JP2010084050A - Method for producing pesticide-containing resin molded form, and pesticide-containing resin molded form - Google Patents

Abstract

Disclosed is a method for producing a drug-containing resin molded article having excellent productivity.
A method of producing a drug-containing resin molded article by bringing a resin molded article into contact with a first liquid containing a first drug and a first surfactant. After the resin molded body is brought into contact with the first liquid containing the first drug and the first surfactant, the second may be the same as or different from the surfactant contained in the first liquid. A method for producing a drug-containing resin molded article by contacting with a second liquid containing a surfactant and a second drug different from the drug contained in the first liquid.
[Selection figure] None

Description

The present invention relates to a resin molded body containing a drug and a manufacturing technique thereof.

As a drug-containing resin molded product, a coated type molded product in which the surface of the resin molded product is coated with a pest control agent, which is a kind of drug, or a kneaded type molded product obtained by melting and kneading a pest control agent into a thermoplastic resin The body is widely used (see Patent Documents 1 and 2).

Japanese Patent Laid-Open No. 4-65509 JP-A-6-24907

However, in the case of producing the above-mentioned kneaded type molded body, since the chemical is kneaded into the resin at a temperature at which the resin melts, depending on the chemical used, it may be evaporated or decomposed and used. The amount of the drug that can be contained in the molded body relative to the amount of the drug is small, and the productivity of the drug-containing resin molded body may be inferior. On the other hand, in the case of a coat-type molded article, there is a problem that it is difficult to hold a large amount of drug.

The present invention provides a method for producing a drug-containing resin molded article having excellent productivity.

That is, the present invention is a method for producing a drug-containing resin molded article by bringing a resin molded article into contact with a first liquid containing a first drug and a first surfactant.

According to the method for producing a drug-containing resin molded article of the present invention, the drug-containing resin molded article can be produced with high productivity.

The present invention is a method for producing a drug-containing resin molded article by bringing a resin molded article into contact with a first liquid containing a first drug and a first surfactant.
Resin which comprises the resin molding in this invention is not specifically limited, It may be comprised from 1 type of resin, and may be comprised from 2 or more types of resin compositions. Moreover, the resin comprised for every part among one resin molding may differ. As resin which comprises a resin molding, a thermoplastic resin and a thermosetting resin are mentioned, It is preferable that it is a thermoplastic resin.

The thermoplastic resin is not particularly limited, and examples thereof include resins obtained by polymerizing vinyl monomers and condensation polymerization resins.
The resin obtained by polymerizing the vinyl monomer is a polyolefin resin described in detail below; polystyrene, poly-α-methylstyrene, styrene-ethylene-propylene copolymer (polystyrene-poly (ethylene / propylene) block copolymer) ), Styrene-ethylene-butene copolymer (polystyrene-poly (ethylene / butene) block copolymer), styrene-ethylene-propylene-styrene copolymer (polystyrene-poly (ethylene / propylene) -polystyrene block copolymer) ), Unsaturated aromatic-containing resins such as ethylene-styrene copolymers; polyvinyl alcohol resins such as polyvinyl alcohol and polyvinyl butyral; polymethyl methacrylate, methacrylic acid esters, acrylic acid esters, methacrylic acid polymers as monomers And acrylic resins containing acrylic amides; chlorinated resins such as polyvinyl chloride and polyvinylidene chloride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene- And fluorine resins such as tetrafluoroethylene-hexafluoropropylene copolymer and polyvinylidene fluoride.
Polycondensation resins include polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polylactic acid, and polyester liquid crystal polymers; ethylenediamine-adipic acid polycondensate (nylon-66), nylon-6, nylon-12, polyamide Polyamide resins such as liquid crystal polymers; polyether resins such as polycarbonate resins, polyphenylene oxide, polymethylene oxide, and acetal resins; polysaccharide resins such as cellulose and derivatives thereof;
Examples of the thermosetting resin include an aramid resin, a polyimide resin, an epoxy resin, an unsaturated polyester resin, a phenol resin, a urea resin, and a melamine urea resin.

Among thermoplastic resins, polyolefin resins are particularly preferably used. The polyolefin resin is a resin obtained by polymerizing one or more monomers selected from α-olefin, cycloolefin, polar vinyl monomer, and the like. Further, it may be further modified after polymerization. When the polyolefin resin is a resin obtained by copolymerizing two or more types of monomers, it may be a random copolymer or a block copolymer.
Examples of polyolefin resins include propylene resins and ethylene resins. These will be described in detail below.

[Propylene resin]
Propylene-based resin is a resin mainly composed of propylene-derived structural units, and is generally crystalline. In addition to propylene homopolymer, it is a copolymer of propylene and a comonomer copolymerizable therewith. There may be.

  Examples of the comonomer copolymerized with propylene include ethylene and α-olefins having 4 to 20 carbon atoms. The α-olefin in this case includes 1-butene, 2-methyl-1-propene; 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene; 1-hexene, 2-ethyl-1 -Butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene; 1-heptene 2-methyl-1-hexene, 2,3-dimethyl-1-pentene, 2-ethyl-1-pentene, 2-methyl-3-ethyl-1-butene; 1-octene, 5-methyl-1-heptene 2-ethyl-1-hexene, 3,3-dimethyl-1-hexene, 2-methyl-3-ethyl-1-pentene, 2,3,4-trimethyl-1-pentene, 2-propyl-1-pentene 2,3-diethyl-1 -Butene; 1-nonene; 1-decene; 1-undecene; 1-dodecene; 1-tridecene; 1-tetradecene; 1-pentadecene; 1-hexadecene; 1-heptadecene; 1-octadecene; 1-nonadecene .

Preferred among the α-olefins are α-olefins having 4 to 12 carbon atoms, specifically 1-butene, 2-methyl-1-propene; 1-pentene, 2-methyl-1- Butene, 3-methyl-1-butene; 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4- Methyl-1-pentene, 3,3-dimethyl-1-butene; 1-heptene, 2-methyl-1-hexene, 2,3-dimethyl-1-pentene, 2-ethyl-1-pentene, 2-methyl- 3-ethyl-1-butene; 1-octene, 5-methyl-1-heptene, 2-ethyl-1-hexene, 3,3-dimethyl-1-hexene, 2-methyl-3-ethyl-1-pentene,
2,3,4-trimethyl-1-pentene, 2-propyl-1-pentene, 2,3-diethyl-1-butene; 1-nonene; 1-decene; 1-undecene; 1-dodecene and the like. it can. From the viewpoint of copolymerizability, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable, and 1-butene and 1-hexene are more preferable.

Preferred propylene copolymers include propylene / ethylene copolymers and propylene / 1-butene copolymers. In the propylene / ethylene copolymer and propylene / 1-butene copolymer, the content of the structural unit derived from ethylene and the content of the structural unit derived from 1-butene are, for example, “Polymer Analysis Handbook” (1995, Kinokuniya). Infrared (IR) spectrum measurement can be performed by the method described on page 616 of the bookstore.

The propylene-based resin can be produced by a method of homopolymerizing propylene using a known polymerization catalyst or a method of copolymerizing propylene and another copolymerizable comonomer. Examples of known polymerization catalysts include the following catalysts (1) to (3).
(1) Ti-Mg-based catalyst comprising a solid catalyst component containing magnesium, titanium and halogen as essential components (2) A solid catalyst component containing magnesium, titanium and halogen as essential components, an organoaluminum compound, and if necessary Catalyst system combining with third component such as electron donating compound (3) Metallocene catalyst

  Examples of the solid catalyst component containing magnesium, titanium and halogen as essential components in the above (1) and (2) include, for example, JP-A-61-218606, JP-A-61-287904, JP-A-7- Examples include the catalyst system described in Japanese Patent No. 216017.

  Preferred examples of the organoaluminum compound in the above (2) include triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, tetraethyldialumoxane and the like, and the electron donating compound is preferably cyclohexylethyldimethoxysilane, Examples thereof include tert-butylpropyldimethoxysilane, tert-butylethyldimethoxysilane, and dicyclopentyldimethoxysilane.

  The propylene resin is, for example, a solution polymerization method using an inert solvent typified by a hydrocarbon compound such as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, or a liquid monomer as a solvent. It can be produced by a bulk polymerization method or a gas phase polymerization method in which a gaseous monomer is polymerized as it is. Polymerization by these methods may be carried out batchwise or continuously.

  The structure of the propylene-based resin is any of the isotactic structure, syndiotactic structure, and attacking structure described in "Polypropylene Handbook" (edited by Edward P. Moore, Jr., published by the Industrial Research Committee (1998)). These structures may be used, or a mixture of these structures may be used. In the present invention, a syndiotactic or isotactic propylene resin is preferably used from the viewpoint of heat resistance.

As the metallocene catalyst in the above (3), a known catalyst is used. For example, JP 58-19309, JP 60-35005, JP 60-35006, JP 60- No. 35007, No. 60-35008, No. 61-130314, No. 3-163088, No. 4-268307, No. 9-12790, No. 9- No. 87313, JP-A-10-508055, JP-A-11-80233, JP10-5080555, JP2587251, JP2627669, JP2668732 and the like Metallocene catalysts can be exemplified. Among these, examples of suitable metallocene catalysts are preferably transition metal complexes of Group 3 to Group 12 of the periodic table having at least one cyclopentadiene-type anion skeleton and a C1-symmetric structure. The metallocene catalyst described in Japanese Patent No. -299334 is preferable.

The propylene-based resin may have a syndiotactic structure. The propylene resin having a syndiotactic structure is a peak intensity observed at 20.2 ppm based on tetramethylsilane in a ¹³ C-NMR spectrum measured with a 1,2,4-trichlorobenzene solution at 135 ° C. A value obtained by dividing the sum of peak intensities attributed to methyl groups of propylene units (syndiotactic pentad fraction [rrrr]) is usually from 0.3 to 0.9, preferably 0. A propylene resin having a viscosity of 0.5 to 0.9, more preferably 0.7 to 0.9. The necessary peaks can be assigned according to A. Zambelli et al, Macromolecules, 6, 925 (1973).

As described in JP-A-5-17589, JP-A-5-131558 and the like, a method for producing a syndiotactic propylene-based resin is carried out using a metallocene-based catalyst having a homogeneous active species. It is manufactured by polymerizing.

  The metallocene catalyst is a catalyst having a homogeneous active species, and the propylene resin having a syndiotactic structure produced using the metallocene catalyst has a characteristic that the molecular weight distribution and composition distribution are narrow. Further, adjustment of molecular weight and regularity can be controlled by selecting a ligand of the metallocene catalyst.

The syndiotactic propylene resin has a melting point of about 130 to 150 ° C., a density of about 880 kg / mm ³ , and a crystallinity of about 30 to 40%. For this reason, the molded object excellent in transparency, glossiness, etc. can be obtained.

  From the viewpoint of moldability, the propylene resin used in the present invention has a melt flow rate (MFR) measured at a temperature of 230 ° C. and a load of 21.18 N in accordance with JIS K 7210 of 0.1 to 200 g / 10. Minute is preferable, and 0.5 to 50 g / 10 minutes is more preferable.

[Ethylene resin]
An ethylene-based resin is a resin mainly composed of ethylene-derived structural units and is generally crystalline. In addition to an ethylene homopolymer, it is a copolymer of ethylene and a comonomer copolymerizable therewith. There may be. Examples thereof include ethylene-α-olefin copolymers, high density polyethylene, high pressure method low density polyethylene, and ethylene-ethylenically unsaturated carboxylic acid copolymers.

The melt flow rate (MFR) of the ethylene-based resin is usually 0.01 to 100 g / 10 min, preferably 0.1 to 80 g / min, from the viewpoint of the balance between workability, mechanical strength of the molded body, and heat resistance. 10 minutes, more preferably 0.5 to 70 g / 10 minutes.

[Ethylene-α-olefin copolymer]
The ethylene-α-olefin copolymer is an ethylene-α-olefin copolymer obtained by copolymerizing ethylene and an α-olefin having 4 to 12 carbon atoms using a metallocene catalyst or a Ziegler-Natta catalyst. It is.

Examples of the α-olefin having 4 to 12 carbon atoms include butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, dodecene-1, 4-methyl. -Pentene-1,4-methyl-hexene-1, vinylcyclohexane, vinylcyclohexene, styrene, norbornene, butadiene, isoprene and the like can be mentioned, preferably hexene-1,4-methyl-pentene-1, octene-1. is there. Furthermore, norbornene and domon are also preferred as cycloolefins as α-olefins in a broad sense. Moreover, said C4-C12 alpha olefin may be used independently and may use at least 2 type together.

As the ethylene-α-olefin copolymer, for example, an ethylene-butene-1 copolymer, an ethylene-4-methyl-pentene-1 copolymer, an ethylene-hexene-1 copolymer, And ethylene-octene-1 copolymer, and the like, preferably ethylene-hexene-1 copolymer, ethylene-4-methyl-pentene-1, ethylene-octene-1 copolymer, more preferably ethylene- It is a hexene-1 copolymer.

The density of the ethylene-α-olefin copolymer is usually from 880 to 945 Kg / m ³ , preferably from 890 to 930 Kg / m ³ , from the viewpoint of the balance of heat resistance and impact strength and transparency of the molded product. Yes, more preferably 900 to 925 Kg / m ³ .

The metallocene catalyst is preferably a catalyst system including a transition metal compound having a group having a cyclopentadiene type anion skeleton. The transition metal compound having a group having a cyclopentadiene type anion skeleton is a so-called metallocene compound, for example, a general formula MLaXn-a (where M is a group 4 or lanthanide series transition of the periodic table of elements) L is a group having a cyclopentadiene-type anion skeleton or a group containing a heteroatom, and at least one is a group having a cyclopentadiene-type anion skeleton. X is a halogen atom, hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, n is a valence of a transition metal atom, and a is an integer of 0 <a ≦ n. You may use independently and may use at least 2 types together.

Further, the above metallocene catalysts include organoaluminum compounds such as triethylaluminum and triisobutylaluminum, alumoxane compounds such as methylalumoxane, and / or trityltetrakispentafluorophenylborate, N, N-dimethylanilinium tetrakispentafluoro. An ionic compound such as phenyl borate is used in combination.

Further, the metallocene-based catalyst described above includes the metallocene-based compound, an organoaluminum compound, an alumoxane compound, and / or an ionic compound, a particulate inorganic carrier such as SiO ₂ and Al ₂ O ₃ , polyethylene, polystyrene, and the like. It may be a catalyst supported or impregnated on a particulate organic polymer carrier.

As an ethylene-alpha-olefin copolymer obtained by superposition | polymerization using said metallocene catalyst, the ethylene-alpha-olefin copolymer described in Unexamined-Japanese-Patent No. 9-183816 is mentioned, for example. Recently, there is a method of using a late transition metal complex catalyst or the like as a homogeneous catalyst.

Examples of the method for producing the ethylene-α-olefin copolymer used in the present invention include known polymerization methods using a metallocene catalyst, a Ziegler-Natta catalyst, and the like. Known polymerization methods include, for example, solution polymerization method, slurry polymerization method, high pressure ion polymerization method, gas phase polymerization method, etc., preferably gas phase polymerization method, solution polymerization method, high pressure ion polymerization method, and more A gas phase polymerization method is preferred.

The density of the high-density polyethylene used in the present invention is usually 945 to 970 Kg / m ³ , preferably 945 to 965 Kg / m ³ , from the viewpoint of the balance between the heat-resistant fusion property and the impact strength of the molded body.

As a manufacturing method of the high density polyethylene used by this invention, the well-known polymerization method using a well-known polymerization catalyst is mentioned. Examples of the known polymerization catalyst include a Ziegler-Natta catalyst and the like, and examples of the known polymerization method include polymerization methods similar to those used in the above-described method for producing an ethylene-α-olefin copolymer. It is done. Examples of the method for producing high-density polyethylene include a slurry polymerization method using a Ziegler-Natta catalyst.

The density of the high-pressure method low-density polyethylene is preferably 915 to 935 Kg / m ³ , more preferably 915 to 930 Kg / m ³ , from the viewpoint of the balance between the heat-resistant fusion property and the impact strength of the molded body. Preferably it is 918-930 kg / m < ³ >.

As a method for producing a high-pressure low-density polyethylene used in the present invention, generally, using a tank reactor or a tube reactor, a polymerization pressure of 140 to 300 MPa, a polymerization temperature of 200 to 300 ° C. in the presence of a radical generator. In order to control the melt flow rate, hydrogen, hydrocarbons such as methane and ethane are used as molecular weight regulators.

[Ethylene-ethylenically unsaturated carboxylic acid copolymer]
The ethylene-ethylenically unsaturated carboxylic acid copolymer is a copolymer of ethylene and an ethylenically unsaturated carboxylic acid. The ethylenically unsaturated carboxylic acids are carboxylic acids and are compounds having an ethylenically unsaturated bond which is a polymerizable carbon-carbon unsaturated bond such as a carbon-carbon double bond.

Examples of the ethylenically unsaturated carboxylic acids include vinyl esters of saturated carboxylic acids, vinyl esters of unsaturated carboxylic acids, α, β-unsaturated carboxylic acid esters, and the like.

The vinyl ester of saturated carboxylic acid is preferably an aliphatic carboxylic acid vinyl ester having about 2 to 4 carbon atoms, and examples thereof include vinyl acetate, vinyl propionate and vinyl butyrate. The vinyl ester of unsaturated carboxylic acid is preferably an aliphatic carboxylic acid vinyl ester having about 2 to 5 carbon atoms, and examples thereof include vinyl acrylate and vinyl methacrylate. The α, β-unsaturated carboxylic acid ester is preferably an ester of an unsaturated carboxylic acid having about 3 to 8 carbon atoms, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-acrylate. -Alkyl esters of acrylic acid such as butyl, isobutyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid and alkyl esters of methacrylic acid such as t-butyl. Such ethylenically unsaturated carboxylic acids are used alone or in combination of two or more. Further, hydrolysates thereof, for example, saponified ethylene-vinyl acetate copolymers obtained by hydrolysis of ethylene-vinyl acetate copolymers are also preferably used.

Among the ethylenically unsaturated carboxylic acids, vinyl acetate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate are preferable, and vinyl acetate is more preferable. The ethylene-ethylenically unsaturated carboxylic acid copolymer may have a constituent unit derived from another monomer.

The content of ethylene-derived structural units in the ethylene-ethylenically unsaturated carboxylic acid copolymer is usually 20 to 99% by weight, preferably 40 to 99% by weight, more preferably 60 to 99% by weight. The content of the structural unit derived from the saturated carboxylic acid is usually 80 to 1% by weight, preferably 60 to 1% by weight, more preferably 40 to 1% by weight (however, an ethylene-ethylenically unsaturated carboxylic acid copolymer is used). 100% by weight).

As a method for producing an ethylene-ethylenically unsaturated carboxylic acid copolymer, generally, a tank reactor or a tube reactor is used, in the presence of a radical generator, a polymerization pressure of 140 to 300 MPa, and a polymerization temperature of 200 to 300. Examples include a method of copolymerizing ethylene and an ethylenically unsaturated carboxylic acid copolymer under the condition of ° C. Hydrogen, hydrocarbons such as methane and ethane are used as molecular weight regulators to control the melt flow rate. . Recently, there is a method of using a late transition metal complex catalyst or the like as a homogeneous catalyst.

The polyolefin resin typified by the above-described propylene resin or ethylene resin may be modified. Examples of the modified polyolefin resin include the following resins (1) to (3).
(1) a modified polyolefin resin obtained by graft polymerization of an unsaturated carboxylic acid and / or a derivative thereof to an olefin homopolymer;
(2) a modified polyolefin resin obtained by graft polymerization of an unsaturated carboxylic acid and / or a derivative thereof to a copolymer of at least two olefins,
(3) A modified polyolefin resin obtained by graft polymerization of an unsaturated carboxylic acid and / or derivative thereof to a block copolymer obtained by homopolymerizing an olefin and then copolymerizing at least two olefins.

  As a method for producing the modified polyolefin resin, for example, “Practical Polymer Alloy Design” (Fumio Ide, Industrial Research Committee (issued in 1996)), Prog. Polym. Sci. 24, 81-142 (1999), Japanese Patent Application Laid-Open No. 2002-308947, and the like, and any of a solution method, a bulk method, and a melt-kneading method may be used. Moreover, the manufacturing method which combined these methods may be sufficient.

Examples of the unsaturated carboxylic acid used for the production of the modified polyolefin resin include maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid and the like.
Further, examples of the unsaturated carboxylic acid derivative include acid anhydrides, ester compounds, amide compounds, imide compounds, metal salts, and the like of the above unsaturated carboxylic acids. Specific examples thereof include maleic anhydride, itaconic anhydride. Acid, methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, Dimethyl fumarate, acrylamide,
Examples include methacrylamide, maleic acid monoamide, maleic acid diamide, fumaric acid monoamide, maleimide, N-butylmaleimide, sodium methacrylate and the like.
Moreover, you may use what dehydrates and produces | generates unsaturated carboxylic acid by the process grafted to a propylene-type resin like citric acid and malic acid.

  The unsaturated carboxylic acid and / or derivative thereof is preferably acrylic acid, glycidyl ester of methacrylic acid, or maleic anhydride.

As modified polyolefin resin, Preferably, resin like the following (4) and (5) is mentioned.
(4) A modified polyolefin resin obtained by graft polymerization of maleic anhydride to a polyolefin resin having a unit derived from ethylene and / or propylene as the main constituent unit of the polymer. (5) Mainly containing ethylene and / or propylene. Modified polyolefin resin obtained by copolymerizing olefin as a major component with glycidyl methacrylate or maleic anhydride

  The amount of the structural unit derived from the unsaturated carboxylic acid and / or derivative thereof contained in the modified polyolefin resin is preferably 0.1 to 10% by weight from the viewpoint of the mechanical strength of the molded product (however, the modification The weight of the polyolefin resin is 100% by weight).

  Examples of other modified polyolefin resins include those obtained by reacting a monomer (coupling agent) containing an element such as silicon, titanium, or fluorine, or a polymer containing them with a polyolefin resin.

It is preferable that the resin molding used by this invention is comprised from resin whose glass transition temperature is 10 degrees C or less. Examples of the resin having a glass transition temperature of 10 ° C. or lower include polyethylene (low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene), polypropylene, polybutene, polybutadiene, ethylene-propylene copolymer, ethylene-1- Ethylene-α- such as butene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer Olefin copolymer, ethylene-norbornene copolymer, ethylene-propylene-norbornene copolymer, etc., ethylene-cycloolefin copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-acrylic acid Copolymer, ethylene-methyl methacrylate copolymer Polymers such as copolymers, copolymers of ethylene and polar vinyl monomers such as ethylene-vinyl acetate-methyl methacrylate copolymer, polyolefin resins such as ionomer resins, polystyrene, poly-α-methylstyrene, styrene-ethylene-propylene copolymer Polymer (polystyrene-poly (ethylene / propylene) block copolymer), styrene-ethylene-butene copolymer (polystyrene-poly (ethylene / butene) block copolymer), styrene-ethylene-propylene-styrene copolymer ( Polystyrene-poly (ethylene / propylene) -polystyrene block copolymer), ethylene-styrene copolymer, etc., unsaturated aromatic-containing resins, ethylene-tetrafluoroethylene copolymer, ethylene-tetrafluoroethylene-hexafluoropro Pile Copolymer, fluorine-based resins such as, and the like. Although the compounding quantity of resin with a glass transition temperature of 10 degrees C or less is not specifically limited, 60% or more is preferable and 80% or more is more preferable. In the present invention, the glass transition temperature is measured according to JIS K7121.

In the molded product of the present invention, at least two kinds of resins may be mixed, and they may be compatible with each other or may form a phase separation structure.
For example, when the sea-island phase separation structure is formed, if the solubility of the resin in the island part to the drug is higher than that in the sea part, the drug is brought into contact with the resin molding, and then the drug is relative to the island part. In particular, it is kept at a high concentration (plays a role of a drug tank), and a long-term sustained release effect is easily obtained. Conversely, if the solubility of the resin in the island part of the sea-island phase separation structure is lower than that in the sea part, the drug is kept at a relatively high concentration in the sea part after the drug is brought into contact with the resin molding. (The island plays an inert filler role) and promotes bleed, so that the initial medicinal effect is easily obtained. In addition, it is possible to increase the rate and efficiency of drug absorption when contacting the molded product with the drug.
In addition, in the compatible structure, the average solubility of the resin constituting the molded body reflects the overall solubility, and the space between resin crystals is expanded, so in many cases, bleeding can be promoted. It is possible to increase the speed and efficiency of drug absorption at the time of drug contact.
In this way, the resin can be combined in accordance with the purpose of use, the structure can be controlled, the release behavior of the drug can be controlled, and the rate and efficiency of drug absorption when contacting the molded product with the drug can be increased.

[Resin additive contained in resin molding]
The resin molding used in the present invention may contain various additives as required. The amount of the additive in the resin molded body is preferably 2 parts by weight or less, preferably 0.5 parts by weight or less, more preferably 0.3 parts by weight or less, even more preferably 0.1 parts by weight or less, and particularly 0.05 It is preferable that it is below the weight part. These resin additives may be used alone or in combination.

The type of resin additive is not limited. For example, phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, UV absorbers, light stabilizers, peroxide scavengers, hydroxylamines, lubricants, plasticizers, flame retardants, nucleating agents, metal inertness Agent, antistatic agent, surfactant (including antifogging agent), pigment, filler, antiblocking agent, processing aid, foaming agent, foaming aid, emulsifier, brightener, neutralizing agent, 9,10- Color improvers such as dihydro-9-oxa-10-phosphophenanthrene-10-oxide, benzofuranones (US Pat. Nos. 4,325,853, 4,338,244, 5,175,312, 5,160,533, and 5,252,643) Gazette, 4316611, German Patent Publication 4316622, 4316876, EP Publication 589839, Etc. 591102 JP), co-stabilizers, such as indoline, and the like can be exemplified.

Examples of phenolic antioxidants include 2,6-di-t-butyl-4-methylphenol, 2,4,6-tri-t-butylphenol, 2,6-di-t-butylphenol, 2-t- Butyl-4,6-dimethylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t-butyl- 4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-diocudadecyl-4-methylphenol, 2,4,6- Tricyclohexylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- ( '-Methylundecyl-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadecyl-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltri) Alkylated monophenols such as decyl-1′-yl) phenol and mixtures thereof;

2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4 -Alkylthiomethylphenols such as nonylphenol and mixtures thereof;

2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2 , 6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyphenyl stearate, bis (3,5-di- hydroquinones and alkylated hydroquinones such as t-butyl-4-hydroxyphenyl) adipate and mixtures thereof;

tocopherols such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof;

2,2′-thiobis (6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,2′-thiobis (4-octylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (2-methyl-6-tert-butylphenol), 4,4′-thiobis (3,6-di-tert-amylphenol), 4 , 4 ′-(2,6-dimethyl-4-hydroxyphenyl) disulfide and the like, hydroxylated thiodiphenyl ether,

2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis [4-methyl-6- ( α-methylcyclohexyl) phenol)], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (4-methyl-6-nonylphenol), 2,2′-methylenebis (4 , 6-di-t-butylphenol), 2,2′-ethylidenebis (4,6-di-t-butylphenol), 2,2′-ethylidenebis (4-isobutyl-6-t-butylphenol), 2, 2′-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2′-methylenebis [6- (α, α-dimethylbenzyl) -4 Nonylphenol], 4,4′-methylenebis (6-tert-butyl-2-methylphenol), 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-butylidenebis (3-methyl) -6-tert-butylphenol), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis ( 3-t-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 1,1- Bis (5-t-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis-3′-t-butyl 4'-hydroxyphenyl) butyrate], bis (3-t-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-t-butyl-2'-hydroxy-5'-) Methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-t-) Butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5 -T-butyl-4-hydroxy-2-methylphenyl) pentane, 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenol Le acrylate, 2,4-di -t- pentyl-6- [1- (2-hydroxy-3,5-di -t- pentylphenyl) ethyl] alkylidene bisphenols and derivatives thereof such as phenyl acrylate, and mixtures thereof,

3,5,3 ′, 5′-tetra-t-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tris (3,5-di-t -Butyl-4-hydroxybenzyl) amine, bis (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide O-, N- and S-benzyl derivatives such as isooctyl-3,5-di-t-butyl-4-hydroxybenzyl mercaptoacetate and mixtures thereof,

Dioctadecyl-2,2-bis (3,5-di-t-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-t-butyl-4-hydroxy-5-methylbenzyl) malonate, di Dodecyl mercaptoethyl-2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2 Hydroxybenzylated malonate derivatives such as bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate and mixtures thereof;

1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,4-bis (3,5-di-t-butyl-4 -Hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-t-butyl-4-hydroxybenzyl) phenol and mixtures thereof ,

2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2-n-octylthio-4,6-bis (4 -Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2-n-octylthio-4,6-bis (4-hydroxy-3,5-di-t-butylphenoxy)- 1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-phenoxy) -1,3,5-triazine, tris (4-tert-butyl-3-hydroxy) -2,6-dimethylbenzyl) isocyanurate, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4,6-tris (3,5-di-t-butyl-4) -Hydroxyphenylethyl) -1,3,5 Triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylpropyl) -1,3,5-triazine, tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate , Triazine derivatives such as tris [2- (3 ′, 5′-di-t-butyl-4′-hydroxycinnamoyloxy) ethyl] isocyanurate and mixtures thereof;

Dimethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-t-butyl-4 -Hydroxybenzylphosphonate, dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoester, and mixtures thereof A benzylphosphonate derivative of

Acylaminophenol derivatives such as 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide, octyl-N- (3,5-di-t-butyl-4-hydroxyphenyl) carbanate and mixtures thereof;

β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid and methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1, 6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) Oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane And so Esters of mono- or polyhydric alcohols, such as mixtures of al,

β- (5-t-butyl-4-hydroxy-3-methylphenyl) propionic acid and methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1, 6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) Oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane And Esters of mono- or polyhydric alcohols such as mixtures thereof,

β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid and methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3- Thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane and Esters of mono- or polyhydric alcohols such as a mixture of these,

3,5-di-t-butyl-4-hydroxyphenylacetic acid and methanol, ethanol, octanol, octadecanol, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, diethylene glycol, thioethylene glycol, spiro glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis (hydroxyethyl) oxamide, 3-thia Undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2,2,2] octane and mixtures thereof Esters of mono- or polyhydric alcohol,

N, N′-bis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionyl] hydrazine, N, N′-bis [3- (3 ′, 5′-di-) t-butyl-4′-hydroxyphenyl) propionyl] hexamethylenediamine, N, N′-bis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionyl] trimethylenediamine and Examples thereof include amides of β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid such as a mixture thereof. Also, for example, a composite type phenolic antioxidant having a unit having both a phenolic antioxidant mechanism and a phosphorus antioxidant mechanism in one molecule can be used.

Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, tridecyl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thio. Dipropionate, lauryl stearyl 3,3′-thiodipropionate, neopentanetetrayltetrakis (3-laurylthiopropionate) and the like can be mentioned.

Examples of phosphorus antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl. Pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) Pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, Tristearyl sorbitol triphosphie Tetrakis (2,4-di-t-butylphenyl) -4,4′-diphenylenediphosphonite, 2,2′-methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, 2,2′-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethyl phosphite, bis (2,4- Di-t-butyl-6-methylphenyl) methyl phosphite, 2- (2,4,6-tri-t-butylphenyl) -5-ethyl-5-butyl-1,3,2-oxaphosphorinane, 2,2 ′, 2 ″ -nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra-t-butyl-1,1′-biphenyl-2,2′-diyl) phosphites and their Mixture etc. It is. Moreover, the phosphorus antioxidant described in JP-A-2002-69260 is also preferable.

Examples of the ultraviolet absorber include phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl 3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, 4-t- Octylphenyl salicylate, bis (4-t-butylbenzoyl) resorcinol, benzoylresorcinol, hesisadecyl 3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, octadecyl 3 ′, 5′-di-t-butyl- Salicylate derivatives such as 4′-hydroxybenzoate, 2-methyl-4,6-di-t-butylphenyl 3 ′, 5′-di-t-butyl-4′-hydroxybenzoate and mixtures thereof;

2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, bis (5-benzoyl-4-hydroxy-2- 2-hydroxybenzophenone derivatives such as methoxyphenyl) methane, 2,2 ′, 4,4′-tetrahydroxybenzophenone and mixtures thereof;

2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3 ′, 5′-di-t-butyl-2′-hydroxyphenyl) benzotriazole, 2- (5′-t-butyl-2) '-Hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (3-t-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzo Triazole, 2- (3′-s-butyl-2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-t-amyl-2'-hydroxyphenyl) benzotriazole, 2- [2'-hydroxy-3', 5'-bis (α, α-di Methylbenzyl) phenyl] -2H-benzotriazole, 2-[(3′-t-butyl-2′-hydroxyphenyl) -5 ′-(2-octyloxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2 -[3'-t-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl] -5-chlorobenzotriazole, 2- [3'-t-butyl-2' -Hydroxy-5 '-(2-methoxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2- [3'-t-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl) phenyl] benzo Triazole, 2- [3′-tert-butyl-2′-hydroxy-5- (2-octyloxycarbonylethyl) phenyl] ben Triazole, 2- [3′-t-butyl-2′-hydroxy-5 ′-[2- (2-ethylhexyloxy) carbonylethyl] phenyl] benzotriazole, 2- [2-hydroxy-3- (3,4) , 5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3′-dodecyl) -2'-hydroxy-5'-methylphenyl) benzotriazole and 2- [3'-t-butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl) phenyl] benzotriazole, 2 , 2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethyl Til) phenol, 2,2′-methylenebis [4-t-butyl-6- (2H-benzotriazol-2-yl) phenol], poly (3-11) (ethylene glycol) and 2- [3′-t -Butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl] benzotriazole condensate, poly (3-11) (ethylene glycol) and methyl 3- [3- (2H-benzotriazole- 2-yl) -5-t-butyl-4-hydroxyphenyl] propionate condensate, 2-ethylhexyl 3- [3-t-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, octyl 3- [3-t-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydride Roxyphenyl] propionate, methyl 3- [3-t-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate, 3- [3-t-butyl-5- 2- (2′-hydroxyphenyl) benzotriazole such as (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionic acid and mixtures thereof.

Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ((2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1, 2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2,2, 6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl) -4-piperidyl) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-butyl malonate, bis (1-acryloyl-2,2,6,6-tetramethyl-4 Piperidyl) 2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1,2,2,6,6-pentamethyl-4-piperidyldecanedioate 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -1- [2- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2,6,6-tetra Methyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2, 3,4- Tantetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1 , 2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol mixed esterified product,

Mixed esterified product of 1,2,3,4-butanetetrabonic acid and 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5 · 5] Mixed esterified product with undecane, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethyl) Ethyl) -2,4,8,10-tetraoxaspiro [5 · 5] undecane mixed ester, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2, , 6-tetramethylpiperidine polycondensate, poly [(6-morpholino-1,3,5-triazine-2,4-diyl) ((2,2,6,6-tetramethyl-4-piperidyl) Imino) hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)], poly [(6- (1,1,3,3-tetramethylbutyl) imino-1,3,5 -Triazine-2,4-diyl ((2,2,6,6-tetramethyl-4-piperidyl) imino) hexamethylene ((2,2,6,6-tetramethyl-4-piperidyl) imino)], N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane polycondensate, N, N ′, 4,7-tetrakis [4 , 6-Bis (N-butyl-N- (2,2,6 6-tetramethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10 diamine, N, N ′, 4-tris [4,6-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine N, N ′, 4,7-tetrakis [4,6-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -1,3,5- Triazin-2-yl] -4,7-diazadecane-1,10-diamine, N, N ′, 4-tris [4,6-bis (N-butyl-N- (1,2,2,6,6) -Pentamethyl-4-piperidyl) amino) -1,3,5-triazin-2-yl] -4,7 Diazadecane-1,10-diamine and hindered amine light stabilizers such as a mixture thereof,

Ethyl α-cyano-β, β-diphenyl acrylate, isooctyl α-cyano-β, β-diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α- Acrylate based light such as cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline and mixtures thereof Stabilizer,

Nickel complex of 2,2′-thiobis- [4- (1,1,3,3-tetramethylbutyl) phenol], nickel dibutyldithiocarbamate, nickel salt of monoalkyl ester, nickel complex of ketoxime and mixtures thereof, etc. Nickel-based light stabilizers,

4,4'-dioctyloxy oxanilide, 2,2'-diethoxy oxanilide, 2,2'-dioctyloxy-5,5'-di-t-butylanilide, 2,2'-didodecyloxy -5,5'-di-t-butylanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl- Oxamide-based light stabilizers such as 2′-ethoxyanilide, 2-ethoxy-5,4′-di-t-butyl-2′-ethyloxanilide and mixtures thereof;

2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazine, 2- [2,4-dihydroxyphenyl-4,6-bis (2,4-dimethylphenyl] -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine , 2- [2 Hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- ( 2- (2-hydroxyphenyl) -1 such as 2-hydroxy-3-octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and mixtures thereof , 3,5-triazine-based light stabilizer and the like.

Examples of the metal deactivator include N, N′-diphenyloxamide, N-salicyl-N′-salicyloylhydrazine, N, N′-bis (salicyloyl) hydrazine, N, N′-bis (3, 5-di-t-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide N, N′-bis (salicyloyl) oxalyl dihydrazide, N, N′-bis (salicyloyl) thiopropionyl dihydrazide, and mixtures thereof.

Examples of the hydroxylamine include N, N-dibenzylhydroxyamine, N, N-diethylhydroxyamine, N, N-dioctylhydroxyamine, N, N-dilaurylhydroxyamine, N, N-ditetradecylhydroxyamine, Examples thereof include N, N-dihexadecylhydroxyamine, N, N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl-N-octadecylhydroxyamine, and mixtures thereof.

Examples of the neutralizing agent include calcium stearate, zinc stearate, magnesium stearate, hydrotalcite (basic magnesium, aluminum, hydroxy, carbonate, hydrate), melamine, amine, polyamide, polyurethane, and mixtures thereof. .

Examples of the lubricant include aliphatic hydrocarbons such as paraffin and wax, higher aliphatic acids having 8 to 22 carbon atoms, higher aliphatic acid metal (Al, Ca, Mg, Zn) salts having 8 to 22 carbon atoms, carbon number 8-22 aliphatic alcohol, polyglycol, ester of higher fatty acid having 4-22 carbon atoms and aliphatic monohydric alcohol having 4-18 carbon atoms, higher aliphatic amide having 8-22 carbon atoms, silicone oil, rosin Derivatives and the like. Examples include erucic acid amide, oleic acid amide, ethylene bisstearyl alumide, erucyl amide, dimethylpolysiloxane and the like.

  The antistatic agent may be any of a polymer type, an oligomer type, and a monomer type. Examples thereof include polyhydric alcohol fatty acid esters such as glycerin fatty acid esters, polyoxyethylene alkylamine mixed compositions, nonionic surfactants, and the like. For example, alkyl diethanolamides, monoesters of alkyl diethanol, lauryl diethanolamide, myristyl diethanolamide, palmityl diethanolamide, stearyl diethanolamide, monolaurate of alkyl diethanolamide, monomyristic ester of alkyl diethanolamide, alkyl diethanolamine Monopalmitic acid ester of alkyl, monostearic acid ester of alkyldiethanolamide, and the like.

Surfactants include cationic surfactants, anionic surfactants, amphoteric surfactants, and nonionic surfactants, and are not particularly limited. From the viewpoint of compatibility with the resin and thermal stability, a nonionic surfactant is preferably used. These surfactants are also used to disperse the drug in water.

Specifically, sorbitan-based interfaces such as sorbitan monopalmitate, sorbitan monostearate, sorbitan monopalmitate, sorbitan monomontanate, sorbitan monooleate, sorbitan fatty acid esters such as sorbitan dioleate, and alkylene oxide adducts thereof Activator, glycerol monopalmitate, glycerol monostearate, diglycerol distearate, triglycerol monostearate, tetraglycerol dimontanate, glycerol monooleate, diglycerol monooleate, diglycerol sesquioleate, tetraglycerol Monooleate, hexaglycerin monooleate, hexaglycerin trioleate, tetraglycerin trioleate, tetraglycerin monolaurate, hexaglyceride Glycerin surfactants such as glycerin fatty acid esters and alkylene oxide adducts thereof such as polyethylene monolaurate, polyethylene glycol surfactants such as polyethylene glycol monopalmitate and polyethylene glycol monostearate, alkylene oxide adducts of alkylphenols, Esters of sorbitan / glycerin condensate and organic acid, polyoxyethylene (2 mol) stearylamine, polyoxyethylene (4 mol) stearylamine, polyoxyethylene (2 mol) stearylamine monostearate, polyoxyethylene (4 Mol) Polyoxyethylene alkylamines such as laurylamine monostearate and fatty acid esters thereof. Furthermore, fluorine compounds (especially fluorine-based surfactants) having a perfluoroalkyl group, ω-hydrofluoroalkyl group, etc., silicon-based compounds having alkylsiloxane groups (particularly silicon-based surfactants), and the like can be mentioned. Specific examples of the fluorosurfactant include Unidyne DS-403, DS-406, DS-401 (trade name) manufactured by Daikin Industries, Ltd., and Surflon KC-40 (trade name) manufactured by Seimi Chemical Co., Ltd. Examples of the silicon-based surfactant include SH-3746 (trade name) manufactured by Toray Dow Corning Silicon Co., Ltd.

  As the anti-blocking agent, fine particles having a spherical shape or a shape close thereto can be used regardless of inorganic type or organic type. Examples thereof include calcium carbonate, silicon dioxide, polymethylsilsesquioxane, aluminum silicate salt, and a crosslinked polymethyl methacrylate.

Examples of the nucleating agent include the following compounds, and these may be used in combination of two or more. Sodium 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate, [-2,2'-methylenebis (4,6-di-t-butylphenyl) phosphate] dihydroxyoxyaluminum, bis [ Phosphate-2,2'-methylenebis (4,6-di-t-butylphenyl)] hydroxyaluminum, tris [phosphate-2,2'-methylenebis (4,6-di-t-butylphenyl)] Aluminum, sodium bis (4-t-butylphenyl) phosphate, benzoic acid metal salts such as sodium benzoate, aluminum p-t-butylbenzoate, 1,3: 2,4-bis (o-benzylidene) sorbitol, 1 , 3: 2,4-bis (o-methylbenzylidene) sorbitol, 1,3: 2,4-bis (o-ethylbenzylidene) sorbitol, 1,3-o-3,4-dimethylbenzylidene-2,4- o-benzylidenesorbitol, 1,3-o-benzylidene-2,4-o-3,4-dimethylbenzylidenesorbitol, 1,3: 2,4-bis (o -3,4-dimethylbenzylidene) sorbitol, 1,3-o-p-chlorobenzylidene-2,4-o-3,4-dimethylbenzylidenesorbitol, 1,3-o-3,4-dimethylbenzylidene-2, 4-o-p-chlorobenzylidene sorbitol, 1,3: 2,4-bis (op-chlorobenzylidene) sorbitol and mixtures thereof, rosin alkali metal salts, alkaline earth metal salts, specifically Compounds such as rosin lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt and aluminum salt. Polymeric nucleating agents such as polyvinylcycloalkane are also used.

Examples of the filler include calcium carbonate, silicate, glass fiber, asbestos, talc, kaolin, mica, barium sulfate, carbon black, carbon fiber, zeolite, and a mixture thereof.

Examples of foaming agents and foaming aids include azocarboxylic acid derivatives such as azodicarboxylic amide, nitroso compounds such as N, N′-dinitrosopentamethylenetetramine, and sulfonyl hydrazide compounds such as p, p′-oxybisbenzenesulfonylhydrazide. Etc.

Examples of the crosslinking agent include dicumyl peroxide, t-butylcumyl peroxide, 3,5-dimethyl-2,5- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di- ( t-butyl-peroxy) hexane-3,4,4′-bis (t-butylperoxy) diisopropylbenzene, 1,1bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, and the like. .

The manufacturing method of the resin molding used by this invention is not specifically limited, It can manufacture by well-known methods, such as extrusion molding, injection molding, press molding, blow molding, and calendar molding. The shape is not particularly limited. Sheets, films, strands, nets, pellets, and the like, and lattice-shaped and three-dimensional shaped products obtained by injection molding or blow molding can be used. Textiles such as mosquito nets and insect nets obtained by processing monofilaments or multifilaments spun from a resin are examples of preferred resin moldings. In a molded body composed of filaments, the contact efficiency with a liquid is generally increased, and the content efficiency of a drug is increased. A molded body made of multifilament is particularly suitable. The molded body may be a single-layer molded body or a multilayer molded body. It is preferable from the viewpoint of drug absorbability that a resin having a glass transition temperature of 10 ° C. or lower constitutes the surface of the molded body.

The resin molding to be used may contain a drug. The method of adding the drug at the time of molding is not particularly limited, but the drug is quantitatively fed in the process of kneading the resin and drug composition in advance with a Banbury mixer or in the process of melt-extruding the resin with a biaxial extruder. And the like. Using the compound or master batch thus obtained as a raw material, various moldings are performed to obtain a resin molded body containing a drug. The chemical | medical agent contained in a resin molding includes the same thing as the 1st chemical | medical agent contained in the 1st liquid mentioned later. The resin molded body may contain two or more kinds of drugs.

The resin molded body may contain porous particles so as to easily contain a drug. Examples of the porous particles include silica particles. By bringing the liquid containing the drug into contact with the resin molded body including the porous particles, the drug is supported on the porous particles, and as a result, the drug can be bleed for a long period of time. The average particle diameter of the porous particles contained in the resin molded body is usually in the range of 0.01 to 40 μm, and more preferably in the range of 0.03 to 20 μm.

  In the present invention, the resin molded body as described above is brought into contact with the first liquid containing the first drug and the first surfactant to produce a drug-containing resin molded body.

  As the first drug contained in the first liquid, pesticides, fungicides used for agriculture, fungicides, insecticides, herbicides, fungicides, plant growth regulators and other agricultural chemicals and fertilizers, Fragrance, Deodorant, Cosmetics, Pharmaceuticals, Quasi-drugs, Antibacterial agents, Antifungal agents, Antiviral agents, Algae inhibitors, Preservatives, Natural herbal extract oils, Birdproof agents, Antibacterial agents, Underwater organisms An inhibitor or the like is used. Two or more types may be included as the first drug.

In the present invention, the pest control agent is a general term for agents having an insecticidal function, an insect repellent function, a pest repellent function, an insect growth inhibition function, and the like. In a preferred embodiment, the pest control agent contains an insecticide effective for vector control (medium control). Vector control refers to controlling insects such as mosquitoes that carry protozoa and viruses in order to prevent infectious diseases such as malaria and dengue fever. It is preferable that a 1st liquid contains a 2 or more types of pest control agent as a 1st chemical | medical agent.

The pest control agent is preferably one or more compounds selected from the group consisting of the following (A) to (D).
Of these, (A) pyrethroid compounds (B) carbamate compounds (C) organophosphorus compounds (D) neonicotinoid compounds are particularly preferred pyrethroid compounds. Of these, it is more preferable to use two or more types of pest control agents having different mechanisms of action because resistance to insect pest control agents that mediate infectious diseases can be hardly exhibited.

Examples of pyrethroid compounds include etofenprox, fenvalerate, esfenvalerate, fenpropathrin, cypermethrin, permethrin, cyhalothrin, deltamesulin, cycloprosulin, fulvalinate, bifenthrin, tralomethrin, silafluophene, D-phenosulin, cypheno. Surin, acrinathrin, cyfluthrin, tefluthrin, transfluthrin, tetramethrin, allethrin, prareslin, empentrin, imiproslin, D-flamesrin, and the like.

Examples of the carbamate compounds include alanicarb, bendiocarb, carbanyl, isoprocarb, carbosulfan, phenoxycarb, indoxacarb, propoxer, pirimicarb, thiodiocarb, mesomil, etiophencarb, phenothiocarb, cartap, fenobucarb, XMC, xylylcarb, and the like. .

Examples of organophosphorus compounds include fenitrothion, diazinon, pyridafenthione, pyrimiphosethyl, pyrimiphosmethyl, etrimphos, fenthion, foxime, chlorpyrifos, chlorpyrifosmethyl, cyanophos, pyracrophos, acephate, azamethifos, malathion, Temefos, dimethoate, formothione, phentoate and the like.

Examples of neonicotinoid compounds include clothianidin, thiamethoxam, nitenpyram, nithiazine, acetamiprid, imidacloprid, thiacloprid, nitenpyram, flonicamid and the like.

Further, as synergists for enhancing the effect of the pest control agent, piperonyl butoxide, N-octylbicycloheptene dicarboximide, N- (2-ethylhexyl) -1-isopropyl-4-methylbicyclo [2,2,2 It is also possible to blend oct-5-ene-2,3-dicarboximide, octachlorodipropyl ether and the like. 0.1-10 times is preferable with respect to a pest control agent, and, as for the compounding quantity of a synergist, 0.1-3 times is more preferable. In particular, it is preferable to use a pyrethroid compound and a synergist in combination.

A 1st chemical | medical agent is made to contact with a molded object in the liquefied state. If the drug is liquid at room temperature, it may be used as it is. Those that are solid at room temperature are preferably heated to a temperature equal to or higher than the melting point and used in a liquid state. Or you may liquefy by making it melt | dissolve or disperse | distribute to the solvent suitable for a chemical | medical agent. At this time, the solvent is not particularly limited, but an aqueous solvent such as water and / or alcohol is preferable, and water is particularly preferable in consideration of safety to the environment.

The concentration of the drug in the first liquid is preferably a concentration that exceeds the saturation solubility of the drug at a temperature at which the resin molded body is brought into contact with the first liquid. By setting the supersaturated state, the concentration of the drug in the liquid can be maintained even if the drug dissolved in the liquid is absorbed by the molded body. The concentration of the drug in the liquid is preferably 10% by weight or less, and particularly preferably 5% by weight or less in order to facilitate uniform inclusion in the resin molding. Moreover, in order to make it easy to contain a chemical | medical agent in a resin molding, it is preferable that it is 0.1 weight% or more, It is more preferable that it is 0.3 weight% or more, It is 0.5 weight% or more Is more preferable. However, these are values when the weight of the first liquid is 100% by weight.

The first liquid contains a first surfactant. The surfactant is not particularly limited, and is selected from the surfactants previously mentioned as the resin additive. For example, anionic surfactants such as alkyl sulfate ester salt, alkyl sulfonate salt, alkyl aryl sulfonate salt, dialkyl sulfosuccinate salt, polyoxyethylene alkyl aryl ether phosphate ester salt, polyoxyethylene alkyl ether, polyoxyethylene Nonionic surfactants such as alkyl aryl ethers, sorbitan fatty acid esters and polyoxyethylene fatty acid esters, glycerin fatty acid esters, lignin sulfonates, abietic acid salts, dinaphthylmethane disulfonates and the like can be mentioned. When the weight of the first liquid is 100% by weight, the surfactant is preferably 0.001 to 1% by weight, and particularly preferably 0.01 to 0.5% by weight.

The ratio of the first surfactant to the first drug contained in the first liquid is usually a weight ratio of drug / surfactant = 100/1 to 1/1, preferably 50/1 to 2/1, more preferably 20/1 to 5/1.

The present invention is particularly effective when the first agent that is incompatible with the aqueous solvent and the aqueous solvent are used. Since the first liquid containing the first drug and the aqueous solvent also contains the first surfactant, the first drug is in an emulsion state in the first liquid. By bringing the first liquid and the resin molded body into contact with each other, a large amount of the first agent can be contained in the resin molded body as compared with the case where the first liquid does not contain a surfactant. .

Furthermore, a binder may be added to the liquid containing the drug for the purpose of promoting adhesion to the molded body. The binder includes an organic type and an inorganic type, but is not particularly limited. Examples of organic binders include resin binders, vinyl resins including homo- or copolymers such as vinyl chloride, vinyl acetate, and vinylidene chloride, acrylic resins, polyester resins, epoxy resins, polyamide resins, fluorine resins, and modified resins thereof. included. It exists in the form of an emulsion or dispersion in the liquid.

As the inorganic binder, inorganic colloid is preferable. As the inorganic colloid, a known inorganic colloid can be used, and examples thereof include a metal colloid solution, an oxide colloid solution, a hydroxide colloid solution, a carbonate colloid solution, and a sulfate colloid solution. Examples of the metal element contained in the metal colloid solution include gold, palladium, platinum, and silver. Elements contained in oxide colloid solutions, hydroxide colloid solutions, carbonate colloid solutions, or sulfate colloid solutions include silicon, aluminum, zinc, magnesium, calcium, barium, titanium, zirconium, manganese, iron, cerium, Examples are nickel and tin. Of these, an oxide colloid solution or a hydroxide colloid solution is preferably used, and a silicon oxide colloid solution is particularly preferable.

In the above case, the size of the particles is not particularly limited as long as it is a size that can be dispersed in a colloidal manner in the solvent, and those having an average particle diameter of 1 to 500 nm are used, but 2 nm to 100 nm are preferable, and 5 nm to 70 nm. Those are more preferred.

When the first liquid and the resin molded body are brought into contact with each other, the first drug moves into the resin constituting the molded body. At this time, in order for the drug to move into the molded body, it is preferable that the glass transition temperature (Tg) of the resin constituting the molded body is sufficiently lower than the temperature at the time of contact. At this time, the higher the temperature of the resin molded body and the first liquid, the faster the transition rate and concentration of the first drug to the resin molded body, and the shorter the processing time can be, the higher the temperature is. Increased transpiration loss of pest control agents during contact treatment. Considering this, the temperature when the resin molded body is brought into contact with the first liquid is preferably adjusted to 100 ° C. or lower, and more preferably 80 ° C. or lower.

The method for bringing the first liquid into contact with the resin molded body is not particularly limited, but it is important that the liquid is in contact with the portion of the resin molded body to which the drug is to be applied. For example, a method of immersing a resin molded body in a first liquid containing a first drug and a first surfactant, or a first mold containing a first drug and a first surfactant in a resin molded body There are methods such as applying and spraying liquid. The amount of the liquid brought into contact with the resin molded body is appropriately determined according to the concentration of the drug in the liquid. When the resin molded body is immersed in the first liquid containing the first agent and the first surfactant, it is preferable to immerse the resin molded body while stirring the first liquid. Thereby, a chemical | medical agent can be contained in the resin molding uniformly in a short time.

The amount of the drug contained in the drug-containing resin molded body is preferably 0.1 to 10 g, more preferably 0.5 g or more, and further preferably 1 g or more, per 1 m ² of the surface area of the molded body. When the drug is added to the molded body in advance, the total amount of the drug in the drug-containing resin molded body is preferably 10% by weight or less, and more preferably 5% by weight or less.

You may repeat the process of this invention in multiple times. If the first liquid and the molded body are repeatedly contacted, the concentration of the first drug contained in the molded body can be increased.

Moreover, after making the resin molding contact with the 1st liquid containing the 1st chemical | medical agent and 1st surfactant, it is the same as or different from the surfactant contained in the 1st liquid. The drug-containing resin molded body may be produced by bringing the surfactant into contact with a second liquid containing the second surfactant and a second drug different from the drug contained in the first liquid. In this way, when the resin molded body is brought into contact with a liquid containing different drugs, a single molded body can contain a plurality of types of drugs simultaneously. The type and concentration of the first surfactant contained in the first liquid and the second surfactant contained in the second liquid may be the same or different. The contacting method may be the same as application or dipping, or may be different. Further, the step of contacting with the third liquid, the step of contacting with the fourth liquid, and the step may be repeated.

Further, the same effect as described above can be obtained by using a resin molded body in which a drug is kneaded in advance as the resin molded body to be used, and bringing the resin molded body into contact with the first liquid. That is, when it is brought into contact with the first liquid containing the same drug as the drug kneaded in advance, the drug concentration in the molded body can be increased, and the first drug containing a drug different from the drug kneaded in advance. When it is made to contact with this liquid, the medicine containing resin molding containing two kinds of medicines can be obtained.

When the first liquid and the resin molded body are once contacted and then contacted with the second liquid, the molded body may remain wet with the first liquid. In order to maintain the purity of the second liquid, it is preferable that the first liquid on the surface of the resin molded body is removed and dried before being immersed in the second liquid.

The method for removing excess liquid on the surface of the resin molded body is not particularly limited, and it can be sucked in contact with a water-absorbing material such as paper or cloth, blown by blowing air, or rotated the molded body. For example, a method of blowing away by centrifugal force can be used.
Furthermore, the method for drying the surface of the molded body is not particularly limited, and examples thereof include a method of heating in an oven, using a vacuum dryer, and applying air with a dryer.

According to this invention, even if it is a chemical | medical agent which decomposes | disassembles easily when processed at high temperature, or a chemical | medical agent which is easy to evaporate, it can be made to contain stably in a molded object. For example, it is a suitable method when the molded product contains a chemical having a decomposition temperature of 200 ° C. or lower or a chemical having a vapor pressure at 20 ° C. of 1.0 × 10 ⁻³ Pa or higher.

The drug-containing resin molded product obtained in the present invention can be used for various applications. For example, interior materials such as wallpaper, wall materials, flooring materials, ceiling materials, lighting covers, fan feathers, air conditioner fans and other household appliances, septic tanks, collars and clothes used for pet fleas, chiffons and closets Such as mold prevention and insect repellent.

The drug-containing fiber obtained when monofilament or multifilament fiber is used as the resin molded body in the present invention is a fiber having an insecticidal function such as clothing, household goods, daily goods, outdoor goods, agriculture, forestry and fishery products, and hygiene goods. Can be used for products.

A monofilament is a continuous yarn composed of one single yarn. Usually, monofilaments are manufactured by drawing and cooling filaments melted and extruded from dozens to hundreds of spinning nozzles on a single die one by one. Monofilaments are used as fishing lines, brushes, tennis racket guts, fishing nets, and the like.
The cross-sectional shape of the monofilament is not particularly limited, and may be any cross-sectional shape such as a circle, a hollow shape, a flat shape, a square shape, a half moon shape, a triangle shape, and a polygon shape having five or more corners. Furthermore, it may be a composite monofilament such as a core-sheath type or a sea-island type. When the resin molding in this invention is a monofilament, 50-1000 denier is good and can be suitably selected according to a use.
A multifilament is a single yarn obtained by twisting several to several tens of filaments, and is used for ropes, nets, carpet pile materials, nonwoven yarns, and the like.
The following method is mentioned as a manufacturing method of a multifilament. First, a large number of molten filaments discharged from the spinning nozzle are cooled by passing through a cooling zone. The cooling here may be such that the single yarn filaments are not fused to each other, and after cooling, an oil agent is applied by an oiling roller. After the undrawn yarn is wound up or subsequently, it is drawn and manufactured by twisting (drafting) in the drawing process.
When the resin molding in this invention is a multifilament, the single fiber is 1-100 denier, 50-500 denier is good as a total, and it can select suitably by a use.

Household goods and daily goods that are textile products include, for example, mosquito nets, insect screens, duvet covers, futon bags, curtains, cushions, cushions, sofa covers, sink mats, bathroom mats, washbasin mats, toilet mats , Toilet seat covers, costume covers, rugs, etc.
Examples of agricultural, forestry, and fishery products include insect nets, pest control sheets, fishing nets, outdoor products include tents, hammocks, ropes, sleeping bags, and the like, and sanitary products include masks, bandages, and bandages.
In particular, when used as a mosquito net, mosquitoes that transmit infectious diseases such as malaria come into contact with a pest control agent on the surface of the fiber to exert an insecticidal effect. Such an insecticidal method is an environmentally safe extermination method and is preferable.
Moreover, various products as described above, for example, a mosquito net can be used as the resin molded body, and a drug-containing mosquito net can be obtained by bringing this into contact with the first liquid.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this Example.
The evaluation was performed by the following method.

[Measurement of pest control content]
The weight (A gram) of the resin molded body before contact with the liquid containing the pest control agent and the weight (B gram) of the resin molded body after contacted with the liquid containing the pest control agent and dried are measured. C (%) defined by C (%) = (B−A) / A × 100 was defined as the content of the pest control agent.

[Net forming]
(1) Production of master batch and raw material 45.8% by weight of porous particles (porous silica, average particle size 12 μ), permethrin as a pyrethroid insecticide (vapor pressure 7 × 10 ⁻⁵ Pa at 20 ° C.) 2% by weight and 1.6% by weight of antioxidant BHT are mixed with a mixer to prepare a drug-containing powder. Further, 29.7 parts by weight of zinc stearate and 14.5 parts by weight of white pigment are mixed and mixed. A containing mixture was obtained.
A core layer in which 35.7% by weight of the drug-containing mixture and 44.2% by weight of LDPE (Sumitomo Chemical Sumikasen G803-1) are mixed, and 20.2% by weight of HDPE (Mitsui Chemicals Hi-Zex 2200J) is added to the sheath layer. The two layers used were extruded with a twin-screw extruder at a melt-kneading zone temperature of 200 ° C. and a die temperature of 200 ° C., and the extruded strand was cooled through a cooling water tank and then cut with a pelletizer to obtain a master batch. It was.
17% by weight of the master batch and 83% by weight of HDPE (Mitsui Chemicals Hi-Zex 440M) were mixed and extruded with a twin screw extruder at a melt-kneading zone temperature of 210 ° C. and a die temperature of 210 ° C., and the extruded strand was put into a cooling water bath. After cooling through, it was cut with a pelletizer to obtain raw material pellets.
(2) Fabrication of fibers Melt spinning was performed using the raw materials. The strand extruded at a cylinder temperature of 130 to 210 ° C. and a die temperature of 230 ° C. is cooled with water while being drawn at a first take-up speed of 13 m / min, and then led to a drawing water tank to bring it into a boiling state (95 ° C. or higher). The inside was taken up at a second take-up speed of 105 m / min to obtain a fiber drawn at a draw ratio of 8 times. This fiber was 190 denier and the yarn diameter was 160 μm.
(3) Production of Net Using the fiber, a net containing 2% by weight of permethrin having a mesh size of 4 mm and a basis weight of 50 g / m ² was obtained by Russell weaving.

[Sheet forming]
Single-layer inflation molding of ethylene-methacrylic acid copolymer (EMMA; "Acrylift WH302" manufactured by Sumitomo Chemical Co., Ltd.) having a copolymer concentration of 15% by weight with a cylinder temperature of 160 ° C, a die temperature of 180 ° C and a take-up speed of 5 m / min. Thus, a sheet having a thickness of 100 μm was obtained.

[Example 1]
1 liter of water, 10 g of fenitrothion (organophosphorus insecticide, vapor pressure 1.8 × 10 ⁻² Pa at 20 ° C.), neutral detergent for dishwashing (containing 30% by weight of alkyl ether sulfate sodium salt as the main component of surfactant) A dispersion liquid in which 5 g was dispersed was prepared. The dispersion was immersed in the net (10 cm × 15 cm, weight 0.72 g) while stirring. Stirring was stopped after 3 hours of stirring, and then immersed for 18 hours. Thereafter, the net was pulled up, the surface was wiped off with a Kim towel, and dried in an environmental test room at a temperature of 23 ° C. and a humidity of 50% RH for 24 hours. The net weight increase after drying was 0.04 g, and the content of fenitrothion was 5.6% by weight. As a result, a net containing 2% by weight of permethrin and 5.6% by weight of fenitrothion was obtained.

[Example 2]
The same procedure as in Example 1 was performed except that 10 g of synergist PBO (piperonyl butoxide) was used instead of fenitrothion. At this time, the net weight before immersion was 0.76 g, the weight increase after drying was 0.06 g, and the PBO content was 7.9 wt%. As a result, a net containing 2% by weight of permethrin and 7.9% by weight of PBO was obtained.

[Example 3]
The same procedure as in Example 1 was performed except that the EMMA sheet was used instead of the net. At this time, the weight of the sheet before immersion was 1.39 g, the weight increase after drying was 0.05 g, and the content of fenitrothion was 3.6% by weight.

[Comparative Example 1]
The same procedure as in Example 1 was conducted except that no neutral detergent for dishwashing was added. At this time, the weight of the net before immersion was 0.71 g, the weight increase after drying was only 0.004 g, and the content of fenitrothion was 0.56% by weight.

Claims (14)

A method for producing a drug-containing resin molded article by bringing a resin molded article into contact with a first liquid containing a first drug and a first surfactant. The method for producing a drug-containing resin molded article according to claim 1, wherein the first liquid further contains water. The method for producing a drug-containing resin molded article according to claim 1 or 2, wherein the first liquid further contains a binder. The method for producing a drug-containing resin molded article according to any one of claims 1 to 3, wherein the first drug is a pest control agent. The method for producing a drug-containing resin molded article according to claim 3, comprising two or more kinds of pest control agents as the first drug. The method for producing a drug-containing resin molded article according to claim 4, wherein the pest control agent is one or more compounds selected from the group consisting of the following (A) to (D).
(A) pyrethroid compound (B) carbamate compound (C) organophosphorus compound (D) neonicotinoid compound The method for producing a drug-containing resin molded product according to any one of claims 1 to 6, wherein the first drug is (A) a pyrethroid compound and a synergist. The said resin molding consists of at least 2 types of resin, The method of manufacturing the chemical | medical agent containing resin molding in any one of Claims 1-7. The method for producing a drug-containing resin molded product according to claim 8, wherein the resin molded product has a phase separation structure. The method for producing a drug-containing resin molded product according to any one of claims 1 to 9, wherein the resin molded product contains a drug. In the method for producing a drug-containing resin molded product according to any one of claims 1 to 10,
After contacting the resin molded body with the first liquid containing the first drug and the first surfactant,
A second liquid comprising a second surfactant, which may be the same as or different from the surfactant contained in the first liquid, and a second drug different from the drug contained in the first liquid. In contact with
A method for producing a drug-containing resin molded article. The method for producing a drug-containing resin molded product according to any one of claims 1 to 11, wherein the resin molded product is a woven fabric made of monofilament or multifilament. The medicine containing resin molding obtained by the method in any one of Claims 1-12. The drug-containing resin molded article according to claim 13, which is a mosquito net.