, slight liquid exudate was observed when wiping the surface of the sample after the sustained-release evaluation.

[0284] In Comparative Example 3, the plasticizer (B) was released completely in the initial stage. Then, the amount of insect repellent (C) released slowly decreased.

[0285] In Comparative Example 4, the plasticizer (B) was almost completely released. Then, the amount of insect repellent (C) released slowly decreased.

[0286] The plasticizer (B) in Comparative Example 5 exhibited a small and unstable sustained-release amount. The insect repellent (C) showed a stable sustained release. Furthermore, layer separation was observed in the resin composition before the sustained-release amount was evaluated, and solid exudates were visibly formed on the sample surface after the evaluation was completed.

[0287] The plasticizer (B) in Comparative Example 6 had a small and unstable sustained-release amount. The insect repellent (C) had a slowly decreasing sustained-release amount.

[0288] In Comparative Example 7, the insect repellent (C) was initially released at a significant rate, followed by a slight decrease in the amount released. Furthermore, before the evaluation of the release rate began, the liquid separated from the resin composition, the sample surface felt sticky, and after the evaluation, clear exudation was observed on the droplets.

Claims

1. A resin composition comprising at least: a copolymer of ethylene and a vinyl monomer containing an oxygen atom, i.e., resin (A), an amount of 10 to 87 mass% of resin (A), an amount of 3 to 30 mass% of a carboxylic acid ester (B), and an amount of 10 to 60 mass% of an insect repellent (C) based on the total amount of the resin composition, a mass ratio of the carboxylic acid ester (B) to the insect repellent (C) is 2: 1 to 1: 5, resin (A) is a copolymer of ethylene and an organic carboxylic acid derivative having an ethylenic unsaturated bond, the carboxylic acid ester (B) is at least one component selected from the group consisting of an ester of a saturated aliphatic acid having 8 to 20 carbon atoms, an ester of a dicarboxylic acid having 2 to 10 carbon atoms, a carbonate, a citrate, and an acetyl citrate, and the insect repellent (C) is a pyrethroid insect repellent. The carboxylic acid ester (B) is at least one component selected from the group consisting of 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 acetyl triethyl citrate. Molecular weight: 255-380, saturated vapor pressure at 25°C: 1.0 x 10 －4 linear or branched carboxylic acid ester (B) having a saturated vapor pressure at 25°C of 1.0 x 10 25°C, 1.0 x 10 －4 insect repellent (C) having a saturated vapor pressure of 1.0 x 10 The insect repellent (C) is at least one component selected from the group consisting of tetrachlorvinphos, methoxychlor, allethrin, profluthrin, chlorofluazuron, and heptafluthrin. 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 satisfy formula (1), 0.2 ≤ Pb / Pc ≤ 500 (1). The dissolution index of resin (A) and the carboxylic acid ester (B), i.e., Rl, the dissolution index of resin (A) and the insect repellent (C), i.e., R2, and the dissolution index of the carboxylic acid ester (B) and the insect repellent (C), i.e., R3, are each 5.0 or less.

2. The resin composition according to claim 1, wherein, 6. A member for an insect repellent sustained-release preparation comprising the resin composition according to any one of claims 1 to 5.

3. The resin composition according to claim 1, wherein, 7. A laminate comprising: a first layer (D) containing the resin composition according to any one of claims 1 to 5, and a second layer (E) that is permeable to the carboxylic acid ester (B) and the insect repellent (C).

4. The resin composition according to claim 1, wherein, The first layer (D) is a single layer, and the second layer (E) is a single layer or a plurality of layers, one face of the second layer (E) is in contact with the first layer (D), and the other face of the second layer (E) is the outermost surface of the laminate. The layers are constituted of at least layer (E) / layer (D) / layer (E), and each layer (E) can be the same as or different from each other.

5. The resin composition according to claim 1, wherein, Further, a third layer (F) different from the layers (E) and (D) is provided. The third layer (F) is at least one layer selected from the group consisting of an adhesive bonding layer, a surface protection layer, a coloring layer, an insect repellent permeation barrier layer, an appearance design layer, and an ultraviolet absorbing layer.

12. An insect repellent sustained-release preparation having the member according to claim 6.

8. The laminate according to claim 7, wherein 13. An insect repellent sustained-release preparation having the laminate according to claim 7.

9. The laminate according to claim 7, wherein ​ 10. The laminate according to claim 7, wherein ​ 11. The laminate according to claim 10, wherein ​ ​ ​

Images