JP2019218310A - Functional sustained-release composition and molding - Google Patents

Abstract

To provide a functional sustained-release composition that can maintain excellent sustained-release effect for a long time, and a molding.SOLUTION: A functional sustained-release composition has a functional sustained-release liquid, a porous coordination polymer having a metal ion and an organic ligand with a specific surface of 900 m/g or more, and a matrix resin.SELECTED DRAWING: None

Description

  The present invention relates to a functional sustained release composition and a molded article.

  By releasing a predetermined amount of a functional component for a long period of time in a functional component such as small animal control, an improvement in the sustainability of the effect can be expected. As a method for increasing the effect persistence of the small animal control function component, a molded article using a small animal control composite material in which the small animal control function component is developed in a matrix resin has been devised (for example, Patent Documents 1 to 3). The molded articles described in Patent Literatures 1 to 3 gradually release the small animal control function component to the surface of the molded article (hereinafter, referred to as “sustained release”), so that the surface of the molded article that comes into contact with small animals such as insect pests. The small animal control function can be maintained. In order to maintain such sustained release for a long period of time, it is conceivable to increase the amount of the functional component developed in the matrix resin. Increasing the amount of the functional component is effective from the viewpoint of further enhancing the function. As a method of increasing the amount of the functional component, in order to increase the affinity between the functional component and the matrix resin, the functional component is modified with a functional group, the polarity of the matrix resin is increased, or the functional component is made porous. For example, a method of carrying the substance on a body can be mentioned (for example, Patent Document 4).

JP 2001-73886 A JP 2000-212005 A JP 2008-206492 A JP 2012-6868 A

  In order to deploy the liquid functional component to the matrix resin, the functional component is placed in the space of the free volume in the matrix resin, or the functional component is placed in the space between the resin and the space between the resins. It is possible to do. At this time, the higher the affinity between the functional component and the matrix resin is, the easier the functional component is arranged, and a larger amount of the functional component can be developed in the matrix resin.

  However, in order to maintain the shape of the molded body, it is necessary to form a skeleton of the matrix resin, so that the free volume in the matrix resin is limited by the type of the resin, thermal vibration due to temperature, and the like. In addition, even if an attempt is made to spread the resin by the functional component, the distance between the resins must be equal to or less than a predetermined distance in order to maintain the shape of the molded body, and the free volume has an upper limit. There is a limit to increasing the amount. When the matrix resin is a thermoplastic resin, the content of the functional component in the whole molded body is generally limited to about 20% by mass even if the resin is modified by adjusting the polarity of the matrix resin. It is. Therefore, such a molded article cannot maintain the sustained release effect for a long time.

  As the porous body carrying the functional component, zeolite or the like (silica, alumina, molecular sieve, activated carbon, etc.) is usually considered. Such a porous body has a low degree of freedom in controlling the affinity of the surface of the pores with the functional component, and cannot carry many functional components. For this reason, the method of modifying the matrix resin seems to be more effective than the method using a porous body. In addition, there are various functional components, and matrix resins having high affinity with the functional components are different from each other. However, the selection of the matrix resin is limited according to the performance required at the time of use, such as the service temperature, the strength, and the material unit price, and the price. As described above, it is extremely difficult to design a material of a molded article in consideration of affinity with a functional component.

  Therefore, an object of the present invention is to provide a functional sustained-release composition and a molded article capable of maintaining an excellent sustained-release effect over a long period of time.

  The present inventors have conducted intensive studies to solve the above problems, as a result, a specific function sustained-release liquid, and a filler containing a specific porous coordination polymer, when combined with a matrix resin, The obtained sustained-release composition for function has been found to be able to solve the above problems, and has completed the present invention.

That is, the present invention is as follows.
(1)
A functional sustained release composition comprising a functional sustained release liquid, a porous coordination polymer having a metal ion and an organic ligand, a specific surface area of at least 900 m ² / g, and a matrix resin.
(2)
The functional sustained release composition according to (1), wherein the functional sustained release liquid has a molecular weight of 600 or less and a melting point of 10 ° C. or more.
(3)
(1) or (2), wherein the average pore diameter of the porous coordination polymer is not less than the molecular diameter of the sustained release liquid.
(4)
The sustained-release composition according to any one of (1) to (3), wherein the surface concentration of the liquid component when compressed at 10 MPa or more is less than 1.0 mg / cm ² .
(5)
A molded article of the functional sustained release composition according to any one of (1) to (4).

  ADVANTAGE OF THE INVENTION According to this invention, the functional sustained-release composition and molded object which can maintain the excellent sustained-release effect over a long period of time can be provided.

It is a figure in Examples 1-4 and 21 which shows the relationship between the content density | concentration of the function sustained release liquid in a function sustained release composite molded object, and the surface quantity of a function sustained release composite molded object. It is a figure in Examples 5-8 which shows the relationship between the content density | concentration of the function sustained release liquid in a function sustained release composite molded object, and the surface quantity of a function sustained release composite molded object. It is a figure in Examples 9-12 which shows the relationship between the content density | concentration of the function sustained release liquid in a function sustained release composite molded object, and the surface quantity of a function sustained release composite molded object. It is a figure in Examples 13-16 which shows the relationship between the content density | concentration of the function sustained release liquid in a function sustained release composite molded object, and the surface quantity of a function sustained release composite molded object. It is a figure in Examples 17-20 which shows the relationship between the content density | concentration of the function sustained release liquid in a function sustained release composite molded object, and the surface quantity of a function sustained release composite molded object. It is a figure in Comparative Examples 1-5 which shows the relationship between the content density | concentration of the function sustained release liquid in a function sustained release composite molded object, and the surface quantity of a function sustained release composite molded object.

  Hereinafter, a mode for carrying out 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 exemplification for describing the present invention, and the present invention is not limited to only the embodiment.

[Functional controlled release composition]
The sustained-release composition of this embodiment comprises a sustained-release liquid, a porous coordination polymer having a metal ion and an organic ligand, and having a specific surface area of 900 m ² / g or more, and a matrix resin. And The functional sustained release composition of the present embodiment can maintain an excellent sustained release effect over a long period of time by combining a functional sustained release liquid, a porous coordination polymer, and a matrix resin. For this reason, the sustained-release composition of this embodiment has advantages such as improvement of product performance and cost reduction by reducing maintenance frequency.

(Functionally controlled release liquid)
The term “functional sustained release” in a functional sustained release liquid includes, for example, a function of controlling small animals, a function of controlling plant growth, an antibacterial function, an antifungal function, a function of imparting plasticity to resin, a sliding function, and a self-control function. It has a function such as a repair function, a catalytic function, and a medical function, and has a sustained release property. The function sustained release liquid may be a liquid component having a function sustained release property, or may be a liquid form of a solid component having a function sustained release property. May be liquefied by dissolving in water.

  Examples of the functional liquid having a small animal control function include, for example, various agricultural pests, sanitary pests and other insects, spiders, mites, drugs having a controlling activity for small animals such as rats, or liquids obtained by dissolving a drug in a solvent. (Hereinafter, also referred to as "small animal control agent"), for example, a compound having small animal repellent activity, a compound having small animal activity such as insecticidal activity, acaricidal activity, spidericidal activity or rodenticidal activity. And compounds having an activity of inhibiting the feeding of small animals, and compounds having an activity of controlling the growth of small animals.

  Specific examples of small animal control agents include metadiamide-based insecticides such as brofuranilide, piperidine-based insecticides such as Icarizine, chloronicotinyl-based insecticides such as imidacloprid, compounds consisting of silicon-containing neophyl radicals such as silafluofen, benflacarb , Alanicarb, methoxydiazone, carbosphan, fenobcarb, carbaryl, mesomil, propoxer, carbamate compounds such as phenoxycarb, pyrethrin, allethrin, dl, d-T80-allethrin, d-T80-resmethrin, bioarethrin, d-T80 -Phthalthrine, phthalthrine, resmethrin, framethrin, propasulin, permethrin, acrinatrine, etofenprox, tralomethrin, phenothrin, d-phenothrin, Pyrethroid compounds such as valerate, empentrin, prarethrin, tefluthrin, benfluthrin, transfluthrin, and metofluthrin, dichlorobos, fenitrothion, diazinon, marathon, promofos, fenthion, trichlorfon, naled, temefos, fenclophos, chlorpyrifosmethyl, aciaphos, meclophos , Pyridafenthion, propetanphos, chlorpyrifos and the like, and isomers, derivatives and analogs thereof. Examples of the compound having small animal growth control activity include methoprene, pyriproxyfen, quinoprene, hydroprene, deohenolan, NC-170, flufenoloxuron, diflubenzuron, lufenuron, chlorazuron, and the like. Compounds having a pesticidal activity include, for example, quercene, chlorfenavir, debufenpyradopyridabene, milbemectin, acaricides such as fenpyroximate, silyloside, norbomide, zinc arsenide, thallium sulfate, noble, antu, warfarin, And rodenticides such as endside, coumarin, coumatetralin, promadiolone, and diffetialone. Examples of small animal control agents include hinokitiol contained in Japanese cypress, asunaro, hinoki asunaro (Aomori Hiba), etc., casinole derivatives (α-casinol, T-casinol) contained in herbs and hinoki, clove, nutmeg, coriander And geraniol, pinene, caryophyllene, borneol, eugenol, ogisugi, and other known naturally-occurring perfumes having a small animal-controlling property, which are often contained in perfume plants such as cumin. In addition, pheromone agents such as insects having an attraction effect, a communication inhibition effect and the like are used as the small animal control agent. As the pheromone agent, for example, Shin-Etsu Chemical's “Confuser R”, “Confuser AA”, “Confuser N”, “Confuser MM”, “Hamakikon-N”, “Sukashibacon L”, “Sinicon-L”, “ Pheromone agents used for fruit trees such as "Nashihimekon", "Bokutokon-H", "Hetachikon" and "Confuser V", "Yotokon-H", "Yotokon-S", "Konagakon-Plus" of Shin-Etsu Chemical products, Pheromone agent used for vegetables such as "Shin-Etsu Konagakon", pheromone agent used for tea such as "Hamakikon-N" manufactured by Shin-Etsu Chemical, "Ochimeric Con", "Yotokon-I", "Kebukakon" manufactured by Shin-Etsu Chemical And pheromone agents used for sugarcane.

  Further, the small animal control agent may be a wasp repellent, and the wasp repellent contains, for example, a compound represented by the following general formula (I) as an active ingredient.

In the formula (I), R ¹ represents a hydrogen atom, a C _1-4 alkyl group _optionally having a substituent β, a C _2-4 alkenyl group _optionally having a substituent β, or a substituent represents a C _1-4 alkyl-carbonyl group _optionally having β, X is a C _1-4 alkylene group optionally having a substituent γ, or optionally having a substituent γ Represents a C _2-4 alkenylene group, α is a C _1-4 alkyl group optionally having a substituent δ, a C _2-4 alkenyl group optionally having a substituent δ, a substituent δ C _1-4 alkoxy group which may have a C _1-4 alkyl-carbonyl group which may have a substituent δ, C _1-4 alkyl-carbonyloxy which may have a substituent δ And represents one or more substituents selected from a group, a halogeno group and a hydroxyl group. Substituents β, γ and δ are each independently selected from the group consisting of C _1-4 alkoxy, C _1-4 alkyl-carbonyl, C _1-4 alkyl-carbonyloxy, halogeno and hydroxyl. And n represents an integer of 0 or more and 5 or less.

  Further specific examples of wasp repellents include, for example, repellents described in JP-A-2017-88548.

  Examples of the sustained-release liquid for controlling 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, naphthaleneacetic acid, zeatin, kinetin, 4-benzylaminobenzimidazole, Natural or synthetic cytokinins such as benzyladenine; gibberellins; brassinosteroids such as brassinolide and castosterone; abscisic acid; These plant hormones are used alone or in combination of two or more.

  Examples of the function sustained-release liquid having an antibacterial function and an antifungal function include a known antibacterial agent having a sustained release property and a fungicide having a sustained release property. Examples of the antibacterial agent and the fungicide include natural organic compounds such as hinokitiol compounds, chitosan compounds, mustard extract compounds, eucalyptus compounds, synthetic organic compounds, and organic complexing agents. These compounds are used alone or in combination of two or more. Among these, synthetic organic compounds are preferred from the viewpoint of effectively acting on both bacteria and mold. Examples of the synthetic organic compound include a nitrogen-containing heterocyclic compound, an aldehyde compound, a phenol compound, a biguanide compound, a nitrile compound, a halogen compound, an anilide compound, a disulfide compound, a thiocarbamate compound, and an organic compound. Examples include silicon quaternary ammonium salt compounds, quaternary ammonium salt compounds, amino acid compounds, organometallic compounds, alcohol compounds, carboxylic acid compounds, ester compounds, thiazoline compounds, and cationic polymers. These synthetic organic compounds are used alone or in combination of two or more.

  Examples of the function sustained-release liquid having a function of imparting plasticity to the resin include a carboxylate derivative, a phosphate derivative, a phosphazene derivative, a carboxylic acid amide derivative, a sulfonic acid ester derivative, and a sulfonamide derivative. . The plasticizer may be used alone or in combination of two or more.

  Examples of the carboxylic acid ester derivative include an alkyl ester of various carboxylic acids which may be substituted with a hydroxyl group, a nitro group, an amino group, an epoxy group, a halogen and the like, and an aromatic ester. Specific examples of the carboxylic acid ester derivative include, for example, dimethyl phthalate, diethyl phthalate, di-n-octyl phthalate, diphenyl phthalate, benzyl phthalate, dimethoxyethyl phthalate, di (2-ethylhexyl) 4,5-epoxyhexahydrophthalate 4,5-epoxycyclohexahydrophthalic acid di (7,8-epoxy-2-octenyl), 4,5-epoxycyclohexahydrophthalic acid di (9,10-epoxyoctadecyl), 4,5-epoxycyclohexyl Phthalate derivatives such as di (10,11-epoxyundecyl) sahydrophthalate, di (tetrahydrofurfuroxyethyl) phthalate, various phthalic acid mixed esters and ethylene oxide adducts of phthalic acid mixed esters, isophthalic acid ester derivatives Tetrahydrophthalic acid ester derivative, butoxyethyl parahydroxybenzoate, cyclohexyloxyethoxyethoxyethyl parahydroxybenzoate, 2-ethylhexyl parahydroxybenzoate, hydroxybenzoic acid ester of ω-alkyl oligoethylene oxide, parahydroxybenzoate of undecyl glycidyl ether Benzoic acid ester derivatives such as acid adducts, propionic acid ester derivatives such as di (tetrahydrofurfuroxyethyl) thiodipropionate, adipic acid ester derivatives, azelaic acid ester derivatives, sebacic acid ester derivatives, dodecane-2-acid ester derivatives , Maleic acid ester derivatives, fumaric acid ester derivatives, trimetic acid ester derivatives, tri (butoxyethoxyethyl) citrate, di-n-octyl citrate Citrate derivatives such as tyl-mono (nonylphenoxyethyl), tri-n-octyl citrate, dioctyl citrate (tetrahydrofurfuroxylethyl), trimyristyl citrate and triethyl citrate, itaconic ester derivatives, tetrahydrofur oleate Oleic acid ester derivatives such as furyl, ricinoleic acid ester derivatives, lactic acid (n-butyl), lactic acid (2-ethylhexyl), lactic acid (n-butoxyethoxyethyl), lactic acid (n-octoxyethoxyethyl), lactic acid (n- Lactate ester derivatives such as decyloxyethoxyethyl), tartaric acid ester derivatives such as di (octoxyethoxyethyl) tartrate, (n-octyl) tartaric acid (nonylphenoxyethyl), di (octoxyethoxyethyl) tartrate, dibutoxy malate ethyl, Examples thereof include malate derivatives such as di (n-butoxyethoxyethyl) malate, distearyl malate and octadecenylisononyl malate, and salicylic acid ester derivatives such as salicylic acid adduct of benzyl glycidyl ether.

  Examples of the phosphate derivative include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri- (2-ethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, and isodecyl. Diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (chloroethyl) phosphate, xyenyl diphenyl phosphate, and tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphate .

  Examples of the phosphazene derivative include a cyclic phosphazene compound represented by the following general formula (1).

In the formula, m represents an integer of 3 to 25, and R ¹ and R ² may be the same or different from each other, and have an alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms. A phenyl group which may be substituted with a group and / or an allyl group; The phosphazene derivative may be composed of one kind of the linear phosphazene compound represented by the formula (1), or may be composed of a mixture of two or more kinds.

  Examples of the phosphazene derivative also include a linear phosphazene compound represented by the following general formula (2).

In the formula, n represents an integer of ³ to 1000, and R ³ and R ⁴ may be the same or different from each other, and have an alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms. represents a group and / or allyl phenyl group which may be substituted with a group, X is a group _{^{-N = P (oR 3) 3}} , group _{^{-N = P (oR 4) 3}} , group -N = P (O ) (OR ³ ) or a group -N = P (O) (OR ⁴ ), and Y represents a group -P (OR ³ ) ₄ , a group -P (OR ⁴ ) ₄ , a group -P (O) (OR ³ ) ₂ or a group -P (O) (OR ⁴ ) ₂ . The phosphazene derivative may be composed of one kind of the linear phosphazene compound represented by the formula (2), or may be composed of a mixture of two or more kinds.

As the phosphazene derivative, an alkyl group is eliminated from R ¹ , R ² , R ³ , and R ^{4 in} the formula (1) or the formula (2) by a crosslinking group represented by the following formula (3), and two oxygens are removed. A phosphazene compound in which atoms are cross-linked may be used.

In the formula, r represents 0 or 1, and A represents a group —SO ₂ —, —S—, —O—, or —C (CH ₃ ) ₂ —.

  Specific examples of the cyclic phosphazene compound represented by the formula (1) include hexaphenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decafenoxycyclopentaphosphazene, hexapropoxycyclotriphosphazene, octapropoxycyclocyclotetraphosphazene, and decapropoxy. And cyclopentaphosphazene. Specific examples of the linear phosphazene compound represented by the formula (2) include a linear phosphazene compound in which a linear dichlorophosphazene is substituted with a propoxy group and / or a phenoxy group. Specific examples of the crosslinked structure represented by the formula (3) include 4,4'-sulfonyldiphenylene (bisphenol-S residue), 4,4'-oxydiphenylene group, and 4,4'-thiodiphenylene And 4,4'-diphenylene groups. These phosphazene derivatives may have an amino group and / or a phenylamino group substituted at an arbitrary position. These phosphazene derivatives may be used alone or in combination of two or more.

  Examples of the carboxylic acid amide derivative include, for example, N-cyclohexylbenzoic acid amide. Examples of the sulfonamide derivative include N-methyl-benzenesulfonamide, N-ethyl-benzenesulfonamide, N-butyl-benzenesulfonamide, N-cyclohexyl-benzenesulfonamide, N-ethyl-P-toluenesulfonamide, N-butyl-toluenesulfonamide and N-cyclohexyl-toluenesulfonamide are exemplified.

  Examples of the sulfonate derivative include ethyl benzenesulfonate.

  Examples of the sulfonamide derivatives include 2-methoxyethyl methanesulfonate, 2,2,2-trifluoroethyl methanesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, and p-toluenesulfonate n -Propyl and the like.

  Examples of the function sustained-release liquid having a sliding function include known sliding agents having a sustained-release property. Known sliding agents include, for example, mineral oil, synthetic oil, wax, paraffin and the like.

  Examples of the function sustained release liquid having a self-healing function include known self-healing agents having a sustained release property. Known self-healing agents include polyrotaxane, self-healing clear (product of Natco Corporation), and the like.

  Examples of the function sustained-release liquid having a catalytic function include known catalysts having a sustained-release property. Known catalysts include ionic liquids, tertiary amines (eg, “PZETA” manufactured by Tosoh Corporation), and organic titanium compounds (eg, tetra-i-propoxytitanium, tetra-n-butoxytitanium, tetrakis (2- Ethylhexyloxine) titanium (for example, a product of Nippon Soda Co., Ltd.) and the like.

  Examples of the function sustained-release liquid having a medical function include known medical products having a sustained-release property.

  The solvent is preferably a solvent having high compatibility with the matrix resin and having little influence on the shape stability of the molded article. Examples of the solvent include water, methanol, ethanol, dimethyl sulfoxide, polyethylene glycol, a sulfonamide derivative, a sulfonate ester derivative, a carboxylic acid amide derivative, a carboxylate ester derivative, a phosphate ester derivative, a hydrocarbon compound, and a silicone compound. No. Examples of the sulfonamide derivative 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 the sulfonic acid ester derivative include 2-methoxyethyl methanesulfonate, 2,2,2-trifluoroethyl methanesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, and p-toluenesulfonic acid n -Propyl and the like. Examples of the carboxylic acid amide derivative include N-cyclohexylbenzoic acid amide. Examples of the carboxylate derivatives include dimethyl phthalate, diethyl phthalate, di-n-octyl phthalate, diphenyl phthalate, benzyl phthalate, dimethoxyethyl phthalate, di (2-ethylhexyl) 4,5-epoxyhexahydrophthalate, 4,4 5-epoxycyclohexahydrophthalic acid di (7,8-epoxy-2-octenyl), 4,5-epoxycyclohexahydrophthalic acid di (9,10-epoxyoctadecyl), 4,5-epoxycyclohexahydrophthalic Acid derivatives such as di (10,11-epoxyundecyl) acid, di (tetrahydrofurfuroxyethyl) phthalate, various phthalic acid mixed esters and ethylene oxide adducts of phthalic acid mixed esters, isophthalic acid ester derivatives, Drophthalic acid ester derivative, butoxyethyl parahydroxybenzoate, cyclohexyloxyethoxyethoxyethyl parahydroxybenzoate, 2-ethylhexyl parahydroxybenzoate, hydroxybenzoic acid ester of ω-alkyl oligoethylene oxide, parahydroxybenzoic acid of undecyl glycidyl ether Benzoic acid ester derivatives such as adducts, propionic acid ester derivatives such as di (tetrahydrofurfuroxyethyl) thiodipropionate, adipic acid ester derivatives, azelaic acid ester derivatives, sebacic acid ester derivatives, dodecane-2-acid ester derivatives, Maleic acid ester derivatives, fumaric acid ester derivatives, trimetic acid ester derivatives, tri (butoxyethoxyethyl) citrate, di-n-octyl citrate-mono Nonylphenoxyethyl), tri-n-octyl citrate, dioctyl citrate (tetrahydrofurfuroxyethyl), citrate derivatives such as trimyristyl citrate and triethyl citrate, itaconate esters, and olein such as tetrahydrofurfuryl oleate Acid ester derivative, ricinoleic acid ester derivative, lactic acid (n-butyl), lactic acid (2-ethylhexyl), lactic acid (n-butoxyethoxyethyl), lactic acid (n-octoxyethoxyethyl), lactic acid (n-decyloxyethoxyethyl) ), Tartrate derivatives such as di (octoxyethoxyethyl) tartrate, (n-octyl) tartaric acid (nonylphenoxyethyl), di (octoxyethoxyethyl) tartrate, dibutoxyethyl malate, malic acid (N- butoxy ethoxyethyl), distearyl malate, malic acid ester derivatives such as malic acid octadecenyl isononyl, salicylic acid ester derivatives of salicylic acid adduct of benzyl glycidyl ether. Examples of the phosphate derivative include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri- (2-ethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, and isodecyl. -Diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (chloroethyl) phosphate, xyenyl diphenyl phosphate, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphate. Examples of the hydrocarbon compound include a chain saturated hydrocarbon compound (paraffins), a chain unsaturated hydrocarbon compound (olefins), an alicyclic hydrocarbon compound (cycloalkane, cycloalkene, cycloalkyne, etc.), And aromatic hydrocarbon compounds. Among these hydrocarbon compounds, paraffin oil having a molecular weight of 330 to 530 and a kinematic viscosity of 10 to 120 cSt is particularly preferably used. A hydrocarbon compound having a molecular weight of 330 to 530 is preferable from the viewpoint of easily penetrating the body of a small animal from the body hole of the small animal. Further, a hydrocarbon compound having a kinematic viscosity of 10 to 120 cSt is preferable from the viewpoint of easily attaching to the body surface of a small animal. Furthermore, it is preferable to use paraffin oil from the viewpoint of being inexpensive and easily available. Examples of the silicone compound include dimethyl silicone, methylphenyl silicone, polyether-modified silicone, long-chain alkyl-modified silicone, and higher fatty acid ester-modified silicone.

  The functional sustained-release liquid preferably has a molecular weight of 600 or less and a melting point of 10 ° C. or more from the viewpoint of the restriction of the processing temperature of the matrix resin.

(Porous coordination polymer)
The porous coordination polymer is a porous material containing a metal ion and an organic ligand. The porous coordination polymer has, for example, a form in which a metal ion is adsorbed on an organic ligand. The organic ligand is, for example, an organic ligand that can bind to a metal ion. The porous coordination polymer is also called MOF (Metal-Organic Framework) or PCP (Porous Coordination Polymer).

  The porous coordination polymer has, for example, a large number of pores in a macropore or mesopore region, and has a uniform pore diameter because the pore diameter (pore diameter) is determined based on the crystal structure. .

The porous coordination polymer can increase the holding power of the functional liquid component and can be finely packed by controlling the affinity depending on the length and chemical structure of the organic ligand. From the same viewpoint, the average pore diameter of the porous coordination polymer is preferably equal to or larger than the molecular diameter of the sustained-release liquid, and the specific surface area of the porous coordination polymer measured by the BET method is 900 m ² / g. or more (e.g., 900 meters ² / g or more 10400m ² / g or less), and preferably at 1000 m ² / g or more, further preferably 1200 m ² / g or more, it is 1500 m ² / g or more Particularly preferred. Further, when the specific surface area by the BET method is 900 m ² / g or more, the porous coordinating polymer is more functional liquid than the case where a functional liquid component is directly kneaded into a matrix resin to form a composite molded body. Can be more effectively developed by the matrix resin. The average pore diameter of the porous coordination polymer is determined by the BET method. In addition, the molecular diameter of the function sustained-release liquid can be determined by the following procedure using open-source “Mol-view”. First, a molecule is drawn, and the major axis and minor axis of the molecule are measured in software. Here, the major axis is the distance between branches of a long part when the molecule is extended linearly, and the minor axis is the distance between branches of a short part when the molecule is similarly extended. Here, the “molecular diameter” corresponds to the minor axis.

  The average pore diameter of the porous coordination polymer is preferably from 0.1 to 5.0 nm, from the viewpoint of enabling the function sustained-release liquid to be effectively developed by the matrix resin and further improving the long-term sustained-release property, More preferably, the thickness is 0.5 to 3.0 nm.

(Metal ions)
Examples of the metal ion include silver, aluminum, beryllium, calcium, cadmium, cerium, cobalt, chromium, copper, dysprosium, erbium, europium, iron, gallium, and gadolinium. Ion, holmium ion, indium ion, lithium ion, magnesium ion, manganese ion, molybdenum ion, neodymium ion, nickel ion, scandium ion, samarium ion, strontium ion, terbium ion, thulium ion, vanadium ion, tungsten ion, yttrium ion , Ytterbium ion, zinc ion, and zirconium ion. These metal ions are 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.

(Organic ligand)
The organic ligand is preferably a cross-linkable ligand capable of cross-linking a metal ion. Examples of the crosslinking ligand include 2-methylimidazole, terephthalic acid, 2,5-dihydroxyterephthalic acid, 1,4-naphthalenedicarboxylic acid, 1,3,5-benzenetricarboxylic acid, and 4,4′-biphenyldicarboxylic acid 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-1,3benzodicarboxylic acid, terephenyl -3,3 ', 5,5'-tetracarboxylic acid, 9,10-anthracenedicarboxylic acid, a Dazole, 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.

  In the method for producing a functional sustained-release composition, the porous coordination polymer is subjected to porous coordination after removing residual substances attached to or present in the surface and / or pores of the porous coordination polymer. It is desirable that the polymer hold a function sustained release liquid. When the residual substance is present, when the porous coordination polymer and the functional liquid are complexed, the pores are narrowed or completely closed by the residual substance, and the functional liquid is transferred to the porous coordination polymer. May be difficult to inject into the fine pores. In addition, since the residual substance is mixed into the functional liquid as an impurity, the physical properties of the function sustained release liquid may change, and the desired effect may not be obtained. Examples of the method for removing the residual substance include a method for washing the porous coordination polymer with a solvent. Examples of the solvent used for washing include water, methanol, THF, and DMF, and the solvent is preferably water and / or methanol. If the solvent is water and / or methanol, the solvent has a small molecular diameter, so that the solvent easily enters the pores of the porous coordination polymer, and the residual substances in the pores can be easily removed. Further, in the step of washing the residual substance, the porous coordination polymer may be immersed in the solvent for a long time. The immersion time is preferably at least 12 hours, more preferably at least 24 hours. As a method for removing unreacted substances or impurities, a method for removing residual substances by heat treatment is given. When the unreacted substance or impurity is an organic substance, and it is desired to remove the organic substance, the heat treatment is preferably performed in air or an oxygen atmosphere. When the unreacted substance or the impurity is a volatile substance and it is desired to remove the volatile substance, it is preferable to perform a vacuum heat treatment. The heating temperature is preferably from 100 to 300 ° C. After washing with a solvent, a method of performing a heat treatment to completely remove the solvent is preferable.

(Matrix resin)
The matrix resin contains one or more resins. Examples of the resin include a thermoplastic resin and a thermosetting resin. As the thermoplastic resin, 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, fluorine resin, polyphenylene sulfide resin, polysulfone resin, polyarylate resin, polyetherimide resin, polyethersulfone resin, polyetherketone resin, liquid crystal polyester Resins, thermoplastic polyimide resins, and thermoplastic polyurethane resins. Examples of the thermosetting resin include epoxy resin, unsaturated polyester resin, phenol resin, urea resin, melamine resin, alkyd resin, silicone resin, polyimide resin, polyurethane resin, vinyl ester resin, diallyl phthalate resin, furan resin, and polyaminobismaleimide. Resins, casein resins, epoxy acrylate resins, urethane acrylate resins, polyurea resins, benzoxazine resins, oxetane resins, xylene resins, dicyclopentadiene resins, and episulfide resins.

  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, 1 It is preferably from 0.5 to 3.0.

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

(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, and examples thereof include a particulate inorganic filler, a fibrous inorganic filler, and a scaly or plate-like inorganic filler. The particulate inorganic filler may be, for example, a micron-sized particulate inorganic filler or a nano-sized particulate inorganic filler. Examples of the particulate inorganic filler having a micron size include, 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, Examples include wollastonite, vermiculite, shirasu balloon, glass balloon and the like. Examples of the nano-sized particulate inorganic filler include nano titanium oxide, nano silica, carbon black, carbon filler and the like. The inorganic filler may be used alone or in combination of two or more. Among them, the particulate inorganic filler is preferably potassium titanate particles from the viewpoint of further improving the sustained release of a function sustained release liquid (particularly, a 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, from the viewpoint of not adversely affecting the appearance of the molded body, More preferably, it is 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. The fibrous inorganic filler may be, for example, a micron-sized fibrous inorganic filler or a nano-sized fibrous inorganic filler. Examples of the fibrous inorganic filler having a micron size include glass fiber, carbon fiber, graphite fiber, aramid fiber, vinylon fiber, polyamide fiber, polyester fiber, cotton, hemp fiber, kenaf fiber, bamboo fiber, rayon, and steel fiber. , Aluminum fiber, gypsum fiber, potassium titanate fiber, potassium hexatitanate fiber, potassium octa titanate fiber, titania fiber, monoclinic titania fiber, silica fiber, wollastonite, zonotolite and the like. Examples of the nano-sized fibrous inorganic filler include carbon fiber, carbon nanotube, fullerene, cotton fibril, silicon nitride whisker, alumina whisker, silicon carbide whisker, nickel whisker, and the like. These fibrous inorganic fillers may be used alone or in combination of two or more. The scaly or plate-like inorganic filler may be, for example, a micron-sized scaly or plate-like inorganic filler, or a nano-sized scaly or plate-like inorganic filler. Examples of the scaly or plate-like inorganic filler having a micron size include talc, kaolin clay, mica (synthetic mica or natural mica), glass flake, aragonite, calcium sulfate, aluminum hydroxide, potassium titanate, potassium titanate Examples include lithium, potassium magnesium titanate, sericite, plate-like alumina, boron nitride, and the like. Examples of the nano-sized scaly or plate-like inorganic filler include organic montmorillonite, swellable synthetic mica, graphite, graphite, and the like. The scaly inorganic filler is used alone or in combination of two or more. The inorganic filler may be used as it is, and from the viewpoint of improving the interfacial adhesion to the resin or further improving the mechanical properties, a silane coupling agent such as aminosilane, epoxysilane, or acrylicsilane or a titanate cup. It may be used in the form of surface treatment with a surface treatment agent such as a ring agent.

(Weather resistance imparting additive)
The functional sustained release composition may contain a weather resistance imparting additive from the viewpoint of further improving the weather resistance when left outdoors. Examples of the weather resistance-imparting additive include one selected from the group consisting of a hindered phenolic antioxidant, a phosphorus-based antioxidant, an ultraviolet light absorbing light stabilizer, a hindered amine light stabilizer, and carbon.

  Examples of hindered phenolic antioxidants include, for example, 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, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propione , 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.

  Examples of the phosphorus-based antioxidant include tris (2,4-di-tert-butylphenyl) phosphite and tris [2-[[2,4,8,10-tetra-tert-butylbenzo [d, f]]. [1,3,2] dioxaphosphefin-6-yl] oxy] ethyl] amine, tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diyl Bisphosphonite, distearylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol phosphite, bis (2,6-di-tert-butyl-4-phenyl) pentaerythritol phosphite And phosphite, and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite.

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

  Examples of the hindered amine light stabilizer include, for example, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethyl) Piperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, poly [(6- (1,1,3,3-tetramethylbutyl) amino-1, 3,5-Triazine-2,4-diyl) (2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino )), Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-dispiro- [5.1. 11.2] -Hen-eicosan-21-one, professional Diacid, [(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.

  The weatherability imparting additive is used alone or in combination of two or more. Among these, the weatherability-imparting 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-hydroxyphenylpropionamito})], 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-butyl) Phenyl) 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- (Nmethyl-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)), 1,3-benzenedicarboxamide, and N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) One or more are preferred.

The functional sustained-release composition of the present embodiment preferably has a surface concentration of the liquid component of less than 1.0 mg / cm ² when compressed at 10 MPa or more. When the surface concentration is 1000 μg / cm ² or more, when processing the functional sustained release composition by injection molding or the like, there is a possibility that a problem such as clogging of material pellets due to stickiness of the surface or the like may occur.

(Application)
The functional sustained-release composition can be used not only after being processed into a molded article having a predetermined shape but also as it is, for example, as a paint, a sealing agent, a cushion material, or a filler. For the function sustained release composition, for example, an appropriate matrix resin is selected, and the amount of the porous coordination polymer to which the function sustained release liquid is adsorbed and the amount of the filler, the plasticizer, etc. are appropriately adjusted. By doing so, a molded article having fluidity, semi-fluidity or rubber-like elasticity can be produced. For this reason, the present invention also includes a molded article molded from the sustained-release composition of the present embodiment. Those having fluidity can be used, for example, as paints, and those having semi-fluidity can be used, for example, as sealing agents. In addition, those having rubber-like elasticity can be used, for example, as cushioning materials and padding. When the functional sustained-release composition is used as a paint, a sealing agent, a cushioning material, or a filling, a coloring material such as a coloring agent or a pigment can be added to the matrix resin as needed. When molding the functional sustained-release composition, for example, injection molding, compression molding, transfer molding, extrusion molding, blow molding, calendar molding, FRP molding, lamination molding, casting molding, solution casting, vacuum / pressure molding An appropriate molding method belonging to the public domain, such as extrusion composite molding, foam molding, thermoforming, insert molding, and melt impregnation, can be applied. There is no particular limitation on the shape of the molded product, which may be any shape such as a flat plate, a rod, a cylinder, a comb, and a sphere. Further, in addition to molding the function sustained release composition alone, molding of two or more colors in combination with a metal or the like can also be performed.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Example 1]
Etofenprox (melting point 37 ° C, boiling point 200 ° C, molecular weight 376.49, molecular diameter (major axis) 1.748 nm, molecular diameter (minor axis) 0.5 nm, Mitsui Chemicals Agro product) as a function sustained release liquid, metal ion And a porous coordination polymer (“HUST-1”, specific surface area by BET method: 2800 m ² / g, average pore diameter: 2.0 to 2.7 nm) composed of chromium ion and terephthalic acid as an organic ligand ) Was used. The sustained-release liquid was adsorbed to the porous coordination polymer so as to have the composition shown in composition A1 in Table 1 below. As an adsorption method, a porous coordinating polymer is placed in a vacuum bell jar, the pressure of the porous coordinating polymer is reduced to 0.01 MPa or less, and etofenprox is dropped in this state. Was used. The porous coordination polymer having adsorbed etofenprox is compounded and mixed with a polyethylene resin (“Novatic UJ310” made by Nippon Polyethylene) as a matrix resin to obtain a functional sustained release composition (molded material). Produced. The content of the polyethylene resin is determined by the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid (etofenprox) and the content of the PCP (porous coordination polymer) in the composition shown in Table 1 below. The amount was as shown in the article A1. In the same manner, compositions A2 to A6 having different contents were prepared.
As a compound processing method, a method of compounding at a processing temperature of 120 ° C. for 10 minutes using a lab plast mill device (manufactured by Toyo Seiki Seisakusho) was used.
Next, using a heating press (“IMC180C” manufactured by Imoto Manufacturing Co., Ltd.), each molded body material was pressed at 120 ° C. for 5 tons to produce a plate-shaped molded body having a size of 50 mm × 50 mm and a thickness of 1.2 mm. This was designated as Example 1.

[Example 2]
A porous coordination polymer (specific surface area by BET method: 1754 m ² / g, average pore diameter: 2.4 to 2.9 nm) composed of iron ion as a metal ion and trimesic acid as an organic ligand was used. Except for the above, a functional sustained-release composition (molded material) was prepared in the same manner as in Example 1. The content of the polyethylene resin is determined by the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid (etofenprox), and the content of the PCP (porous coordination polymer) in the composition shown in Table 2 below. The amount was as shown in the article B1. Similarly, compositions B2 to B7 having the above contents different from each other were produced. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 1, and this was designated as Example 2.

[Example 3]
Example except that a porous coordination polymer (specific surface area by BET method: 2100 m ² / g, average pore diameter: 0.9 nm) composed of copper ion as a metal ion and trimesic acid as an organic ligand was used. In the same manner as in Example 1, a function sustained release composition (molded material) was produced. The content of the polyethylene resin is as follows: the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid (etofenprox), and the content of the PCP (porous coordination polymer) are shown in Table 3 below. The amount was as shown in the object C1. In the same manner, compositions C2 to C6 having different contents were prepared. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 1, and this was designated as Example 3.

[Example 4]
Porous coordination polymer composed of zinc ion as metal ion and 4,4′-biphenyldicarboxylic acid as organic ligand (“UIO-67”, specific surface area by BET method: 1530 m ² / g, average fineness) Except for using a pore size of 0.6 nm), a function sustained release composition (molded material) was prepared in the same manner as in Example 1. The content of the polyethylene resin is determined by the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid (etofenprox), and the content of the PCP (porous coordination polymer) in the composition shown in Table 4 below. The amount was as shown in the article D1. Similarly, compositions D2 to D7 having the above-mentioned different contents were prepared. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 1, and this was designated as Example 4.

[Example 5]
Same as Example 1 except that permethrin (melting point: 34 ° C., boiling point: 200 ° C., molecular weight: 391.29, molecular diameter (major axis): 1.431 nm, molecular diameter (minor axis): 0.5 nm) was used as the sustained-release liquid. Thus, a functional sustained release composition (molded material) was prepared. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition E1 in Table 5 below. Amount. Similarly, compositions E2 to E7 having the above contents different from each other were produced. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 1, and this was designated as Example 5.

[Example 6]
Porous coordination polymer composed of zinc ion as metal ion and 4,4′-biphenyldicarboxylic acid as organic ligand (“UIO-67”, specific surface area by BET method: 1530 m ² / g, average fineness) Except for using (pore diameter: 0.6 nm), a function sustained release composition (molded material) was prepared in the same manner as in Example 5. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition F1 in Table 6 below. Amount. Similarly, compositions F2 to F7 having the above contents different from each other were produced. Thereafter, a molded body was prepared from each molded body material in the same manner as in Example 5, and this was designated as Example 6.

[Example 7]
The function was the same as in Example 1 except that trimellitic acid ester (boiling point: 414 ° C., molecular weight: 547, molecular diameter (major axis): 1.326 nm, molecular diameter (minor axis): 1.304 nm) was used as the sustained-release liquid. A sustained release composition (molded material) was prepared. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition G1 in Table 7 below. Amount. Similarly, compositions G2 to G7 having the above contents different from each other were produced. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 1, and this was designated as Example 7.

Example 8
Zinc ion as the metal ion, and a 4,4'-biphenyl dicarboxylate acid as organic ligand porous coordination polymer ( "UIO-67", a specific surface area by BET method: 1530 m ² / g, an average pore Except for using (pore size: 0.6 nm), a function sustained release composition (molded material) was prepared in the same manner as in Example 7. The content of the polyethylene resin was such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) were as shown in the composition H1 in Table 8 below. Amount. Similarly, compositions H2 to H7 having the above contents different from each other were produced. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 5, and this was designated as Example 8.

[Example 9]
Same as Example 1 except that sulfonic acid amide (boiling point: 314 ° C., molecular weight: 213.3, molecular diameter (major axis): 1.081 nm, molecular diameter (minor axis): 0.5 nm) was used as the function sustained-release liquid. Thus, a functional sustained release composition (molded material) was prepared. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition I1 in Table 9 below. Amount. Similarly, compositions I2 to I7 having the above contents different from each other were produced. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 1, and this was designated as Example 9.

[Example 10]
Porous coordination polymer composed of zinc ion as metal ion and 4,4′-biphenyldicarboxylic acid as organic ligand (“UIO-67”, specific surface area by BET method: 1530 m ² / g, average fineness) Except for using a pore diameter of 0.6 nm), a function sustained release composition (molded material) was prepared in the same manner as in Example 9. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition J1 in Table 10 below. Amount. Similarly, compositions J2 to J7 having the above contents different from each other were produced. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 9, and this was designated as Example 10.

[Example 11]
Except for using methoprene (boiling point: 100 ° C., molecular weight: 310.48, molecular diameter (major axis): 1.426 nm, molecular diameter (minor axis): 0.434 nm) as the functional sustained-release liquid, the same procedure as in Example 1 was repeated. A release composition (molded material) was prepared. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition K1 in Table 11 below. Amount. Similarly, compositions K2 to K7 having the above contents different from each other were produced. 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 11.

[Example 12]
Porous coordination polymer composed of zinc ion as metal ion and 4,4′-biphenyldicarboxylic acid as organic ligand (“UIO-67”, specific surface area by BET method: 1530 m ² / g, average fineness) A functional sustained-release composition (molded material) was prepared in the same manner as in Example 11 except that the pore size was 0.6 nm. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition L1 in Table 12 below. Amount. Similarly, compositions L2 to L7 having the above-mentioned different contents were prepared. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 11, and this was designated as Example 12.

Example 13
Performed with the exception that Olfuralua (boiling point: 300 ° C., molecular weight: 226.36, molecular diameter (major axis): 1.645 nm, molecular diameter (minor axis): 0.18 nm) dissolved in polyethylene glycol was used as the function sustained-release liquid. In the same manner as in Example 1, a function sustained-release composition (molded material) was produced. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition M1 in Table 13 below. Amount. Similarly, compositions M2 to M7 having the above contents different from each other were produced. 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 13.

[Example 14]
Porous coordination polymer composed of zinc ion as metal ion and 4,4′-biphenyldicarboxylic acid as organic ligand (“UIO-67”, specific surface area by BET method: 1530 m ² / g, average fineness) Except for using (pore diameter: 0.6 nm), a function sustained release composition (molded material) was prepared in the same manner as in Example 13. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition N1 in Table 14 below. Amount. Similarly, compositions N2 to N7 having the above-described different contents were prepared. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 13, and this was designated as Example 14.

[Example 15]
Except for using indole triacetic acid (melting point: 168 ° C., molecular weight: 175.18, molecular diameter (major axis): 0.882 nm, molecular diameter (minor axis): 0.5 nm) dissolved in DMSO as a function sustained-release liquid In the same manner as in Example 1, a function sustained release composition (molded material) was produced. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition O1 in Table 15 below. Amount. Similarly, compositions O2 to O7 having the above contents different from each other were produced. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 1, and this was designated as Example 15.

[Example 16]
Porous coordination polymer composed of zinc ion as metal ion and 4,4′-biphenyldicarboxylic acid as organic ligand (“UIO-67”, specific surface area by BET method: 1530 m ² / g, average fineness) Except for using a pore size of 0.6 nm), a function sustained release composition (molded material) was produced in the same manner as in Example 15. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition P1 in Table 16 below. Amount. Similarly, compositions P2 to P7 having different contents were prepared. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 13, and this was designated as Example 16.

[Example 17]
Example 1 except that thiabendazole (melting point: 305 ° C., molecular weight: 201.25, molecular diameter (major axis): 1.004 nm, molecular diameter (minor axis): 0.5 nm) dissolved in methanol was used as the function sustained-release liquid. In the same manner as in Example 1, a function sustained release composition (molded material) was produced. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition Q1 in Table 17 below. Amount. Similarly, compositions Q2 to Q7 having the above-mentioned different contents were prepared. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 1, and this was designated as Example 17.

[Example 18]
Porous coordination polymer composed of zinc ion as metal ion and 4,4′-biphenyldicarboxylic acid as organic ligand (“UIO-67”, specific surface area by BET method: 1530 m ² / g, average fineness) Except for using (pore size: 0.6 nm), a function sustained release composition (molded material) was prepared in the same manner as in Example 17. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition R1 in Table 18 below. Amount. Similarly, compositions R2 to R7 having the above contents different from each other were produced. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 17, and this was designated as Example 18.

[Example 19]
Example 1 except that catechin (melting point: 175 ° C., molecular weight: 290.27, molecular diameter (major axis): 1.195 nm, molecular diameter (minor axis): 0.524 nm) dissolved in ethanol was used as the functional sustained-release liquid. In the same manner as in Example 1, a function sustained release composition (molded material) was produced. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition S1 in Table 19 below. Amount. Similarly, compositions S2 to S7 having the above contents different from each other were produced. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 1, and this was designated as Example 19.

[Example 20]
Zinc ion as the metal ion, and a 4,4'-biphenyl dicarboxylate acid as organic ligand porous coordination polymer ( "UIO-67", a specific surface area by BET method: 1530 m ² / g, an average pore A functional sustained-release composition (molded material) was prepared in the same manner as in Example 19 except that the pore size was 0.6 nm. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition T1 of Table 20 below. Amount. Similarly, compositions T2 to T7 having the above contents different from each other were produced. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 19, and this was designated as Example 20.

[Example 21]
A porous coordination polymer (“Al-PCP”, specific surface area by BET method: 1100 m ² / g, average pore diameter: 0.7 nm) composed of aluminum ion as a metal ion and terephthalic acid as an organic ligand Except for using, a functional sustained-release composition (molded material) was prepared in the same manner as in Example 1. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition U1 of Table 21 below. Amount. Similarly, compositions U2 to U7 having the above contents different from each other were produced. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 1, and this was designated as Example 21.

[Comparative Example 1]
Etofenprox used in Example 1 as a functional sustained-release liquid was compounded and mixed with a polyethylene resin (LDPE not modified with a polar group and a functional group) as a matrix resin, and a composition (molded material) was formed. Was prepared. The mixing amount of the polyethylene resin was such that the content of the matrix resin (polyethylene resin) and the content of the sustained-release liquid were as shown in the composition a1 in Table 22 below. Similarly, compositions a2 to a7 having the above contents different from each other were produced.
The method described in Example 1 was used as the compounding method. The mixed molded body material was formed into a plate-shaped molded body having a size of 50 × 50 mm and a thickness of 1.2 mm.

[Comparative Example 2]
Etofenprox used in Example 1 as a functional sustained-release liquid was compounded into a polyethylene resin having been modified with a polar group and a functional group as a matrix resin, as described in Example 6 of Patent Document 4, and By mixing, a composition (molded material) was prepared. The compounding amount of the polyethylene resin was such that the content of the matrix resin (polyethylene resin) and the content of the sustained-release liquid were as shown in composition b1 in Table 23 below. Similarly, compositions b2 to b7 having different contents were prepared.
The method described in Example 1 was used as the compounding method. The mixed molded body material was formed into a plate-shaped molded body having a size of 50 × 50 mm and a thickness of 1.2 mm.

[Comparative Example 3]
A porous coordination polymer (“MIL-88A”, specific surface area by BET method: 170 m ² / g, average pore diameter: 0.6 nm) composed of iron ions as metal ions and fumaric acid as organic ligands Except for using, a functional sustained-release composition (molded material) was prepared in the same manner as in Example 1. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition c1 in Table 24 below. Amount. Similarly, compositions c2 to c7 having different contents were prepared. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 1, and this was designated as Comparative Example 3.

[Comparative Example 4]
A porous coordination polymer (“UiO-66”, specific surface area by BET method: 740 m ² / g, average pore diameter: 0.6 nm) composed of zirconium ion as a metal ion and terephthalic acid as an organic ligand. Except for using, a functional sustained-release composition (molded material) was prepared in the same manner as in Example 1. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition d1 in Table 25 below. Amount. Similarly, compositions d2 to d7 having different contents were prepared. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 1, and this was designated as Comparative Example 4.

[Comparative Example 5]
Except for using zeolite instead of the porous coordination polymer, a function sustained release composition (molded material) was prepared in the same manner as in Example 1. The content of the polyethylene resin is such that the content of the matrix resin (polyethylene resin), the content of the sustained-release liquid and the content of the PCP (porous coordination polymer) are as shown in the composition e1 in Table 26 below. Amount. Similarly, compositions e2 to e7 having the above contents different from each other were produced. Thereafter, a molded body was produced from each molded body material in the same manner as in Example 1, and this was designated as Comparative Example 5.

  With respect to the prepared samples of Examples and Comparative Examples, the surface amount of the function sustained-release liquid (surface concentration of the function sustained-release liquid surface) was measured by the following method.

First, each sample (molded product) was immersed in 50 mL of tetrahydrofuran in a 20 ° C. environment to wash the function sustained release liquid deposited on the surface. Next, the surface amount (surface concentration) (μg / cm ² ) of the functional sustained-release liquid per unit area of the sample in the washed liquid was measured using high performance liquid chromatography. Here, as the concentration of the functional sustained-release liquid in the sample increases, the surface amount increases, but when the concentration exceeds the allowable concentration, the upper limit is reached, which is a critical point at which the amount increases extremely. Even if the content concentration of the functional sustained-release liquid is increased, if the surface amount does not show a tendency to increase extremely, it indicates that the long-term sustained-release property is excellent. Further, when the surface amount is 1000 μg / cm ² or more, when processing by injection molding or the like as a material of the functional sustained release composite molded article, there is a possibility that a problem such as clogging of the material pellet due to a sticky surface or the like may occur. is there. Therefore, the example and the comparative example were evaluated in consideration of these two points.

The evaluation results are shown in Tables 1 to 26 and FIGS. The graphs shown in FIGS. 1 to 6 show the relationship between the concentration of the function-releasing liquid in the function-releasing composite molding and the surface amount of the function-releasing composite molding. As is clear from FIGS. 1 to 6, the surface amount also tends to increase as the concentration of the functional sustained-release liquid increases in each of the Examples and Comparative Examples, but in each Comparative Example, It was found that when the concentration of the functional sustained-release liquid exceeds 20% by mass, the surface amount sharply increases. Thereby, it turned out that the upper limit of each comparative example is 20 weight%. On the other hand, in each of the examples, even if the concentration of the functional sustained-release liquid exceeds 40% by weight, it does not reach the critical point where the surface amount increases extremely, and further, the processing upper limit of 1000 μg / cm ^2. Was.

  As described above, it is possible to add more functional liquid by adsorbing it on the porous coordination polymer than by directly developing the functional liquid on the matrix resin, and it is possible to enhance the efficacy and the effect persistence. I understood.

  The functional sustained-release composition of the present embodiment is used, for example, for molded articles provided with functional components such as a small animal control function, a sliding function, an antibacterial function, an antifungal function, a self-healing function, a catalytic function, and a medical function. it can. Specifically, the functional sustained release composite molded article of the present embodiment can be used in the industrial fields such as automobiles and electric appliances, the amenity field such as sanitary services, and the medical field such as pharmaceuticals.

Claims (5)

A functional sustained release composition comprising a functional sustained release liquid, a porous coordination polymer having a metal ion and an organic ligand, a specific surface area of at least 900 m ² / g, and a matrix resin.   The functional sustained-release composition according to claim 1, wherein the functional sustained-release liquid has a molecular weight of 600 or less and a melting point of 10 ° C or more.   The sustained release composition according to claim 1 or 2, wherein the average pore diameter of the porous coordination polymer is equal to or larger than the molecular diameter of the sustained release liquid. Function sustained-release composition according to claim 1, the surface concentration of the liquid component when compressed than 10MPa is less than 1.0 mg / cm ^2.   A molded article of the functional sustained-release composition according to any one of claims 1 to 4.