Functional sustained release composition and molded product thereof

Abstract

To provide a functional sustained release composition capable of sustaining an excellent a sustained release effect for a long term and its compact.SOLUTION: In a functional sustained release composition made of a functional sustained release liquid having a function such as an insect repellent, antibacterial and antiviral, and a porous material such as a porous coordination polymer and its compact, when a radius of a metal ion blended in the porous body is made within a range of a value determined from the acid dissociation constant of the function release liquid, excellent sustained release effect can be sustained for a long period of time.SELECTED DRAWING: Figure 73

Description

[Technical field]

[0001] The present invention relates to a functional sustained-release composition and a molded article thereof. [Background technology]

[0002] In functional components such as small animal control, antibacterial, antiviral, and sliding oil, the durability of the effect can be improved by releasing a predetermined amount of the functional component for a long period of time. As a method for improving the durability of the effect of the small animal control functional component, a molded body using a small animal control composite material in which the small animal control functional component is developed in a matrix resin has been devised (for example, Patent Documents 1 to 3). The molded bodies described in Patent Documents 1 to 3 can maintain the small animal control function on the surface of the molded body that comes into contact with small animals such as pests by gradually releasing the small animal control functional component on the surface of the molded body (hereinafter referred to as "slow release"). In order to maintain such slow release for a long period of time, it is considered to increase the amount of the functional component developed in the matrix resin. Increasing the amount of the functional component is also effective from the viewpoint of further strengthening the function. Methods for increasing the amount of the functional component include modifying the functional component with a functional group, increasing the polarity of the matrix resin, and supporting the functional component on a porous body in order to increase the affinity between the functional component and the matrix resin (for example, Patent Document 4). Furthermore, a functional sustained-release composition has been devised in which a porous coordination polymer, which has a large specific surface area among porous bodies, is used as a porous body (Patent Document 5). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2001-73886 A [Patent Document 2] JP 2000-212005 A [Patent Document 3] JP 2008-206492 A [Patent Document 4] JP 2012-6868 A [Patent Document 5] JP 2019-218310 A Summary of the Invention [Problem to be solved by the invention]

[0004] In order to spread a liquid functional component in a matrix resin, it is possible to arrange the functional component in the free volume space in the matrix resin, or to spread the space between the resins and arrange the functional component in the space between them. In this case, the higher the affinity between the functional component and the matrix resin, the easier it is to arrange the functional component, and a larger amount of the functional component can be spread in the matrix resin.

[0005] However, in order to maintain the shape of the molded body, a skeleton needs to be formed by the matrix resin, so the free volume in the matrix resin is limited in size due to the type of resin, thermal vibration due to temperature, etc. In addition, even if the resin spacing is increased by the functional component, the distance between the resins needs to be less than a certain distance in order to maintain the shape of the molded body, and there is an upper limit to the free volume, so there is a limit to increasing the amount of the functional component. When the matrix resin is a thermoplastic resin, the content of the functional component in the entire molded body is usually limited to around 20% by mass even if the polarity of the matrix resin is adjusted to modify the resin. However, the selection of the matrix resin is limited depending on the performance and price required during use, such as the durable temperature, strength, and material unit price. Therefore, it is difficult to realize a functional sustained-release composition and its molded body that can maintain the sustained-release effect for a long period of time.

[0006] On the other hand, the functional component is not limited to the matrix resin, and can be adsorbed and supported by a porous body and added to the matrix resin by melt kneading or the like. Porous bodies capable of supporting functional components are usually considered to be porous coordination polymers, zeolites, silica, alumina, molecular sieves, activated carbon, etc. In order for these porous bodies to support and adsorb functional components, the affinity with the adsorption surface as well as the adsorption area of ​​the pores is important. The affinity greatly affects not only the amount of functional components supported and adsorbed by the porous body, but also the rate at which the functional components are gradually released from the matrix resin. However, there are various functional components, and the porous bodies having high affinity with the functional components are different from one another, making it difficult to match them. Therefore, it is extremely difficult to design a material for a molded body taking into account the affinity with the functional components.

[0007] Therefore, an object of the present invention is to provide a functional sustained-release composition capable of maintaining an excellent sustained-release effect for a long period of time, and a molded product thereof. [Means for solving the problem]

[0008] As a result of extensive research to solve the above problems, the inventors discovered that when the metal ion radius of the porous body is within a specific range relative to the acid dissociation constant of the functional sustained-release liquid, the resulting functional sustained-release composition can solve the above problems, and thus completed the present invention.

[0009] That is, the present invention is as follows. ( 1 ) A functional sustained-release composition and a molded body thereof, which has a porous body having a functional sustained-release liquid and a metal ion, and is characterized in that when the acid dissociation constant α of the functional sustained-release liquid is α, the radius R of the metal ion satisfies the range of the following formula 1. JPEG0007671484000001.jpg22129 ( 2 ) The functional sustained-release composition and its molded product according to (1), wherein the metal ion has at least one of an alkali metal, an alkaline earth metal, and a transition metal. ( 3 ) The radius R of the metal ion is 40×10-12 m to 150×10 -12 A functional sustained-release composition and a molded body thereof, the functional sustained-release composition being within the range of (1) or (2). ( 4 ) The functional sustained-release composition and its molded product according to any one of (1) to (3), wherein the acid dissociation constant α of the functional sustained-release liquid is within the range of −10 to 40. ( 5 ) The functional sustained-release composition and its molded body according to any one of (1) to (4), wherein the porous body is a porous coordination polymer comprising metal ions and organic ligands. Effect of the Invention

[0010] According to the present invention, it is possible to provide a functional sustained-release composition and a molded article that can maintain an excellent sustained-release effect for a long period of time. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a graph showing the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded body in Example 1, where the functional sustained-release liquid is etofenprox. [Diagram 2] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded article in Reference Example 2, where the functional sustained-release liquid is etofenprox. [Diagram 3] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded article in Reference Example 3, where the functional sustained-release liquid is etofenprox. [Figure 4] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded body in Reference Example 4, where the functional sustained-release liquid is etofenprox. [Diagram 5] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded body in Example 5, where the functional sustained-release liquid is etofenprox. [Figure 6]FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded body in Example 6, where the functional sustained-release liquid is etofenprox. [Figure 7] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded article in Reference Example 7, where the functional sustained-release liquid is etofenprox. [Figure 8] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded article in Reference Example 8, where the functional sustained-release liquid is etofenprox. [Figure 9] FIG. 1 shows the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded body in Comparative Example 1-1, where the functional sustained-release liquid is etofenprox. [Figure 10] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded body in Comparative Example 1-2, where the functional sustained-release liquid is etofenprox. [Figure 11] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded body in Comparative Example 1-3, where the functional sustained-release liquid is etofenprox. [Figure 12] FIG. 13 is a diagram showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Example 9, where the function-release liquid is 2-n-octyl-4-isothiazolin-3-one. [Figure 13] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Example 10, where the function-release liquid is 2-n-octyl-4-isothiazolin-3-one. [Figure 14] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Example 11, where the function-release liquid is 2-n-octyl-4-isothiazolin-3-one. [Figure 15]FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Example 12, where the function-release liquid is 2-n-octyl-4-isothiazolin-3-one. [Figure 16] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Example 13, where the function-release liquid is 2-n-octyl-4-isothiazolin-3-one. [Figure 17] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Example 14, where the function-release liquid is 2-n-octyl-4-isothiazolin-3-one. [Figure 18] FIG. 13 is a diagram showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Comparative Example 2-1, where the function-release liquid is 2-n-octyl-4-isothiazolin-3-one. [Figure 19] FIG. 13 is a diagram showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Comparative Example 2-2, where the function-release liquid is 2-n-octyl-4-isothiazolin-3-one. [Figure 20] FIG. 13 is a diagram showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Comparative Example 2-3, where the function-release liquid is 2-n-octyl-4-isothiazolin-3-one. [Figure 21] FIG. 13 is a diagram showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Comparative Example 2-4, where the function-release liquid is 2-n-octyl-4-isothiazolin-3-one. [Figure 22] FIG. 13 is a diagram showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Comparative Example 2-5, where the function-release liquid is 2-n-octyl-4-isothiazolin-3-one. [Figure 23] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Example 15, where the function-release liquid is methyl anthranilate. [Figure 24] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Example 16, where the function-release liquid is methyl anthranilate. [Diagram 25] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Example 17, where the function-release liquid is methyl anthranilate. [Figure 26] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Example 18, where the function-release liquid is methyl anthranilate. [Figure 27] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Example 19, where the function-release liquid is methyl anthranilate. [Figure 28] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Example 20, where the function-release liquid is methyl anthranilate. [Figure 29] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Comparative Example 3-1, where the function-release liquid is methyl anthranilate. [Diagram 30] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Comparative Example 3-2, where the function-release liquid is methyl anthranilate. [Diagram 31] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Comparative Example 3-3, where the function-release liquid is methyl anthranilate. [Diagram 32] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Comparative Example 3-4, where the function-release liquid is methyl anthranilate. [Diagram 33]FIG. 2 shows the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Example 21, where the function-release liquid is 5-heptyloxolan-2-one. [Diagram 34] FIG. 2 shows the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Example 22, where the function-release liquid is 5-heptyloxolan-2-one. [Diagram 35] FIG. 2 shows the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Example 23, where the function-release liquid is 5-heptyloxolan-2-one. [Diagram 36] FIG. 2 shows the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Example 24, where the function-release liquid is 5-heptyloxolan-2-one. [Figure 37] FIG. 2 shows the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded body in Example 25, where the functional sustained-release liquid is 5-heptyloxolan-2-one. [Figure 38] FIG. 2 shows the relationship between the number of repeated washings and the surface amount of the functional-release liquid in the functional-release composite molded body in Example 26, where the functional-release liquid is 5-heptyloxolan-2-one. [Figure 39] FIG. 2 shows the relationship between the number of repeated washings and the surface amount of the functional-release liquid in the functional-release composite molded body in Example 27, where the functional-release liquid is 5-heptyloxolan-2-one. [Diagram 40] FIG. 2 shows the relationship between the number of repeated washings and the surface amount of the functional-release liquid in the functional-release composite molded body in Example 28, where the functional-release liquid is 5-heptyloxolan-2-one. [Diagram 41] FIG. 13 is a diagram showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Comparative Example 4, where the function-release liquid is 5-heptyloxolan-2-one. [Diagram 42]FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded product in Example 31, where the functional sustained-release liquid is chlorpyrifos. [Diagram 43] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded product in Example 32, where the functional sustained-release liquid is chlorpyrifos. [Diagram 44] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded body in Comparative Example 5-1, where the functional sustained-release liquid is chlorpyrifos. [Diagram 45] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded body in Comparative Example 5-2, where the functional sustained-release liquid is chlorpyrifos. [Figure 46] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded body in Comparative Example 5-3, where the functional sustained-release liquid is chlorpyrifos. [Figure 47] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded body in Comparative Example 5-4, where the functional sustained-release liquid is chlorpyrifos. [Figure 48] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded body in Comparative Example 5-5, where the functional sustained-release liquid is chlorpyrifos. [Figure 49] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the functional sustained-release liquid in the functional sustained-release composite molded body in Comparative Example 5-6, where the functional sustained-release liquid is chlorpyrifos. [Figure 50] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Example 36, where the function-release liquid is dimethyl sulfoxide. [Figure 51] FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Example 37, where the function-release liquid is dimethyl sulfoxide. [Figure 52]FIG. 13 is a graph showing the relationship between the number of repeated washings and the surface amount of the function-release liquid in the function-release composite molded body in Comparative Example 6-1, where the function-release liquid is dimethyl sulfoxide. [Diagram 53] FIG. 1 shows the relationship between the metal ion radius of the porous body and the exponential ratio of the surface amount of the functional sustained-release liquid after repeated washing in Examples 1, 5 to 6, Comparative Examples 1-1 to 1-3, and Reference Examples 2 to 4, and 7 to 8, where the functional sustained-release liquid is etofenprox. [Figure 54] FIG. 13 is a graph showing the relationship between the metal ion radius of the porous body and the exponential ratio of the surface amount of the function-release liquid after repeated washing in Examples 9 to 14 and Comparative Examples 2-1 to 2-5, where the function-release liquid is 2-n-octyl-4-isothiazolin-3-one. [Figure 55] FIG. 13 is a diagram showing the relationship between the metal ion radius of the porous body and the exponential ratio of the surface amount of the function-release liquid after repeated washing in Examples 15 to 20 and Comparative Examples 3-1 to 3-4, where the function-release liquid is methyl anthranilate. [Figure 56] FIG. 11 is a diagram showing the relationship between the metal ion radius of the porous body and the exponential ratio of the surface amount of the function-release liquid after repeated washing in Examples 21 to 28 and Comparative Example 4, where the function-release liquid is 5-heptyloxolan-2-one. [Figure 57] FIG. 11 is a diagram showing the relationship between the metal ion radius of the porous body and the exponential ratio of the surface amount of the function sustained-release liquid after repeated washing in Examples 31 to 32 and Comparative Examples 5-1 to 5-6, where the function sustained-release liquid is chlorpyrifos. [Figure 58] FIG. 13 is a diagram showing the relationship between the metal ion radius of the porous body and the exponential ratio of the surface amount of the functional sustained-release liquid after repeated washing in Examples 36 to 37 and Comparative Example 6-1, where the functional sustained-release liquid is dimethyl sulfoxide. [Figure 59] FIG. 62 is a diagram showing the relationship between the acid dissociation constant of the functional sustained-release liquid and the slope of the linear approximation equation of FIGS. [Figure 60] FIG. 62 is a diagram showing the relationship between the acid dissociation constant of the functional sustained-release liquid and the intercept of the linear approximation equation of FIGS. [Figure 61]FIG. 1 is a diagram showing the relationship between the acid dissociation constant of a functional sustained-release liquid and the metal ion radius R of a porous body. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, an embodiment of the present invention (hereinafter, simply referred to as "the present embodiment") will be described with reference to the drawings as necessary. The present embodiment is an example for explaining the present invention, and the present invention is not limited to the embodiment.

[0013] [Functional sustained release composition] The functional sustained-release composition of this embodiment has a porous body made of a functional sustained-release liquid and a metal ion having a metal ion radius within the range of the numerical value of the acid dissociation constant of the functional sustained-release liquid, and includes a matrix resin. The functional sustained-release composition of this embodiment can maintain an excellent sustained-release effect for a long period of time by combining the functional sustained-release liquid, the porous coordination polymer, and the matrix resin. Therefore, the functional sustained-release composition of this embodiment has advantages such as improved product performance and reduced maintenance frequency, resulting in cost reduction.

[0014] [Functional sustained release liquid] The "function-sustained release" in the function-sustained release liquid refers to the property of having a function such as a small animal control function, a function for controlling plant growth, an antibacterial function, an antifungal function, a function for imparting plasticity to resins, a sliding function, a self-repairing function, a catalytic function, a medical function, an antiviral function, a self-cleaning function, etc., and having a sustained release property. The function-sustained release liquid may be a liquid component having a function-sustained release property, may be a form in which a solid component having a function-sustained release property has been liquefied, or may be a form in which a solid component having a function-sustained release property has been liquefied by dissolving it in a solvent.

[0015] Examples of functional liquids having a small animal control function include agents having control activity against various agricultural pests, sanitary pests, other insects, spiders, mites, mice, and other small animals, or liquid forms in which agents are dissolved in a solvent (hereinafter also referred to as "small animal control agents"). Examples include compounds having small animal repellent activity, compounds having small animal killing activity such as insecticidal activity, acaricidal activity, spidericidal activity, or rodenticidal activity, compounds having feeding inhibition activity for small animals, and compounds having growth control activity for small animals.

[0016] Specific examples of small animal control drugs include metadiamide-based insecticides such as brofuranilide, piperidine-based insecticides such as icaridin, chloronicotinyl-based insecticides such as imidacloprid, compounds consisting of a neophyl radical having a silicon atom such as silafluofen, carbamate-based compounds such as benfuracarb, alanycarb, methoxydiazone, carbosphan, fenobucarb, carbaryl, methomyl, propoxar, and fenoxycarb, pyrethrins, allethrin, dl, Examples of the compound include pyrethroid compounds such as d-T80-allethrin, d-T80-resmethrin, bioallethrin, d-T80-phthalthrin, phthalthrin, resmethrin, furamethrin, propathrin, permethrin, acrinathrin, etofenprox, tralomethrin, fenothrin, d-fenothrin, fenvalerate, empenthrin, prallethrin, tefluthrin, benfluthrin, transfluthrin, and metofluthrin; and organophosphorus compounds such as dichlorovos, fenitrothion, diazinon, malathion, bromophos, fenthion, trichlorfon, naled, temephos, fenclofos, chlorpyrifos-methyl, cyafos, carclofos, azamethiphos, pyridaphenthion, propetamphos, and chlorpyrifos; and isomers, derivatives, and analogs thereof.

[0017] Furthermore, examples of compounds having growth control activity for small animals include methoprene, pyriproxyfen, kinoprene, hydroprene, deohenolan, NC-170, flufenoloxuron, diflubenzuron, lufenuron, and chlorazuron.

[0018] Examples of compounds having small animal killing activity include acaricides such as kelthane, chlorfenavir, debufenpyradopyridaben, milbemectin, and fenpyroximate, and rodenticides such as sciliroside, norbomide, zinc phosphide, thallium sulfate, yellow phosphorus, anthu, warfarin, endocide, coumarin, coumatetralin, promagdiolone, and difethialone.

[0019] Examples of small animal control agents include hinokitiol, which is found in Taiwan cypress, asarum, and Hinoki asarum (Aomori hiba), etc., cadinol derivatives (α-cadinol, T-cadinol) found in herbs and cypress, geraniol, pinene, caryophyllene, borneol, eugenol, which are abundantly found in aromatic plants such as cloves, nutmeg, coriander, and cumin, and known aromatic oils having small animal control properties, such as those of natural origin.

[0020] Pheromone agents for insects, etc., having an attracting effect, a communication-inhibiting effect, etc., are also used as small animal control drugs. Examples of pheromone agents include pheromone agents used for fruit trees such as Shin-Etsu Chemical's products "Confuser R", "Confuser AA", "Confuser N", "Confuser MM", "Hamakikon-N", "Sukashibakon L", "Shinkuikon-L", "Nashihimekon", "Bokutokon-H", and "Hetamushikon", pheromone agents used for vegetables such as Shin-Etsu Chemical's products "Confuser V", "Yotokon-H", "Yotokon-S", "Konagakon-Plus", and "Shin-Etsu Konagakon", pheromone agents used for tea such as Shin-Etsu Chemical's product "Hamakikon-N", and pheromone agents used for sugar cane such as Shin-Etsu Chemical's products "Okimerakon", "Yotokon-I", and "Kebukkakon".

[0021] Furthermore, the small animal control agent may be a repellent for vespid bees, and the repellent for vespid bees contains, for example, a compound represented by the following general formula (I) as an active ingredient.

[0022] [ka]

[0023] In formula (I), R1 is a hydrogen atom, a C 1 - 4 C which may have an alkyl group or a substituent β 2 - 4 C which may have an alkenyl group or a substituent β 1 - 4 represents an alkyl-carbonyl group, and X is a C 1 - 4 C which may have an alkylene group or a substituent γ 2 - 4 represents an alkenylene group, α optionally having a substituent δ 1 - 4 C which may have an alkyl group or a substituent δ 2 - 4 Alkenyl group, optionally having a substituent δ 1 - 4 Alkoxy group, C optionally having a substituent δ 1 - 4 Alkyl-carbonyl group, optionally having a substituent δ 1 - 4 Each of the substituents β, γ and δ is independently selected from the group consisting of C 1 - 4 Alkoxy group, C 1 - 4 Alkyl-carbonyl group, C 1 - 4 It represents one or more substituents selected from the group consisting of an alkyl-carbonyloxy group, a halogeno group, and a hydroxyl group, and n represents an integer of 0 or more and 5 or less.

[0024] Further specific examples of repellents for the Vespidae family include the repellents described in JP 2017-88548 A.

[0025] Examples of functional sustained-release liquids that control plant growth include plant hormones. Examples of plant hormones include natural or synthetic auxins such as indole-3-acetic acid, 2,4-dichlorophenoxyacetic acid, 2,6-dichlorobenzoic acid, and naphthaleneacetic acid, natural or synthetic cytokinins such as zeatin, kinetin, 4-benzylaminobenzimidazole, and benzyladenine, gibberellins, brassinosteroids such as brassinolide and castasterone, and abscisic acid. These plant hormones can be used alone or in combination of two or more.

[0026] Examples of functional sustained-release liquids having antibacterial and antifungal functions include known sustained-release antibacterial agents and sustained-release antifungal agents. Examples of antibacterial and antifungal agents include natural organic compounds such as hinokitiol compounds, chitosan compounds, mustard extract compounds, and eucalyptus compounds, synthetic organic compounds, and organic composite agents. These compounds may be used alone or in combination of two or more. Among these, synthetic organic compounds are preferred from the viewpoint of being effective against both bacteria and fungi.

[0027] Examples of synthetic organic compounds include nitrogen-containing heterocyclic compounds, aldehyde compounds, phenol compounds, biguanide compounds, nitrile compounds, halogen compounds, anilide compounds, disulfide compounds, thiocarbamate compounds, organosilicon quaternary ammonium salt compounds, quaternary ammonium salt compounds, amino acid compounds, organometallic compounds, alcohol compounds, carboxylic acid compounds, ester compounds, thiazoline compounds, cationic polymers, etc. These synthetic organic compounds may be used alone or in combination of two or more.

[0028] Examples of functional sustained-release liquids that have the function of imparting plasticity to resins include carboxylate derivatives, phosphate derivatives, phosphazene derivatives, carboxylic acid amide derivatives, sulfonate derivatives, and sulfonamide derivatives. The plasticizers may be used alone or in combination of two or more.

[0029] Examples of the carboxylate derivatives include alkyl esters of various carboxylic acids which may be substituted with a hydroxyl group, a nitro group, an amino group, an epoxy group, a halogen, etc., and aromatic esters. Specific examples of the carboxylate derivatives include dimethyl phthalate, diethyl phthalate, di-n-octyl phthalate, diphenyl phthalate, benzyl phthalate, dimethoxyethyl phthalate, 4,5-epoxyhexahydrophthalic acid di(2-ethylhexyl), 4,5-epoxycyclohexahydrophthalic acid di(7,8-epoxy-2-octenyl), 4,5-epoxycyclohexahydrophthalic acid di(9,10-epoxyoctadecyl), 4,5-epoxycyclohexahydrophthalic acid di(10,11-epoxyundecyl), di(tetrahydrofurfuryloxyethyl) phthalate, phthalate derivatives such as various mixed phthalate esters and ethylene oxide adducts of mixed phthalate esters, isophthalate derivatives, tetrahydrophthalate derivatives, butoxyethyl parahydroxybenzoate, cyclohexyloxyethoxyethoxyethyl parahydroxybenzoate, 2-ethylhexyl parahydroxybenzoate, hydroxybenzoate esters of ω-alkyl oligoethylene oxide, undecyl glycidyl ether Benzoic acid ester derivatives such as parahydroxybenzoic acid adducts of benzoic acid, propionic acid ester derivatives such as di(tetrahydrofurfuryloxyethyl) thiodipropionate, adipic acid ester derivatives, azelaic acid ester derivatives, sebacic acid ester derivatives, dodecanoic acid ester derivatives, maleic acid ester derivatives, fumaric acid ester derivatives, trimellitic acid ester derivatives, tri(butoxyethoxyethyl) citrate, di-n-octyl-mono(nonylphenoxyethyl) citrate, tri-n-octyl citrate, di-octyl citrate ( tetrahydrofurfuryloxyethyl), trimyristyl citrate, triethyl citrate and other citrate ester derivatives, itaconic acid ester derivatives, oleic acid ester derivatives such as tetrahydrofurfuryl oleate, ricinoleic acid ester derivatives, lactate derivatives such as n-butyl lactate, 2-ethylhexyl lactate, n-butoxyethoxyethyl lactate, n-octoxyethoxyethyl lactate, n-decyloxyethoxyethyl lactate, di(octoxyethoxyethyl) tartrate, tartrate (n Examples of the esters include tartaric acid ester derivatives such as di(n-octyl)(nonylphenoxyethyl) and di(octoxyethoxyethyl) tartrate, malic acid ester derivatives such as dibutoxyethyl malate, di(n-butoxyethoxyethyl) malate, distearyl malate, and octadecenyl isononyl malate, and salicylic acid ester derivatives such as an adduct of benzyl glycidyl ether with salicylic acid.

[0030] Examples of phosphate derivatives include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-(2-ethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, isodecyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri(chloroethyl) phosphate, xylenyl diphenyl phosphate, and tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonate.

[0031] An example of the phosphazene derivative is a cyclic phosphazene compound represented by the following general formula (1).

[0032] [ka]

[0033] In the formula, m represents an integer of 3 to 25; 1 , and R 2 may be the same or different, and each represents an alkyl group having 1 to 8 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 8 carbon atoms and / or an allyl group. The phosphazene derivative may be composed of one type of cyclic phosphazene compound represented by formula (1), or may be composed in the form of a mixture of two or more types.

[0034] The phosphazene derivatives include, for example, linear phosphazene compounds represented by the following general formula (2).

[0035] [ka]

[0036] In the formula, n represents an integer of 3 to 1000; 3 , and R 4may be the same or different and represent an alkyl group having 1 to 8 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 8 carbon atoms and / or an allyl group; X represents a group -N=P(OR 3 ) 3 , group -N=P(OR 4 ) 3 , the group -N=P(O)(OR 3 ) or the group -N=P(O)(OR 4 ), Y represents a group -P(OR 3 ) 4 , group -P(OR 4 ) 4 , the group -P(O)(OR 3 ) 2 or the group -P(O)(OR 4 ) 2 The phosphazene derivative may be composed of one type of linear phosphazene compound represented by formula (2) or may be composed of a mixture of two or more types.

[0037] The phosphazene derivative is a bridging group represented by the following formula (3): 1 , R 2 , R 3 , R 4 The phosphazene compound may be one in which an alkyl group is eliminated from the above group and two oxygen atoms are bridged.

[0038] [ka]

[0039] In the formula, r represents 0 or 1, and A represents a group -SO 2 -, -S-, -O- or -C(CH 3 ) 2 - indicates.

[0040] Specific examples of the cyclic phosphazene compound represented by formula (1) include hexaphenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decafenoxycyclopentaphosphazene, hexapropoxycyclotriphosphazene, octapropoxycyclotetraphosphazene, and decapropoxycyclopentaphosphazene.

[0041] Specific examples of the linear phosphazene compound represented by formula (2) include linear dichlorophosphazene substituted with a propoxy group and / or a phenoxy group. Specific examples of the crosslinked structure represented by formula (3) include 4,4'-sulfonyldiphenylene (bisphenol-S residue), 4,4'-oxydiphenylene group, 4,4'-thiodiphenylene group, and 4,4'-diphenylene group.

[0042] These phosphazene derivatives may be substituted with an amino group and / or a phenylamino group at any position. These phosphazene derivatives may be used alone or in combination of two or more.

[0043] Examples of the carboxylic acid amide derivatives include N-cyclohexylbenzoic acid amide, etc. Examples of the sulfonamide derivatives include N-methyl-benzenesulfonamide, N-ethyl-benzenesulfonamide, N-butyl-benzenesulfonamide, N-cyclohexyl-benzenesulfonamide, N-ethyl-p-toluenesulfonamide, N-butyl-toluenesulfonamide, and N-cyclohexyl-toluenesulfonamide.

[0044] Examples of sulfonic acid ester derivatives include ethyl benzenesulfonate. Examples of sulfonic acid amide derivatives include 2-methoxyethyl methanesulfonate, 2,2,2-trifluoroethyl methanesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, and n-propyl p-toluenesulfonate.

[0045] Examples of the functional sustained-release liquid having a sliding function include known sustained-release sliding agents, such as mineral oil, synthetic oil, wax, and paraffin.

[0046] Examples of the self-repairing function-releasing liquid include known self-repairing agents having sustained release properties, such as polyrotaxane and self-healing clear (a product of Natoco Shoji Co., Ltd.).

[0047] Examples of functional sustained-release liquids having catalytic functions include known catalysts having sustained-release properties. Examples of known catalysts include ionic liquids, tertiary amines (e.g., "PZETA" manufactured by Tosoh Corporation), organic titanium compounds (e.g., tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetrakis(2-ethylhexyloxine) titanium (e.g., Nippon Soda Co., Ltd. products), and the like.

[0048] Examples of functional sustained-release liquids having medical functions include known medical products having sustained-release properties.

[0049] Examples of functional sustained-release liquids having antiviral functions include aromatic compounds (Amorden V-1000HP, manufactured by Yamato Chemical Industry Co., Ltd.) and cationic polymers (Amorden D-CL50, D-CLH, manufactured by Yamato Chemical Industry Co., Ltd.).

[0050] Examples of functional sustained-release liquids with self-cleaning properties include ionic surfactants (Aminoion AS200, AS400, manufactured by Nippon Nyukazai Co., Ltd.), nonionic surfactants (Amit 102, 105, manufactured by Kao Co., Ltd.), and fluorine-based surfactants (Surflon S-242, S-243, S-386, manufactured by AGC Sei Chemical Co., Ltd.).

[0051] The solvent is preferably one that has high compatibility with the matrix resin and has little effect on the shape stability of the molded body. Examples of the solvent include water, methanol, ethanol, dimethyl sulfoxide, polyethylene glycol, sulfonamide derivatives, sulfonic acid ester derivatives, carboxylic acid amide derivatives, carboxylic acid ester derivatives, phosphate ester derivatives, hydrocarbon compounds, and silicone compounds.

[0052] Examples of sulfonamide derivatives include N-methyl-benzenesulfonamide, N-ethyl-benzenesulfonamide, N-butyl-benzenesulfonamide, N-cyclohexyl-benzenesulfonamide, N-ethyl-p-toluenesulfonamide, N-butyl-toluenesulfonamide, and N-cyclohexyl-toluenesulfonamide. Examples of sulfonate derivatives include 2-methoxyethyl methanesulfonate, 2,2,2-trifluoroethyl methanesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, and n-propyl p-toluenesulfonate.

[0053] An example of the carboxylic acid amide derivative is N-cyclohexylbenzoic acid amide.

[0054] Examples of the carboxylate derivatives include dimethyl phthalate, diethyl phthalate, di-n-octyl phthalate, diphenyl phthalate, benzyl phthalate, dimethoxyethyl phthalate, 4,5-epoxyhexahydrophthalic acid di(2-ethylhexyl), 4,5-epoxycyclohexahydrophthalic acid di(7,8-epoxy-2-octenyl), 4,5-epoxycyclohexahydrophthalic acid di(9,10-epoxyoctadecyl), 4,5-epoxycyclohexahydrophthalic acid di(10,11-epoxyundecyl), di(tetrahydrofurfuryloxyethyl) phthalate, various mixed phthalate esters and ethylene oxide adducts of mixed phthalate esters, and other phthalate derivatives; isophthalate derivatives; tetrahydrophthalate derivatives; butoxyethyl parahydroxybenzoate, cyclohexyloxyethoxyethoxyethyl parahydroxybenzoate, 2-ethylhexyl parahydroxybenzoate, hydroxybenzoate esters of ω-alkyl oligoethylene oxides; benzoate derivatives such as parahydroxybenzoic acid adducts of undecyl glycidyl ether; propionate derivatives such as di(tetrahydrofurfuryloxyethyl) thiodipropionate; adipate derivatives; Zelate derivatives, sebacate derivatives, dodecane-2-acid ester derivatives, maleate derivatives, fumarate derivatives, trimellitate derivatives, citrate derivatives such as tri(butoxyethoxyethyl) citrate, di-n-octyl-mono(nonylphenoxyethyl) citrate, tri-n-octyl citrate, dioctyl(tetrahydrofurfuryloxyethyl) citrate, trimyristyl citrate, and triethyl citrate, itaconic acid ester derivatives, oleate derivatives such as tetrahydrofurfuryl oleate, ricinoleic acid ester derivatives, n-butyl lactate, 2-ethylhexyl lactate, n-butoxyethoxyethyl lactate, and n-octoxyethoxyethyl lactate. Examples of the ester derivatives include lactate derivatives such as (n-decyloxyethoxyethyl) lactate, tartrate derivatives such as di(octoxyethoxyethyl) tartrate, (n-octyl)(nonylphenoxyethyl) tartrate, and di(octoxyethoxyethyl) tartrate, malate derivatives such as dibutoxyethyl malate, di(n-butoxyethoxyethyl) malate, distearyl malate, and octadecenyl isononyl malate, and salicylate derivatives such as a salicylic acid adduct of benzyl glycidyl ether.

[0055] Examples of phosphate derivatives include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-(2-ethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, isodecyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri(chloroethyl) phosphate, xylenyl diphenyl phosphate, and tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonate.

[0056] Examples of the hydrocarbon compounds include chain-type saturated hydrocarbon compounds (paraffins), chain-type unsaturated hydrocarbon compounds (olefins), alicyclic hydrocarbon compounds (cycloalkanes, cycloalkenes, cycloalkynes, etc.), and aromatic hydrocarbon compounds. Among these hydrocarbon compounds, paraffin oil having a molecular weight of 330 to 530 and a kinetic viscosity of 10 to 120 cSt is particularly suitable. Hydrocarbon compounds having a molecular weight of 330 to 530 are preferred from the viewpoint of easily penetrating into the body of small animals through the body openings of small animals. Moreover, hydrocarbon compounds having a kinetic viscosity of 10 to 120 cSt are preferred from the viewpoint of easily adhering to the body surface of small animals. Furthermore, paraffin oil is preferred from the viewpoint of being inexpensive and easily available. Examples of the silicone compounds include dimethyl silicone, methylphenyl silicone, polyether-modified silicone, long-chain alkyl-modified silicone, and higher fatty acid ester-modified silicone.

[0057] Examples of the flame retardant include non-halogen flame retardants such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate, aromatic condensed phosphate esters, aliphatic phosphoric acid amidates, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, melamine cyanurate, Adeka STAB FP-600 (ADEKA), Adeka STAB PFR (ADEKA), and Adeka STAB FP-900L (ADEKA). Manufactured by ADEKA, halogen-based flame retardants include tris(chloropropyl) phosphate, tris(tribromoneopentyl) phosphate, halogen-containing condensed phosphate ester, tribromoneopentyl alcohol, dibromoneopentyl glycol, tribromophenol, pentabromobenzyl polyacrylate, decabromodiphenyl oxide, tetrabromobisphenol-A, and brominated epoxy.

[0058] Since the functional sustained-release liquid must be liquid, it is preferable that the acid dissociation constant is in the range of -10 to 40, and further, from the viewpoint of the constraints on the processing temperature of the matrix resin, it is preferable that the functional sustained-release liquid has a molecular weight of 600 or less and a melting point of 10°C or higher.

[0059] The acid dissociation constant of the functional sustained-release liquid is as follows, assuming that the general formula of the acid is HA and the solvent is Hsol: JPEG0007671484000006.jpg33147In this case, the acid dissociation constant Ka can be expressed as follows, including the solvent concentration [Hsol] in the constant: JPEG0007671484000007.jpg27133http: / / www.fm.ehcc.kyoto-u.ac.jp / pKa_compilation_Williams_RipinEvans.pdf The acid dissociation constants of the functional sustained-release liquids were experimentally determined using the above-mentioned literature and neutralization titration, absorption spectrophotometer method, and capillary electrophoresis method.

[0060] (Porous body) Porous bodies capable of supporting functional components include structures made of metal ions, such as porous coordination polymers, zeolites, silica, alumina, and molecular sieves. In addition, the radius of the metal ions in the porous body is within the range of the acid dissociation constant of the functional sustained-release liquid, so that the excellent sustained-release effect can be maintained for a long period of time. Furthermore, among the porous bodies, porous coordination polymers have a large support adsorption area and a high degree of freedom in designing metal ions, and therefore have the advantage of being able to cover a wide range of types of functional sustained-release liquids. A detailed explanation of the porous coordination polymer is given below.

[0061] (Porous coordination polymer) A porous coordination polymer is a porous material containing metal ions and organic ligands. The porous coordination polymer has a form in which, for example, metal ions are adsorbed to organic ligands. The organic ligand is, for example, an organic ligand capable of bonding with metal ions. The porous coordination polymer is also called MOF (Metal-Organic Framework) or PCP (Porous Coordination Polymer).

[0062] A porous coordination polymer has, for example, a large number of pores in the macropore or mesopore region, and the pore size (diameter of the pores) is determined from the crystal structure, and therefore has a uniform pore size.

[0063] By controlling the length of the organic ligands and the affinity due to the chemical structure, the porous coordination polymer can increase the retention of the functional liquid component and achieve fine packing. From the same viewpoint, the average pore size of the porous coordination polymer is preferably equal to or larger than the molecular size of the functional sustained-release liquid, and the specific surface area of ​​the porous coordination polymer measured by the BET method is 900 m or more. 2 / g or more (e.g., 900m 2 / g or more 10400m 2 / g or less) at 1000m 2 / g or more, and 2 / g or more is more preferable, and 2It is particularly preferable that the specific surface area according to the BET method is 900 m 2 / g or more, the porous coordination polymer can effectively develop the functional liquid with the matrix resin, compared to the case where the functional liquid component is directly kneaded into the matrix resin to form a composite molding. The average pore size of the porous coordination polymer is determined by the BET method. The molecular diameter of the functional sustained-release liquid is determined by the following procedure using the open source "Mol-view." First, the molecule is drawn, and the long and short diameters of the molecule are measured in the software. Here, the long diameter is the intermolecular distance of the long part when the molecule is stretched in a straight line, and the short diameter is the intermolecular distance of the short part when the molecule is stretched in a straight line. Here, the above "molecular diameter" corresponds to the above short diameter.

[0064] The average pore size of the porous coordination polymer is preferably 0.1 to 5.0 nm, more preferably 0.5 to 3.0 nm, from the viewpoint of enabling the functional sustained-release liquid to be effectively developed by the matrix resin and further improving the long-term sustained release.

[0065] (Metal ions) Examples of metal ions include silver ions, aluminum ions, beryllium ions, calcium ions, cadmium ions, cerium ions, cobalt ions, chromium ions, copper ions, dysprosium ions, erbium ions, europium ions, iron ions, gallium ions, gadolinium ions, holmium ions, indium ions, lithium ions, magnesium ions, manganese ions, molybdenum ions, neodymium ions, nickel ions, scandium ions, samarium ions, strontium ions, terbium ions, thulium ions, vanadium ions, tungsten ions, yttrium ions, ytterbium ions, zinc ions, and zirconium ions. These metal ions may be used alone or in combination of two or more. These metal ions may be present in the porous coordination polymer in the form of a compound such as a salt.

[0066] In this embodiment, the metal ion radius of the porous coordination polymer can be obtained from the Diploma Program Chemistry Collection, Shannon et al., Acta A 32 (1976) 751, or the like.

[0067] (organic ligand) The organic ligand is preferably a bridging ligand capable of bridging with a metal ion. Examples of the bridging ligand include 2-methylimidazole, terephthalic acid, 2,5-dihydroxyterephthalic acid, 1,4-naphthalenedicarboxylic acid, 1,3,5-benzenetricarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4"-p-terphenyldicarboxylic acid, isophthalic acid, 1,3,5-benzenetricarboxylic acid, 1,3,5-tri-4-carboxylphenylbenzene, methylimidazole, 4,4'-biphenyldicarboxylic acid, fumaric acid, naphthalenedicarboxylic acid, hexaazatriphenylene, 2,5-dihydroxybenzoic acid, trimesic acid, 5-cyano-benzenedicarboxylic acid, 5-ethyl-1,3 Benzodicarboxylic acid, terephenyl-3,3',5,5'-tetracarboxylic acid, 9,10-anthracene dicarboxylic acid, imidazole, 2,2'-diamino-4,4'-stilbene dicarboxylic acid, 2,2'-dinitro-stilbene dicarboxylic acid, 2,5-dihydroxyterephthalic acid, 3,3',5,5'-tetracarboxydiphenylmethane, 1,2,4,5-tetrakis(4-carboxyphenyl)benzene, 4,4',4"-s-triazine-2,4,6-trail-tribenzoic acid, 2-hydroxyterephthalic acid, biphenyl-3,3',5,5'-tetracarboxylic acid, biphenyl-3,4,5-tricarboxylic acid, 5-bromoisophthalic acid, malonic acid, and the like.

[0068] In the method for producing a functional sustained-release composition, it is desirable to remove residual substances attached to or present on the surface and / or in the pores of the porous coordination polymer before making the porous coordination polymer retain the functional sustained-release liquid. If residual substances are present, when the porous coordination polymer and the functional liquid are composited, the pores may be narrowed or completely blocked by the residual substances, making it difficult to inject the functional liquid into the pores of the porous coordination polymer. In addition, the residual substances may be mixed into the functional liquid as impurities, and the physical properties of the functional sustained-release liquid may change, making it difficult to obtain the desired effect.

[0069] As a method for removing residual substances, for example, a method for washing the porous coordination polymer with a solvent can be mentioned. As a solvent used for washing, for example, water, methanol, THF, and DMF can be mentioned, and the solvent is preferably water and / or methanol. When the solvent is water and / or methanol, the molecular diameter of the solvent is small, so that the solvent easily enters the pores of the porous coordination polymer, and the residual substances in the pores can be easily removed. In addition, in the process of washing the residual substances, the porous coordination polymer may be immersed in the solvent for a long time. The immersion time is preferably 12 hours or more, and more preferably 24 hours or more. As a method for removing unreacted substances or impurities, a method for desorbing residual substances by heat treatment can be mentioned. When the unreacted substances or impurities are organic substances and it is desired to remove the organic substances, it is preferable to perform heat treatment in air or an oxygen atmosphere. When the unreacted substances or impurities are volatile substances and it is desired to remove the volatile substances, it is preferable to perform vacuum heat treatment. The heating temperature is preferably 100 to 300°C. It is preferable to carry out washing with a solvent and then carrying out a heat treatment to completely remove the solvent.

[0070] (Matrix resin) The matrix resin includes one or more kinds of resins. Examples of the resin include thermoplastic resins and thermosetting resins. Examples of the thermoplastic resin include polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polystyrene resin, AS resin, ABS resin, methacrylic resin, polyvinyl alcohol resin, EVA resin, polyamide resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polyethylene terephthalate resin, polybutylene terephthalate resin, fluororesin, polyphenylene sulfide resin, polysulfone resin, polyarylate resin, polyetherimide resin, polyethersulfone resin, polyetherketone resin, liquid crystal polyester resin, thermoplastic polyimide resin, and thermoplastic polyurethane resin. Examples of the thermosetting resin include epoxy resins, unsaturated polyester resins, phenolic resins, urea resins, melamine resins, alkyd resins, silicone resins, polyimide resins, polyurethane resins, vinyl ester resins, diallyl phthalate resins, furan resins, polyamino bismaleimide resins, casein resins, epoxy acrylate resins, urethane acrylate resins, polyurea resins, benzoxazine resins, oxetane resins, xylene resins, dicyclopentadiene resins, and episulfide resins.

[0071] The ratio of the content of the functional sustained-release liquid to the content of the porous coordination polymer is, for example, 1.0 to 5.0, and from the viewpoint of more effectively and reliably achieving the effects of the present invention, is preferably 1.5 to 3.0.

[0072] The content of the matrix resin in the functional sustained-release composition may be, for example, about 10 to 95% by mass.

[0073] (Inorganic filler) The functional sustained-release composition may contain an inorganic filler from the viewpoint of improving mechanical properties. As the inorganic filler, a known inorganic filler is used, for example, a particulate inorganic filler, a fibrous inorganic filler, and a scaly or plate-like inorganic filler. As the particulate inorganic filler, for example, it may be a particulate inorganic filler having a micron size or a particulate inorganic filler having a nano size. As the particulate inorganic filler having a micron size, for example, calcium carbonate particles, silica particles, glass beads, titanium oxide particles, zinc oxide particles, potassium titanate particles, titania particles, monoclinic titania particles, calcium phosphate particles, wollastonite, vermiculite, silas balloons, glass balloons, etc. As the particulate inorganic filler having a nano size, for example, nano titanium oxide, nano silica, carbon black, carbon filler, etc. are included. The inorganic filler is used alone or in combination of two or more.

[0074] Among these, the particulate inorganic filler is preferably potassium titanate particles from the viewpoint of being more excellent in the sustained release property of the functional sustained release liquid (particularly the small animal control agent).The fibrous inorganic filler is preferably a fibrous inorganic filler having an average fiber diameter of 0.05 to 10 μm and an average fiber length of 3 to 150 μm, more preferably a fibrous inorganic filler having an average fiber diameter of 0.1 to 7 μm and an average fiber length of 5 to 50 μm, from the viewpoint of not adversely affecting the appearance of the molded article.

[0075] The fibrous inorganic filler may be, for example, a micron-sized fibrous inorganic filler or a nano-sized fibrous inorganic filler. Examples of the micron-sized fibrous inorganic filler include glass fiber, carbon fiber, graphite fiber, aramid fiber, vinylon fiber, polyamide fiber, polyester fiber, cotton, hemp fiber, kenaf fiber, bamboo fiber, rayon, steel fiber, aluminum fiber, gypsum fiber, potassium tetratitanate fiber, potassium hexatitanate fiber, potassium octatitanate fiber, titania fiber, monoclinic titania fiber, silica fiber, wollastonite, and xonotlite. Examples of the nano-sized fibrous inorganic filler include carbon fiber, carbon nanotube, fullerene, cotton fibril, silicon nitride whisker, alumina whisker, silicon carbide whisker, and nickel whisker. These fibrous inorganic fillers may be used alone or in combination of two or more.

[0076] The scale-like or plate-like inorganic filler may be, for example, a scale-like or plate-like inorganic filler having a micron size, or a scale-like or plate-like inorganic filler having a nano size. Examples of the scale-like or plate-like inorganic filler having a micron size include talc, kaolin clay, mica (synthetic mica or natural mica), glass flakes, aragonite, calcium sulfate, aluminum hydroxide, potassium titanate, potassium lithium titanate, potassium magnesium titanate, sericite, plate-like alumina, and boron nitride. Examples of the scale-like or plate-like inorganic filler having a nano size include organic montmorillonite, swellable synthetic mica, graphite, and graphite. The scale-like inorganic filler may be used alone or in combination of two or more. The inorganic filler may be used as it is, or from the viewpoint of improving the interfacial adhesion with the resin and further improving the mechanical properties, it may be used in a form that has been surface-treated with a surface treatment agent such as a silane coupling agent, e.g., aminosilane, epoxysilane, or acrylicsilane, or a titanate coupling agent.

[0077] (Weather resistance additive) The functional sustained-release composition may contain a weather resistance additive in order to further improve weather resistance when left outdoors. The weather resistance additive may be one selected from the group consisting of hindered phenol-based antioxidants, phosphorus-based antioxidants, ultraviolet absorbing light stabilizers, hindered amine-based light stabilizers, and carbon.

[0078] Examples of the hindered phenol-based antioxidants include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], bis-[3,3-bis-(4'-hydroxy-3'-tert-butylphenyl)-butanoic acid]-glycol ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], phenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,3′,3″,5,5′,5″-hexa-tert-butyl-a,a′,a″-(methylene-2,4,6-triyl)tri-p-cresol, hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, and methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0079] Examples of phosphorus-based antioxidants include tris(2,4-di-tert-butylphenyl)phosphite, tris[2-[[2,4,8,10-tetra-tert-butylbenzo[d,f][1,3,2]dioxaphosphen-6-yl]oxy]ethyl]amine, tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol phosphite, bis(2,6-di-tert-butyl-4-phenyl)pentaerythritol phosphite, and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite.

[0080] Examples of ultraviolet absorbers include 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol, propanediol, and [(4-methoxyphenyl)-methylene]-dimethyl ester.

[0081] Examples of the hindered amine light stabilizer include N,N',N'',N'''-tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine, poly[(6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl)(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)), bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, 2,2,4, 4-Tetramethyl-7-oxa-3,20-diazadispiro-[5.1.11.2]-heneicosan-21-one, propanedioic acid, [(4-methoxyphenyl)-methylene]-, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 1,3-benzenedicarboxamide, N,N-bis(2,2,6,6-tetramethyl-4-piperidinyl), and 2-ethyl, 2′-ethoxy-oxalanilide.

[0082] The weather resistance additives may be used alone or in combination of two or more. Among these, the weather resistance additives include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, tris(2,4-di-tert-butylphenyl)phosphite, tetrakis(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonite, bis(2,4-di-tert-butylphenyl)propionate ... ethylphenyl)pentaerythritol phosphite, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-ethyl,2′-ethoxy-oxalanilide, N,N′,N″,N′′′-tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine, poly[(6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl)(2,2,6,6-tetramethyl-4-piperidyl)imino] One or more selected from the group consisting of hexamethylene((2,2,6,6-tetramethyl-4-piperidyl)imino)), 1,3-benzenedicarboxamide, and N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl) are preferred.

[0083] The functional sustained-release composition of this embodiment has a surface concentration of the liquid component of 1.0 mg / cm when compressed at 10 MPa or more. 2 It is preferred that the surface concentration is less than 1000 μg / cm 2 If the above conditions are met, when the functional sustained-release composition is processed by injection molding or the like, problems such as clogging of the material pellets may occur due to reasons such as a sticky surface.

[0084] (Application) The functional sustained release composition can be used not only by processing it into a molded body having a predetermined shape, but also as it is, for example, as a paint, a sealant, a cushioning material, or a filling material. The functional sustained release composition can be used to produce a molded body having fluidity, semi-fluidity, or rubber-like elasticity, for example, by selecting an appropriate matrix resin and appropriately adjusting the amount of the porous coordination polymer adsorbed with the functional sustained release liquid and the amount of the filler, plasticizer, etc. added. For this reason, the present invention also includes a molded body molded from the functional sustained release composition of this embodiment. Those having fluidity can be used, for example, as a paint, and those having semi-fluidity can be used, for example, as a sealant. Those having rubber-like elasticity can be used, for example, as a cushioning material or a filling material. In addition, when the functional sustained release composition is used as a paint, a sealant, a cushioning material, or a filling material, a coloring material such as a colorant or a pigment can be added to the matrix resin as necessary. In molding the functional sustained-release composition, any suitable known molding method can be applied, such as injection molding, compression molding, transfer molding, extrusion molding, blow molding, calendar molding, FRP molding, lamination molding, cast molding, solution casting, vacuum / pressure molding, composite extrusion molding, foam molding, thermoforming, insert molding, melt impregnation, etc. The shape of the molded product is not particularly limited, and it can be any shape, such as a flat plate, rod, cylinder, comb, sphere, etc. The functional sustained-release composition can be molded by itself, or can be molded in two or more colors in combination with metal, etc. EXAMPLES

[0085] The present invention will be described in detail below using examples and comparative examples, but the present invention is not limited to the following examples in any way.

[0086] [Example 1] The functional sustained-release liquid was etofenprox (melting point 37°C, boiling point 200°C, molecular weight 376.49, acid dissociation constant 20, Mitsui Chemicals Agro product), the porous medium was a porous coordination polymer (MOF-74-Mg, specific surface area by BET method: 1,200 m) consisting of magnesium ions (oxidation number 2, ionic radius 45 pm) as metal ions, and 2,5-dihydroxyterephthalic acid as organic ligands. 2 / g, average pore size: 1.1 nm) was used. The functional sustained-release liquid was adsorbed to the porous body so as to have the composition shown in Table 1 below. The adsorption method was a method in which the porous body was placed in a vacuum bell jar, the pressure of the porous body was reduced to 0.01 MPa or less, and etofenprox was dropped into this state and adsorbed to the porous body. The porous body with etofenprox adsorbed was compounded and mixed with polyethylene resin (Novatec UJ310, a product of Japan Polyethylene) as a matrix resin to prepare a functional sustained-release composition (molded body material). The amount of polyethylene resin blended was such that the content of the matrix resin (polyethylene resin), the content of the functional sustained-release liquid (etofenprox), and the content of the porous body (porous coordination polymer) were each as shown in Table 1 below. The compounding method was a method in which a Labo Plastomill device (a product of Toyo Seiki Seisakusho) was used, and compounding was performed for 10 minutes at a processing temperature of 120°C. Next, using a press (Imoto Manufacturing Co., Ltd.'s "IMC180C type"), the green body material was pressed with 5 tons at 120° C. to produce a plate green body of 50 mm×50 mm and 1.2 mm thick.

[0087] Regarding Table 1 shown below: *Exponential function formula: y (surface amount of functional sustained-release liquid), x (number of repeated washings), A (initial value of surface amount of functional sustained-release liquid), B (magnitude of change in surface amount of functional sustained-release liquid due to repeated washing). [Table 1]

[0088] [ Reference example 2] A porous coordination polymer ("Al-PCP-F") consisting of aluminum ions (oxidation number 3, ionic radius 54 pm) as metal ions and fumaric acid as organic ligands, with a BET specific surface area of ​​900 m 2 Functional sustained-release compositions (molded body materials) were prepared in the same manner as in Example 1, except that polyethylene resin was used (0.05% polyethylene resin, 0.05% polyethylene terephthalate ... Reference example I chose 2.

[0089] [ Reference example 3] A porous coordination polymer (Fe-BTC) consisting of iron ions (oxidation number 3, ionic radius 55 pm) as metal ions and trimesic acid as organic ligands, with a BET specific surface area of ​​1,754 m 2 Functional sustained-release compositions (molded body materials) were prepared in the same manner as in Example 1, except that polyethylene resin was used (0.1% by weight, 0.1% by weight, average pore size: 2.4-2.9 nm). The blending amount of polyethylene resin was set so that the content of matrix resin (polyethylene resin), the content of functional sustained-release liquid (etofenprox), and the content of porous body (porous coordination polymer) were as shown in Table 1 above. Thereafter, molded bodies were prepared from each molded body material in the same manner as in Example 1, and these were Reference example I chose 3.

[0090] [ Reference example 4] A porous coordination polymer ("MIL-101(Cr)") consisting of a chromium ion (oxidation number 3, ionic radius 63 pm) as a metal ion and terephthalic acid as an organic ligand, with a BET surface area of ​​2,200 m 2Functional sustained-release compositions (molded body materials) were prepared in the same manner as in Example 1, except that polyethylene resin was used (0.1% by weight, 0.1% by weight, average pore size: 2.0-2.7 nm). The blending amount of polyethylene resin was set so that the content of matrix resin (polyethylene resin), the content of functional sustained-release liquid (etofenprox), and the content of porous body (porous coordination polymer) were as shown in Table 1 above. Thereafter, molded bodies were prepared from each molded body material in the same manner as in Example 1, and these were Reference example The score was 4.

[0091] [Example 5] A porous coordination polymer (MOF-74-Ni) consisting of nickel ions (oxidation number 1, ionic radius 68 pm) as metal ions and 2,5-dihydroxyterephthalic acid as organic ligands, with a BET surface area of ​​1,360 m 2 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 1, except that a polyethylene resin having a molecular weight of 1.00 g / g and an average pore size of 1.0 nm was used. The amount of polyethylene resin was set so that the content of the matrix resin (polyethylene resin), the content of the functional sustained-release liquid (etofenprox), and the content of the porous body (porous coordination polymer) were as shown in Table 1. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 5.

[0092] [Example 6] A porous coordination polymer (Uio-66) consisting of a zirconium ion (oxidation number 4, ionic radius 72 pm) as the metal ion and terephthalic acid as the organic ligand, with a BET surface area of ​​1,000 m 2 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 1, except that a polyethylene resin having a molecular weight of 1.0001 to 1.0001 mm (average pore size: 0.9 nm, pore size: 0.1 to 0.2 nm) was used. The amount of polyethylene resin was set so that the content of the matrix resin (polyethylene resin), the content of the functional sustained-release liquid (etofenprox), and the content of the porous body (porous coordination polymer) were as shown in Table 1. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 6.

[0093] [ Reference example 7] A porous coordination polymer (Cu-BTC) consisting of copper ions (oxidation number 2, ionic radius 73 pm) as metal ions and trimesic acid as organic ligands, with a BET surface area of ​​1,500 m 2 Functional sustained-release compositions (molded body materials) were prepared in the same manner as in Example 1, except that polyethylene resin was used (0.05% polyethylene resin, 0.05% polyethylene terephthalate ... Reference example The score was 7.

[0094] [ Reference example 8] A porous coordination polymer ("ZIF-8"; BET surface area: 1,400 m2) consisting of zinc ions (oxidation number 2, ionic radius 74 pm) as metal ions and 2-methylimidazole as organic ligands. 2 Functional sustained-release compositions (molded body materials) were prepared in the same manner as in Example 1, except that polyethylene resin was used (0.01% by weight, 0.01% by weight, average pore size: 0.3-1.1 nm). The blending amount of polyethylene resin was set so that the content of matrix resin (polyethylene resin), the content of functional sustained-release liquid (etofenprox), and the content of porous body (porous coordination polymer) were each as shown in Table 1 above. Thereafter, molded bodies were prepared from each molded body material in the same manner as in Example 1, and these were Reference example The score was 8.

[0095] [Example 9] The functional sustained-release liquid was 2-n-octyl-4-isothiazolin-3-one (melting point 23°C, boiling point 142°C, molecular weight 213.34, acid dissociation constant -0.23, manufactured by Tokyo Chemical Industry Co., Ltd.), the porous medium was a metal ion, nickel ion (oxidation number 1, ionic radius 68 pm), and the organic ligand was a porous coordination polymer ("MOF-74-Ni", surface area by BET method: 1,360 m2). 2A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 1, except that a pore size distribution of 1.0 μm / g, average pore size: 1.0 nm) and an ethylene vinyl acetate resin ("Suntech EM6415" manufactured by Asahi Kasei) were used as the matrix resin. The amount of ethylene vinyl acetate resin was set so that the content of the matrix resin (ethylene vinyl acetate resin), the content of the functional sustained-release liquid (2-n-octyl-4-isothiazolin-3-one), and the content of the porous body (porous coordination polymer) were as shown in Table 2 below. Thereafter, molded bodies were prepared from each molded body material in the same manner as in Example 1, and these were designated as Example 9.

[0096] Regarding Table 2 below. *Exponential function formula: y (surface amount of functional sustained-release liquid), x (number of repeated washings), A (initial value of surface amount of functional sustained-release liquid), B (magnitude of change in surface amount of functional sustained-release liquid due to repeated washing). [Table 2]

[0097] [Example 10] A porous coordination polymer (Uio-66) consisting of a zirconium ion (oxidation number 4, ionic radius 72 pm) as the metal ion and terephthalic acid as the organic ligand, with a BET surface area of ​​1,000 m 2 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 9, except that a 100% ethylene vinyl acetate resin (100% ethylene vinyl acetate resin, 100% propylene glycol) was used (average pore size: 0.9 nm ...). The amount of ethylene vinyl acetate resin was set so that the content of the matrix resin (ethylene vinyl acetate resin), the content of the functional sustained-release liquid (2-n-octyl-4-isothiazolin-3-one), and the content of the porous body (porous coordination polymer) were as shown in Table 2. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 10.

[0098] [Example 11] A porous coordination polymer (Cu-BTC) consisting of copper ions (oxidation number 2, ionic radius 73 pm) as metal ions and trimesic acid as organic ligands, with a BET surface area of ​​1,500 m 2A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 9, except that a 100% ethylene vinyl acetate resin (100% ethylene vinyl acetate resin, 100% propylene glycol) was used (average pore size: 0.9 nm ...). The amount of ethylene vinyl acetate resin was set so that the content of the matrix resin (ethylene vinyl acetate resin), the content of the functional sustained-release liquid (2-n-octyl-4-isothiazolin-3-one), and the content of the porous body (porous coordination polymer) were as shown in Table 2. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 11.

[0099] [Example 12] A porous coordination polymer ("ZIF-8"; BET surface area: 1,400 m2) consisting of zinc ions (oxidation number 2, ionic radius 74 pm) as metal ions and 2-methylimidazole as organic ligands. 2 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 9, except that a 100% ethylene vinyl acetate resin (100% ethylene vinyl acetate resin, ...

[0100] [Example 13] Zeolite (Union Showa's "USKY-790", surface area by BET method: 792 m) composed of sodium ions (oxidation number 1, ionic radius 103 pm) as metal ions and aluminosilicate as ligands. 2 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 9, except that a 100% ethylene vinyl acetate resin (100% ethylene vinyl acetate resin, 100% propylene glycol) was used (average pore size: 0.5 nm ...). The amount of ethylene vinyl acetate resin was set so that the content of the matrix resin (ethylene vinyl acetate resin), the content of the functional sustained-release liquid (2-n-octyl-4-isothiazolin-3-one), and the content of the porous body (zeolite) were as shown in Table 2. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 13.

[0101] [Example 14] A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 9, except that a silver ion (oxidation number 1, ionic radius 115 pm) was used as the metal ion, and a porous coordination polymer ("Ag-PCP") composed of di-p-xylylene was used as the ligand. The amount of ethylene vinyl acetate resin was set so that the content of the matrix resin (ethylene vinyl acetate resin), the content of the functional sustained-release liquid (2-n-octyl-4-isothiazolin-3-one), and the content of the porous body (zeolite) were each as shown in Table 2. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 14.

[0102] [Example 15] The functional sustained-release liquid was methyl anthranilate (melting point 24°C, boiling point 256°C, molecular weight 151.16, acid dissociation constant 2.23, manufactured by Tokyo Chemical Industry Co., Ltd.), the porous medium was a metal ion with nickel ion (oxidation number 1, ionic radius 68 pm), and the organic ligand was a porous coordination polymer (MOF-74-Ni, surface area by BET method: 1,360 m2) composed of 2,5-dihydroxyterephthalic acid. 2 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 1, except that a polypropylene resin (Prime Polymer product "Prime Polypro J105G") was used as the matrix resin, and the matrix resin was a polypropylene resin. The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin), the content of the functional sustained-release liquid (methyl anthranilate), and the content of the porous body (porous coordination polymer) were as shown in Table 3 below. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 15.

[0103] Regarding Table 3 below. *Exponential function formula: y (surface amount of functional sustained-release liquid), x (number of repeated washings), A (initial value of surface amount of functional sustained-release liquid), B (magnitude of change in surface amount of functional sustained-release liquid due to repeated washing). [Table 3]

[0104] [Example 16] A porous coordination polymer (Uio-66) consisting of a zirconium ion (oxidation number 4, ionic radius 72 pm) as the metal ion and terephthalic acid as the organic ligand, with a BET surface area of ​​1,000 m 2 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 15, except that a polypropylene resin having a molecular weight of 1.0001 to 1.0001 mm (average pore size: 0.9 nm, pore size: 0.1 to 0.2 nm) was used. The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin), the content of the functional sustained-release liquid (methyl anthranilate), and the content of the porous body (porous coordination polymer) were as shown in Table 3. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 16.

[0105] [Example 17] A porous coordination polymer (Cu-BTC) consisting of copper ions (oxidation number 2, ionic radius 73 pm) as metal ions and trimesic acid as organic ligands, with a BET surface area of ​​1,500 m 2 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 15, except that a polypropylene resin having a molecular weight of 1.0001 to 1.0001 mm (average pore size: 0.9 nm, pore size: 0.1 to 0.2 nm) was used. The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin), the content of the functional sustained-release liquid (methyl anthranilate), and the content of the porous body (porous coordination polymer) were as shown in Table 3. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 17.

[0106] [Example 18] A porous coordination polymer ("ZIF-8"; BET surface area: 1,400 m2) consisting of zinc ions (oxidation number 2, ionic radius 74 pm) as metal ions and 2-methylimidazole as organic ligands. 2A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 15, except that a polypropylene resin having a molecular weight of 1.0001 to 1.0001 (wt. / g, average pore size: 0.3 to 1.1 nm) was used. The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin), the content of the functional sustained-release liquid (methyl anthranilate), and the content of the porous body (porous coordination polymer) were as shown in Table 3. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 18.

[0107] [Example 19] Zeolite (Union Showa's "USKY-790", surface area by BET method: 792 m) composed of sodium ions (oxidation number 1, ionic radius 103 pm) as metal ions and aluminosilicate as ligands. 2 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 15, except that a polypropylene resin having a molecular weight of 1.0001 to 1.0001 mm (average pore size: 0.5 nm) was used. The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin), the content of the functional sustained-release liquid (methyl anthranilate), and the content of the porous body (zeolite) were as shown in Table 3. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 19.

[0108] [Example 20] A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 15, except that a silver ion (oxidation number 1, ionic radius 115 pm) was used as the metal ion, and a porous coordination polymer ("Ag-PCP") composed of di-p-xylylene was used as the ligand. The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin), the content of the functional sustained-release liquid (methyl anthranilate), and the content of the porous body (zeolite) were as shown in Table 3. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated as Example 20.

[0109] [Example 21] The functional sustained-release liquid was 5-heptyloxolan-2-one (melting point 164°C, boiling point 286°C, molecular weight 184.27, acid dissociation constant 12.87, pure chemical product), the porous medium was a porous coordination polymer ("MOF-74-Mg"; specific surface area by BET method: 1,200 m) composed of magnesium ions (oxidation number 2, ionic radius 45 pm) as metal ions, and 2,5-dihydroxyterephthalic acid as organic ligands. 2 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 15, except that a polypropylene resin having a molecular weight of 1.0001 to 1.0001 (wt. / g, average pore size: 1.1 nm) was used. The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin), the content of the functional sustained-release liquid (5-heptyloxolan-2-one), and the content of the carrier (porous coordination polymer) were as shown in Table 4 below. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 21.

[0110] Regarding Table 4 below. *Exponential function formula: y (surface amount of functional sustained-release liquid), x (number of repeated washings), A (initial value of surface amount of functional sustained-release liquid), B (magnitude of change in surface amount of functional sustained-release liquid due to repeated washing). [Table 4]

[0111] [Example 22] A porous coordination polymer ("Al-PCP-F") consisting of aluminum ions (oxidation number 3, ionic radius 54 pm) as metal ions and fumaric acid as organic ligands, with a BET specific surface area of ​​900 m 2 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 21, except that a polypropylene resin having a molecular weight of 1.0001 to 1.0001 mm (average pore size: 0.6 nm) was used. The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin), the content of the functional sustained-release liquid (5-heptyloxolan-2-one), and the content of the carrier (porous coordination polymer) were as shown in Table 4. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 22.

[0112] [Example 23] A porous coordination polymer (Fe-BTC) consisting of iron ions (oxidation number 3, ionic radius 55 pm) as metal ions and trimesic acid as organic ligands, with a BET specific surface area of ​​1,754 m 2 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 21, except that a polypropylene resin having a molecular weight of 1.0001 to 1.0001 mm (average pore size: 2.4-2.9 nm) was used. The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin), the content of the functional sustained-release liquid (5-heptyloxolan-2-one), and the content of the carrier (porous coordination polymer) were as shown in Table 4. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 23.

[0113] [Example 24] A porous coordination polymer ("MIL-101", surface area measured by BET method: 2,200 m) consisting of chromium ions (oxidation number 3, ionic radius 63 pm) as metal ions and terephthalic acid as organic ligands. 2 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 21, except that a polypropylene resin having a molecular weight of 1.0001 to 1.0001 (wt. / g, average pore size: 2.0 to 2.7 nm) was used. The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin), the content of the functional sustained-release liquid (5-heptyloxolan-2-one), and the content of the carrier (porous coordination polymer) were as shown in Table 4. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 24.

[0114] [Example 25] A porous coordination polymer (MOF-74-Ni) consisting of nickel ions (oxidation number 1, ionic radius 68 pm) as metal ions and 2,5-dihydroxyterephthalic acid as organic ligands, with a BET surface area of ​​1,360 m 2A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 21, except that a polypropylene resin having a molecular weight of 1.0001 to 1.0001 (wt. / g, average pore size: 1.0 nm) was used. The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin), the content of the functional sustained-release liquid (5-heptyloxolan-2-one), and the content of the carrier (porous coordination polymer) were as shown in Table 4. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 25.

[0115] [Example 26] A porous coordination polymer (Uio-66) consisting of a zirconium ion (oxidation number 4, ionic radius 72 pm) as the metal ion and terephthalic acid as the organic ligand, with a BET surface area of ​​1,000 m 2 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 21, except that a polypropylene resin having a molecular weight of 1.0001 to 1.0001 (wt. / g, average pore size: 0.9 nm) was used. The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin), the content of the functional sustained-release liquid (5-heptyloxolan-2-one), and the content of the carrier (porous coordination polymer) were as shown in Table 4. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 26.

[0116] [Example 27] A porous coordination polymer (Cu-BTC) consisting of copper ions (oxidation number 2, ionic radius 73 pm) as metal ions and trimesic acid as organic ligands, with a BET surface area of ​​1,500 m 2 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 21, except that a polypropylene resin having a molecular weight of 1.0001 to 1.0001 (wt. / g, average pore size: 0.9 nm) was used. The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin), the content of the functional sustained-release liquid (5-heptyloxolan-2-one), and the content of the carrier (porous coordination polymer) were as shown in Table 4. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 27.

[0117] [Example 28] A porous coordination polymer ("ZIF-8"; BET surface area: 1,400 m2) consisting of zinc ions (oxidation number 2, ionic radius 74 pm) as metal ions and 2-methylimidazole as organic ligands. 2 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 21, except that a polypropylene resin having a molecular weight of 1.0001 to 1.0001 (wt. / g, average pore size: 0.3 to 1.1 nm) was used. The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin), the content of the functional sustained-release liquid (5-heptyloxolan-2-one), and the content of the carrier (porous coordination polymer) were as shown in Table 4. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 28.

[0120] [Example 31] The functional sustained-release liquid was chlorpyrifos (melting point 41°C, boiling point 160°C, molecular weight 350.58, acid dissociation constant -5.28, Fujifilm Wako Pure Chemical Industries, Ltd.), the porous material was sodium ion (oxidation number 1, ionic radius 103 pm) as metal ion, and the ligand was zeolite composed of aluminosilicate (Union Showa's "USKY-790", surface area by BET method: 792 m). 2 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 21, except that a polypropylene resin having a molecular weight of 1.0001 to 1.0001 mm (average pore size: 0.5 nm) was used. The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin), the content of the functional sustained-release liquid (chlorpyrifos), and the content of the carrier (porous coordination polymer) were as shown in Table 5 below. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 31.

[0121] Regarding Table 5 below. *Exponential function formula: y (surface amount of functional sustained-release liquid), x (number of repeated washings), A (initial value of surface amount of functional sustained-release liquid), B (magnitude of change in surface amount of functional sustained-release liquid due to repeated washing). [Table 5]

[0122] [Example 32] A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 31, except that a silver ion (oxidation number 1, ionic radius 115 pm) was used as the metal ion, and a porous coordination polymer ("Ag-PCP") composed of di-p-xylylene was used as the ligand. The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin), the content of the functional sustained-release liquid (chlorpyrifos), and the content of the carrier (porous coordination polymer) were as shown in Table 5. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated as Example 32.

[0124] Regarding Table 6 below. *Exponential function formula: y (surface amount of functional sustained-release liquid), x (number of repeated washings), A (initial value of surface amount of functional sustained-release liquid), B (magnitude of change in surface amount of functional sustained-release liquid due to repeated washing). [Table 6]

[0127] [Example 36] Dimethyl sulfoxide (melting point 19°C, boiling point 189°C, molecular weight 78.13, acid dissociation constant 33, Fujifilm Wako Pure Chemical product) as a functional sustained-release liquid; A porous coordination polymer ("MIL-101", surface area measured by BET method: 2,200 m) consisting of chromium ions (oxidation number 3, ionic radius 63 pm) as metal ions and terephthalic acid as organic ligands. 2 / g, average pore size: 2.0 to 2.7 nm) was used in the examples. 31 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 3. The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin), the content of the functional sustained-release liquid (dimethyl sulfoxide), and the content of the carrier (porous coordination polymer) were as shown in Table 6. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 36.

[0128] [Example 37] Dimethyl sulfoxide (melting point 19°C, boiling point 189°C, molecular weight 78.13, acid dissociation constant 33, Fujifilm Wako Pure Chemical product) as a functional sustained-release liquid;A porous coordination polymer (MOF-74-Ni) consisting of nickel ions (oxidation number 1, ionic radius 68 pm) as metal ions and 2,5-dihydroxyterephthalic acid as organic ligands, with a BET surface area of ​​1,360 m 2 / g, average pore size: 1.0 nm) was used in the examples. 31 A functional sustained-release composition (molded body material) was prepared in the same manner as in Example 3. The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin), the content of the functional sustained-release liquid (dimethyl sulfoxide), and the content of the carrier (porous coordination polymer) were as shown in Table 6. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 1, and this was designated Example 37.

[0129] [Comparative Example 1-1] The etofenprox used in Example 1 as the functional sustained-release liquid was compounded and mixed with a polyethylene resin (LDPE not modified with polar groups or functional groups) as the matrix resin to prepare a composition (molded body material). The amount of polyethylene resin was set so that the content of the matrix resin (polyethylene resin) and the content of the functional sustained-release liquid were as shown in Table 1 above. The compound processing method used was the same as that described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 1.

[0130] [Comparative Example 1-2] The etofenprox used in Example 1 was used as the functional sustained-release liquid, and the metal ion was sodium ion (oxidation number 1, ionic radius 103 pm) and the ligand was zeolite composed of aluminosilicate (Union Showa's "USKY-790", surface area by BET method: 792 m 2 / g, average pore size: 0.5 nm) was compounded and mixed with polyethylene resin (LDPE with no polar or functional group modification) as a matrix resin to prepare a composition (molded body material). The amount of polyethylene resin blended was set so that the content of the matrix resin (polyethylene resin), the content of the functional sustained-release liquid (etofenprox), and the content of the porous body (porous coordination polymer) were as shown in Table 1 above. The compound processing method was the same as that described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 1-2.

[0131] [Comparative Example 1-3] The etofenprox used in Example 1 as the functional sustained-release liquid was compounded and mixed with a porous coordination polymer ("Ag-PCP") consisting of silver ions (oxidation number 1, ionic radius 115 pm) as the metal ion and di-p-xylylene as the ligand, and a polyethylene resin (LDPE without polar group or functional group modification) as the matrix resin to prepare a composition (molded body material). The amount of polyethylene resin blended was set so that the content of the matrix resin (polyethylene resin), the content of the functional sustained-release liquid (etofenprox), and the content of the porous body (porous coordination polymer) were as shown in Table 1 above. The compound processing method used was the same as that described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 1-3.

[0132] [Comparative Example 2-1] The 2-n-octyl-4-isothiazolin-3-one used in Example 9 as the functional sustained-release liquid was compounded and mixed with an ethylene vinyl acetate resin (Asahi Kasei's "Suntech EM6415") as the matrix resin to prepare a composition (molded body material). The amount of ethylene vinyl acetate resin was set so that the content of the matrix resin (vinyl acetate resin) and the content of the functional sustained-release liquid were as shown in Table 2 above. The compound processing method used was the same as that described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 2-1.

[0133] [Comparative Example 2-2] The functional sustained-release liquid was 2-n-octyl-4-isothiazolin-3-one, which was used in Example 9, and the metal ion was magnesium ion (oxidation number 2, ionic radius 45 pm), and the organic ligand was 2,5-dihydroxyterephthalic acid. The porous coordination polymer ("MOF-74-Mg", specific surface area by BET method: 1,200 m2) was used. 2 / g, average pore size: 1.1 nm) was compounded and mixed with ethylene vinyl acetate resin (Asahi Kasei product "Suntech EM6415") as a matrix resin to prepare a composition (molded body material). The amount of ethylene vinyl acetate resin was set so that the content of the matrix resin (vinyl acetate resin), the content of the functional sustained-release liquid (2-n-octyl-4-isothiazolin-3-one), and the content of the porous body (porous coordination polymer) were as shown in Table 2 above. The compound processing method used was the method described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 2-2.

[0134] [Comparative Example 2-3] The functional sustained-release liquid was 2-n-octyl-4-isothiazolin-3-one used in Example 9, which was mixed with a porous coordination polymer ("Al-PCP-F", specific surface area by BET method: 900 m2) consisting of aluminum ion (oxidation number 3, ionic radius 54 pm) as metal ion and fumaric acid as organic ligand. 2 / g, average pore size: 0.6 nm) was compounded and mixed with ethylene vinyl acetate resin (Asahi Kasei product "Suntech EM6415") as a matrix resin to prepare a composition (molded body material). The amount of ethylene vinyl acetate resin was set so that the content of the matrix resin (vinyl acetate resin), the content of the functional sustained-release liquid (2-n-octyl-4-isothiazolin-3-one), and the content of the porous body (porous coordination polymer) were as shown in Table 2 above. The compound processing method was the same as that described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 2-3.

[0135] [Comparative Example 2-4] The functional sustained-release liquid was 2-n-octyl-4-isothiazolin-3-one, which was used in Example 9, and the metal ion was iron ion (oxidation number 3, ionic radius 55 pm), and the organic ligand was trimesic acid. The porous coordination polymer (Fe-BTC, specific surface area by BET method: 1,754 m2) was used. 2 / g, average pore size: 2.4-2.9 nm) was compounded and mixed with ethylene vinyl acetate resin (Asahi Kasei product "Suntech EM6415") as a matrix resin to prepare a composition (molded body material). The amount of ethylene vinyl acetate resin was set so that the content of the matrix resin (vinyl acetate resin), the content of the functional sustained-release liquid (2-n-octyl-4-isothiazolin-3-one), and the content of the porous body (porous coordination polymer) were as shown in Table 2 above. The compound processing method used was the same as that described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 2-4.

[0136] [Comparative Example 2-5] The functional sustained-release liquid was 2-n-octyl-4-isothiazolin-3-one, which was used in Example 9, and the metal ion was chromium ion (oxidation number 3, ionic radius 63 pm), and the organic ligand was terephthalic acid. The porous coordination polymer ("MIL-101(Cr)", surface area by BET method: 2,200 m 2 / g, average pore size: 2.0-2.7 nm) was compounded and mixed with ethylene vinyl acetate resin (Asahi Kasei product "Suntech EM6415") as a matrix resin to prepare a composition (molded body material). The amount of ethylene vinyl acetate resin was set so that the content of the matrix resin (vinyl acetate resin), the content of the functional sustained-release liquid (2-n-octyl-4-isothiazolin-3-one), and the content of the porous body (porous coordination polymer) were as shown in Table 2 above. The compound processing method was the same as that described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 2-5.

[0137] [Comparative Example 3-1] The methyl anthranilate used in Example 15 as the functional sustained-release liquid was compounded and mixed with polypropylene resin (Prime Polymer product "Prime Polypro J105G") as the matrix resin to prepare a composition (molded body material). The amount of polypropylene resin blended was set so that the content of the matrix resin (polypropylene resin) and the content of the functional sustained-release liquid were as shown in Table 3 above. The compound processing method used was the same as that described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 3-1.

[0138] [Comparative Example 3-2] The functional sustained-release liquid was methyl anthranilate, as used in Example 15, and the metal ion was magnesium ion (oxidation number 2, ionic radius 45 pm), and the organic ligand was 2,5-dihydroxyterephthalic acid. The porous coordination polymer ("MOF-74-Mg", specific surface area by BET method: 1,200 m2) was used. 2 / g, average pore size: 1.1 nm) was compounded and mixed with polypropylene resin (Prime Polymer product "Prime Polypro J105G") as a matrix resin to prepare a composition (molded body material). The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene), the content of the functional sustained-release liquid (methyl anthranilate), and the content of the porous body (porous coordination polymer) were as shown in Table 3 above. The compound processing method was the same as that described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 3-2.

[0139] [Comparative Example 3-3] Methyl anthranilate, which was used as the functional sustained-release liquid in Example 15, was mixed with a porous coordination polymer ("Al-PCP-F", specific surface area by BET method: 900 m2) consisting of aluminum ion (oxidation number 3, ionic radius 54 pm) as metal ion and fumaric acid as organic ligand. 2 / g, average pore size: 0.6 nm) was compounded and mixed with polypropylene resin (Prime Polymer product "Prime Polypro J105G") as a matrix resin to prepare a composition (molded body material). The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene), the content of the functional sustained-release liquid (methyl anthranilate), and the content of the porous body (porous coordination polymer) were as shown in Table 3 above. The compound processing method used was the method described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 3-3.

[0140] [Comparative Example 3-4] The functional sustained-release liquid was methyl anthranilate, as used in Example 15, and the metal ion was iron ion (oxidation number 3, ionic radius 55 pm), and the organic ligand was trimesic acid. The porous coordination polymer (Fe-BTC, specific surface area by BET method: 1,754 m2) was used. 2 / g, average pore size: 2.4-2.9 nm) was compounded and mixed with polypropylene resin (Prime Polymer product "Prime Polypro J105G") as a matrix resin to prepare a composition (molded body material). The amount of polypropylene resin blended was set so that the content of the matrix resin (polypropylene), the content of the functional sustained-release liquid (methyl anthranilate), and the content of the porous body (porous coordination polymer) were as shown in Table 3 above. The compound processing method was the same as that described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 3-4.

[0142] [Comparative Example 4] The 5-heptyloxolane-2-one used in Example 21 as the functional sustained-release liquid was compounded and mixed with polypropylene resin (Prime Polypro J105G, a Prime Polymer product) as the matrix resin to prepare a composition (molded body material). The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin) and the content of the functional sustained-release liquid were as shown in Table 4 above. The compound processing method was the same as that described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 4.

[0143] [Comparative Example 5-1] Chlorpyrifos used in Example 31 as a functional sustained-release liquid was compounded and mixed with polypropylene resin (Prime Polymer product "Prime Polypro J105G") as a matrix resin to prepare a composition (molded body material). The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin) and the content of the functional sustained-release liquid were as shown in Table 5 above. The compounding method used was the same as that described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 5-1.

[0144] [Comparative Example 5-2] The functional sustained-release liquid was chlorpyrifos, which was used in Example 31, and the porous coordination polymer ("MOF-74-Mg", specific surface area by BET method: 1,200 m2) composed of magnesium ions (oxidation number 2, ionic radius 45 pm) as metal ions and 2,5-dihydroxyterephthalic acid as organic ligands was used. 2 / g, average pore size: 1.1 nm) was compounded and mixed with polypropylene resin (Prime Polymer product "Prime Polypro J105G") as a matrix resin to prepare a composition (molded body material). The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene), the content of the functional sustained-release liquid (chlorpyrifos), and the content of the porous body (porous coordination polymer) were as shown in Table 5 above. The compound processing method was the same as that described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 5-2.

[0145] [Comparative Example 5-3] The chlorpyrifos used in Example 31 as the functional sustained-release liquid was mixed with a porous coordination polymer ("Al-PCP-F", specific surface area by BET method: 900 m2) composed of aluminum ion (oxidation number 3, ionic radius 54 pm) as the metal ion and fumaric acid as the organic ligand. 2 / g, average pore size: 0.6 nm) was compounded and mixed with polypropylene resin (Prime Polymer product "Prime Polypro J105G") as a matrix resin to prepare a composition (molded body material). The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene), the content of the functional sustained-release liquid (chlorpyrifos), and the content of the porous body (porous coordination polymer) were as shown in Table 5 above. The compound processing method was the same as that described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 5-3.

[0146] [Comparative Example 5-4] The functional sustained-release liquid was prepared by dissolving chlorpyrifos, which was used in Example 31, in a porous coordination polymer (Fe-BTC, specific surface area by BET method: 1,754 m2) composed of iron ions (oxidation number 3, ionic radius 55 pm) as metal ions and trimesic acid as organic ligands. 2 / g, average pore size: 2.4-2.9 nm) was compounded and mixed with polypropylene resin (Prime Polymer product "Prime Polypro J105G") as a matrix resin to prepare a composition (molded body material). The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene), the content of the functional sustained-release liquid (chlorpyrifos), and the content of the porous body (porous coordination polymer) were as shown in Table 5 above. The compound processing method was the same as that described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 5-4.

[0147] [Comparative Example 5-5] The functional sustained-release liquid was prepared by dissolving chlorpyrifos, which was used in Example 31, in a porous coordination polymer ("MIL-101(Cr)" consisting of chromium ions (oxidation number 3, ionic radius 63 pm) as metal ions and terephthalic acid as organic ligands (surface area measured by BET method: 2,200 m). 2 / g, average pore size: 2.0-2.7 nm) was compounded and mixed with polypropylene resin (Prime Polymer product "Prime Polypro J105G") as a matrix resin to prepare a composition (molded body material). The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene), the content of the functional sustained-release liquid (chlorpyrifos), and the content of the porous body (porous coordination polymer) were as shown in Table 5 above. The compound processing method was the same as that described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 5-5.

[0148] [Comparative Example 5-6] The functional sustained-release liquid was the chlorpyrifos used in Example 31, and the metal ion was a nickel ion (oxidation number 1, ionic radius 68 pm), while the organic ligand was a porous coordination polymer ("MOF-74-Ni", surface area measured by BET method: 1,360 m2) composed of 2,5-dihydroxyterephthalic acid. 2 / g, average pore size: 1.0 nm) was compounded and mixed with polypropylene resin (Prime Polymer product "Prime Polypro J105G") as a matrix resin to prepare a composition (molded body material). The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene), the content of the functional sustained-release liquid (chlorpyrifos), and the content of the porous body (porous coordination polymer) were as shown in Table 5 above. The compound processing method was the same as that described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 5-6.

[0152] [Comparative Example 6-1] As a functional sustained release liquid Teji Methyl sulfoxide was compounded and mixed with polypropylene resin (Prime Polymer product "Prime Polypro J105G") as a matrix resin to prepare a composition (molded body material). The amount of polypropylene resin was set so that the content of the matrix resin (polypropylene resin) and the content of the functional sustained-release liquid were as shown in Table 6 above. The compound processing method was the same as that described in Example 1. The mixed green body material was formed into a plate-like green body having a size of 50×50 mm and a thickness of 1.2 mm, which was designated as Comparative Example 6-1.

[0156] (Evaluation of liquid sustained release properties) The functional sustained release properties of the prepared samples of the examples and comparative examples were evaluated by the following method. First, each sample (molded body) was immersed in 50 mL of tetrahydrofuran in a 20°C environment, and the functional sustained release liquid precipitated on the surface was washed off. Next, the concentration of the functional sustained release liquid component in the washed liquid was measured using high performance liquid chromatography, and the surface amount per unit area of ​​the sample (unit: μg / cm 2 This was measured 10 times, once every 24 hours.

[0157] The evaluation results are shown in Tables 1 to 6. The exponential function formulas shown in Tables 1 to 6 are shown in FIG. 52 This is an approximation of the graph of the surface area of ​​the functional sustained release composite molded body against the number of repeated washings as shown in the figure. The exponential function formula y = Ae -Bx In the formula, y is the surface amount of the functional sustained-release liquid, x is the number of repeated washings, A is the initial value of the surface amount of the functional sustained-release liquid, and the power index B is the magnitude of change in the surface amount of the functional sustained-release liquid due to repeated washing. The larger the power index, the larger the change in the surface amount due to repeated washing, and the less stable the release rate from the resin. Therefore, in order to stabilize the sustained release of the functional sustained-release liquid, it is desirable to have a smaller power index. Therefore, the power index was used as an index of the sustained release of the liquid.

[0158] In order to find a functional sustained-release material with more stable sustained release than when the functional sustained-release liquid is kneaded into the base material alone (Comparative Examples 1 to 6), the ratio of the power index value of the approximation formula when the functional sustained-release liquid is kneaded into the base material alone (Comparative Examples 1 to 6) was calculated for each functional sustained-release liquid component in each Example. The upper limit for pass / fail judgment that can maintain excellent sustained release effect for a long period of time was set to 0.90, and the lower limit was set to 0.1 because sustained release cannot be obtained if the power index value ratio is too low. Therefore, the pass range of the power index ratio was set to 0.10 to 0.90.

[0159] From the results obtained, we thoroughly examined the physical properties of the functional sustained-release liquid and the porous body, and found the following relationship to the exponent ratio. First, the relationship between the power exponent ratio of each example and the metal ion radius of the porous body is shown in FIG. 53 ~FIG. 58 . As is clear from FIGS. 53 ~FIG. 58 , it was found that in any of the examples, the power exponent ratio and the metal ion radius of the porous body showed a strong correlation with a determination coefficient of 0.90 or more for each functional sustained-release liquid. Therefore, the power exponent can be expressed by the following approximate formula. Approximate formula for power exponent ratio; Y = C×R + D ··· Formula 4 However, in Formula 4, R represents the metal ion radius, C represents the slope, and D represents the intercept. Furthermore, regarding the slope C and intercept D of the linear approximation formula shown in FIGS. 53 ~FIG. 58 , the relationship with the acid dissociation constant of each functional sustained-release liquid is shown in FIGS. 59 and 60 respectively. These relationships each showed a high correlation with a determination coefficient of 0.90 or more for the linear approximation formula. C = 0.0013α - 0.079 ··· Formula 5 D = -0.1082α + 1.436 ··· Formula 6 However, in Formulas 5 and 6, α represents the acid dissociation constant of the functional sustained-release liquid. Therefore, since the acceptable range of the power exponent ratio is from 0.10 to 0.90, the power exponent ratio can be arranged as follows in terms of the acid dissociation constant α and metal ion radius R of the functional sustained-release liquid. 0.10 < Y = C×R + D < 0.90 ··· Formula 7 0.10 < (0.0013α - 0.0079)R + (-0.1082α + 1.436) < 0.90 ··· Formula 8 JPEG0007671484000014.jpg12170

[0160] From the above Formula 1, the range of the acid dissociation constant and metal ion radius that gives excellent sustained release is shown (FIG. 61 ). The range where excellent sustained release can be obtained is the shaded part in FIG. 61 . It can be seen that all the plots shown in the part outside the shaded part have a power exponent ratio exceeding 0.90 or less than 0.10, which is an inappropriate combination. Therefore, in order to maintain an excellent sustained-release effect for a long period of time, it is necessary to make the acid dissociation constant of the functional sustained-release liquid and the metal ion radius of the porous body satisfy formula 1. [Industrial Applicability]

[0161] The functional sustained release composition of this embodiment can be used for a molded article imparted with functional components such as a small animal control function, a sliding function, an antibacterial function, an antifungal function, a self-repair function, a catalytic function, a medical function, etc. Specifically, the functional sustained release composite molded article of this embodiment can be used in the industrial field such as automobiles and electrical products, the amenity field such as sanitation services, and the pharmaceutical field.

Claims

1. A functional sustained-release composition comprising a functional sustained-release liquid and a porous body having metal ions, wherein when the acid dissociation constant α of the functional sustained-release liquid is greater than 0.0079 / 0.0013, the radius R (pm) of the metal ion satisfies the range of the following formula 1, and when α is less than 0.0079 / 0.0013, the radius R (pm) of the metal ion satisfies the range of the following formula 2: The functional sustained-release composition is used so as to be contained in a molded product containing a matrix resin containing one or more selected from the group consisting of thermoplastic resins and thermosetting resins, The metal ion has at least one of an alkali metal, an alkaline earth metal, and a transition metal; the metal ion includes at least one selected from the group consisting of silver ions, beryllium ions, calcium ions, cadmium ions, cerium ions, cobalt ions, dysprosium ions, erbium ions, europium ions, gallium ions, gadolinium ions, holmium ions, indium ions, lithium ions, magnesium ions, manganese ions, molybdenum ions, neodymium ions, nickel ions, scandium ions, samarium ions, terbium ions, thulium ions, vanadium ions, tungsten ions, yttrium ions, ytterbium ions, and zirconium ions; the radius R of the metal ion is within the range of 45×10 −12 m to 115×10 −12 m; The functional sustained-release composition, wherein the functional sustained-release liquid has an acid dissociation constant α in the range of −5.28 to 33.

2. A functional sustained-release composition comprising a functional sustained-release liquid and a porous body having metal ions, wherein when the acid dissociation constant α of the functional sustained-release liquid is greater than 0.0079 / 0.0013, the radius R (pm) of the metal ion satisfies the range of the following formula 1, and when α is less than 0.0079 / 0.0013, the radius R (pm) of the metal ion satisfies the range of the following formula 2: The functional sustained-release composition is used so as to be contained in a molded product containing a matrix resin containing one or more selected from the group consisting of thermoplastic resins and thermosetting resins, the thermoplastic resin is at least one selected from the group consisting of polypropylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polystyrene resin, AS resin, ABS resin, methacrylic resin, polyvinyl alcohol resin, EVA resin, polyamide resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polyethylene terephthalate resin, polybutylene terephthalate resin, fluororesin, polyphenylene sulfide resin, polysulfone resin, polyarylate resin, polyetherimide resin, polyethersulfone resin, polyetherketone resin, liquid crystal polyester resin, thermoplastic polyimide resin, and thermoplastic polyurethane resin; the thermosetting resin is at least one selected from the group consisting of an epoxy resin, an unsaturated polyester resin, a phenol resin, a urea resin, a melamine resin, an alkyd resin, a silicone resin, a polyimide resin, a polyurethane resin, a vinyl ester resin, a diallyl phthalate resin, a furan resin, a polyamino bismaleimide resin, a casein resin, an epoxy acrylate resin, a urethane acrylate resin, a polyurea resin, a benzoxazine resin, an oxetane resin, a xylene resin, a dicyclopentadiene resin, and an episulfide resin; the radius R of the metal ion is within the range of 45×10 −12 m to 115×10 −12 m; A functional sustained-release composition, wherein the functional sustained-release liquid has an acid dissociation constant α in the range of −5.28 to 33.

3. 3. The functional sustained-release composition according to claim 1, wherein the porous body is a porous coordination polymer comprising metal ions and organic ligands.

4. A molded body comprising the functional sustained release composition according to any one of claims 1 to 3 and a matrix resin, wherein the matrix resin comprises at least one selected from the group consisting of thermoplastic resins and thermosetting resins.

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