WO2009131078A1 - Fungicide composition and fungicidal resin composition including the same - Google Patents

Abstract

Provided are a fungicidal resin composition and a fungicide composition that are capable of controlling proliferation of fungi, bacteria (including yeasts, spore fungi, antinomyces), wood destroying fungi, algae and marine life, further, are excellent in fungicidal property, antifungal property, algae resistant property, antibromic property and antiputrefactive property, and are available in the form of a molded article or a membrane to be also excellent in continuity of effects thereof. The resin composition contains a resin, and the fungicide composition including, in predetermined quantities respectively, a benzimidazole system compound, an organic iodive system compound, a thiazole system compound and a haloalkylthio system compound. A content of the antifungal composition is 0.01 - 10 parts by mass with respect to 100 parts by mass of the resin.

Description

Antifungal agent composition and antifungal resin composition containing the same

The present invention controls the growth of fungi, bacteria (including yeast, spore fungi, actinomycetes), wood-rotting fungi, algae and marine organisms, and further has fungicidal, fungicidal, antialgal, deodorizing and The present invention relates to an antifungal resin composition which provides a molded article, a film and the like which are excellent in antiseptic properties and excellent in sustainability of these effects, and an antifungal agent composition contained therein.

Conventionally, for the purpose of obtaining a clean, comfortable and healthy environment, or for the purpose of suppressing the deterioration of resources and products due to microorganisms, bacteria, etc., molded articles, films, and the like containing antibacterial agents and fungicides, etc. Forming materials are widely used.
For example, Patent Document 1 discloses that a bioresistant agent to be blended in a resin includes a nitrile compound, a pyridine compound, a haloalkylthio compound, an organic iodo compound, a thiazole compound, and a benzimidazole compound. Disclosed is a bioresistant molded article that is at least four selected compounds and that has a drug content in the range of 0.05 to 30% by weight with respect to all components constituting the molded article. .
Patent Document 2 discloses an industrial antibacterial composition comprising 2- (n-octyl) -4-isothiazolin-3-one, bis (2-pyridylthio-1-oxide) zinc salt and a benzimidazole compound as active ingredients. A resin composition comprising polyvinyl chloride is disclosed.
Patent Document 3 contains 0.01 to 5 parts by mass of an inorganic composite containing zinc as an essential component with respect to 100 parts by mass of a thermoplastic resin mainly composed of a specific rubber-reinforced styrene resin. An antibacterial thermoplastic resin composition is disclosed.

In addition, antibacterial agents, fungicides, etc. are extremely important in products used in various industries for the purpose of obtaining a clean, comfortable and healthy environment, or for the purpose of suppressing degradation of resources and products by microorganisms. Occupies a position.
For example, Patent Document 4 discloses an antibacterial composition containing a nitrile antibacterial agent, a pyridine antibacterial agent, a haloalkylthio antibacterial agent, an organic iodine antibacterial agent and a thiazole antibacterial agent as active ingredients, and these antibacterial agents. And an antibacterial composition containing a benzimidazole antibacterial agent.
Patent Document 5 includes 2-pyridinethiol-1-oxide sodium, 2,3,5,6-tetrachloro-4-methylsulfonylpyridine, 2- (n-octyl) -4-isothiazolin-3-one, and diiodomethyl. -Antibacterial and fungicidal substances containing at least 0.1% (mass) of p-tolyl-sulfone, methyl (benzimidazol-2-yl) carbamate and 1,2-benzisothiazolin-3-one, An anti-algae and antibacterial composition is disclosed.
Patent Document 6 discloses a deodorizing composition containing a titanium phosphate compound having a specific structure or a condensate thereof as an active ingredient, a nitrile antibacterial agent, a pyridine antibacterial agent, a haloalkylthio antibacterial agent, and a benzimidazole type. Antifungal agent, antibacterial agent and antibacterial agent containing 1 to 10% by mass of a mixture containing 0.1 to 40% by mass of each of two or more of antibacterial agent, organic iodine antibacterial agent, isothiazolyl antibacterial agent and thiazole antibacterial agent An odorant is disclosed.

Patent Document 7 discloses a wood preservative containing, as an active ingredient, an anionic surfactant containing a sulfonate or a lauryl sulfate ester salt, which has an effect of controlling against wood-rotting fungi (such as Prunus edulis and Kawaratake). Yes.
Patent Document 8 discloses an underwater harmful organism control agent containing an indole compound and a pyridine compound as active ingredients.

JP-A-9-157111 Japanese Patent Laying-Open No. 2005-23017 JP 2006-239904 A JP-A-8-92012 JP 2005-298494 A JP 2006-52209 A JP 2007-15959 A JP-A-10-45512

As is apparent from the above Patent Documents 1 to 3, in recent years, most of the proposed resin compositions and the like contain an antifungal agent comprising a combination of a plurality of components in a predetermined ratio according to the purpose. In such a composition, there have been a problem that the resistance (repellency) spectrum and the sustainability of the effect are not yet sufficient, and a heavy metal component causes water pollution.
The object of the present invention is to control the growth of fungi, bacteria (including yeast, spore fungi, actinomycetes), wood-rotting fungi, algae and marine organisms, and furthermore, fungicidal, antifungal, antialgal, and deodorant It is an object of the present invention to provide an antifungal resin composition which gives a molded article (solid body, foam), a film and the like which are excellent in properties and antiseptic properties and have excellent sustainability of these effects.

Further, as is apparent from the above Patent Documents 4 to 8, most of the recently proposed antibacterial agents, fungicides and the like contain a plurality of components at a predetermined ratio in accordance with the purpose. . However, there are problems such as a narrow antibacterial spectrum and a problem that the sustainability of the effect is not yet sufficient.
The object of the present invention is to control the growth of fungi, bacteria (including yeast, spore fungi, actinomycetes), wood-rotting fungi, algae and marine organisms, and furthermore, fungicidal, antifungal, antialgal, and deodorant It is providing the antifungal agent composition which is excellent in the property and antiseptic property, and is excellent in the sustainability of these effects.

As a result of diligent research to solve the above problems, the present inventor has found that a resin, a benzimidazole compound, an organic iodo compound, a thiazole compound, and a haloalkylthio compound at a specific ratio. The fungicide composition and the resin composition containing the fungicide, bacteria (including yeast, spore fungus, actinomycetes), wood-rot fungi, algae and marine organisms and wood decay are controlled and further prevented. It was found that a molded article having excellent fungiability, antibacterial properties, algae-proofing properties, deodorizing properties and antiseptic properties and excellent sustainability of these effects was obtained.

The present invention is shown below.
1. (B1) benzimidazole-based compound 85 to 99.97 mass when the total of [A] resin and [B] the following compounds (b1), (b2), (b3) and (b4) is 100 mass% %, (B2) 0.01 to 5% by mass of an organic iodine compound, (b3) 0.01 to 5% by mass of a thiazole compound and (b4) 0.01 to 5% by mass of a haloalkylthio compound And the fungicide composition [B] is contained in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the resin [A]. Resin composition.
2. 2. The antifungal resin composition according to 1 above, wherein the benzimidazole compound (b1) is a benzimidazole carbamic acid derivative.
3. 3. The fungicidal resin composition according to 2 above, wherein the benzimidazole carbamate derivative is at least one selected from methyl 1H-2-benzimidazole carbamate and methyl 1-butylcarbamoyl-2-benzimidazole carbamate.
4). The organic iodo compound (b2) is an iodosulfonylbenzene derivative, the thiazole compound (b3) is a benzimidazole derivative having a thiazole group, and the haloalkylthio compound (b4) is a haloalkylthiosulfamide derivative. The antifungal resin composition as described in 1 above.
5). The antifungal composition [B] further contains an organic bromide compound (b5), and the content of the organic bromide compound (b5) is determined based on the compounds (b1), (b2), and (b3). And the antifungal resin composition as described in 1 above, wherein the total amount of (b4) is 0.01 to 3 parts by mass, when the total is 100 parts by mass.
6). The antifungal property as described in 5 above, wherein the organic bromide compound is at least one selected from 2-bromo-2-nitro-1,3-propanediol and 1,2-dibromo-2,4-dicyanobutane. Resin composition.
7). A molded product comprising the antifungal resin composition as described in 1 above.
8). It contains a benzimidazole compound (b1), an organic iodo compound (b2), a thiazole compound (b3), and a haloalkylthio compound (b4), and the content of each component is 100 in total. When the mass percentage is 85% to 99.97% by mass, 0.01% to 5% by mass, 0.01% to 5% by mass, and 0.01% to 5% by mass, respectively, Fungi composition.
9. Furthermore, it contains an organic bromide compound (b5), and the content of the organic bromide compound (b5) is such that the benzimidazole compound (b1), the organic iodine compound (b2), and the thiazole compound (b3). ) And the haloalkylthio-based compound (b4) are 0.01 to 3 parts by mass when the total of the haloalkylthio compounds (b4) is 100 parts by mass.

According to the antifungal resin composition of the present invention, fungi, bacteria (including yeast, spore fungus, actinomycetes), wood-rotting fungi, algae and marine organisms are propagated, and wood decay is further controlled. It is possible to obtain molded articles (solid bodies, foams), films and the like that are excellent in the properties, antibacterial properties, algae-proofing properties, deodorization properties and antiseptic properties and are excellent in the sustainability of these effects. Therefore, the antifungal resin composition of the present invention is suitable for a wide range of applications such as molding materials, paints (including inks), adhesives, sealing agents, and surface treatment agents. In addition, in the case of a molding material, molded article or the like containing the antifungal resin composition of the present invention, bleed-out is unlikely to occur, and thus the above effect and the surface appearance are not deteriorated. . Further, when the molded article or film containing the antifungal resin composition of the present invention is used on the bottom of a ship, an arrangement in the sea, a portion that comes into contact with water such as fishing gear, barnacles, mussels, etc. Adhesion and overgrowth of underwater harmful organisms can be suppressed, and since it does not contain heavy metals, it hardly causes water pollution.
When the antifungal resin composition of the present invention further contains an organic bromide compound (b5), it is excellent in antibacterial properties against spore bacteria such as Bacillus genus, Clostridium genus, etc. and wood rot fungi. The organic iodo compound (b2) is an iodosulfonylbenzene derivative, the thiazole compound (b3) is a benzimidazole derivative having a thiazole group, and the haloalkylthio compound (b4) is a haloalkylthiosulfamide. When the content of the organic bromide compound (b5) is 0.01 to 3 parts by mass, it is difficult to obtain an effect with a conventional resin composition containing an antifungal agent. Spore fungi such as Bacillus cereus, Clostridium botulinum, Clostridium perfringens, etc., as well as Sugihiratake, Kawaratake, Statake, Namidatake, , Excellent resistance to wood-rotting fungi such as Fomitopsis palustris.

The fungicide composition of the present invention can be used as a powder-based composition; water, an organic solvent, or a composition dispersed or dissolved in a mixed medium thereof. Further, it is suitable for molding materials and molded articles prepared by blending with resins and the like; antiseptics; antifouling agents and the like.
According to the fungicide composition of the present invention, fungi, bacteria (including yeast, spore fungus, actinomycetes), wood-rotting fungi, algae and marine organisms are propagated and the decay of wood is further controlled. It is excellent in antibacterial properties, algae control properties, deodorization properties and antiseptic properties, and is excellent in sustainability of these effects. In the case of a molding material, molded article or the like containing the fungicidal composition of the present invention, bleeding out is unlikely to occur, and thus the above effect and the surface appearance are not deteriorated. In addition, when used on the bottom of a ship, underwater arrangements, parts that come into contact with water such as fishing gear, it is possible to suppress the adhesion and overgrowth of underwater harmful organisms such as barnacles and mussels, and Because it does not contain heavy metals, it hardly causes water pollution.

The present invention will be described in detail below.
The antifungal resin composition of the present invention comprises [A] resin (hereinafter also referred to as “component [A]”) and [B] the following compounds (b1), (b2), (b3) and (b4). (B1) benzimidazole compound 85 to 99.97% by mass, (b2) organic iodine compound 0.01 to 5% by mass, (b3) thiazole compound 0.01 And a fungicide composition (hereinafter also referred to as “component [B]”) containing 5 to 5% by mass and (b4) 0.01 to 5% by mass of a haloalkylthio compound. The content of the product [B] is 0.01 to 10 parts by mass with respect to 100 parts by mass of the resin [A].

Since the antifungal resin composition of the present invention can be applied to a wide range of uses, the component [A] is selected according to the purpose, use and the like. The said component [A] may consist of only 1 type, and may consist of 2 or more types. Moreover, the property is not specifically limited, either, it may be solid or liquid.
In the present invention, the component [A] can be a polymer, a polymer-forming compound (precursor), a composition containing it (a composition for forming a polymer), or the like.

The component [A] may be either a thermoplastic resin or a curable (thermosetting, photocurable, electron beam curable, room temperature curable, etc.) resin. In the former case, the antifungal resin composition of the present invention is used. The product is a thermoplastic resin composition, and in the latter case, it is a curable resin composition. In the present invention, a preferred component [A] is a thermoplastic resin.

When the component [A] is a thermoplastic resin, it is not particularly limited as long as it contains a polymer having thermoplasticity; rubber reinforced resin such as ABS resin, ASA resin, AES resin; polystyrene, styrene / acrylonitrile Styrene (co) polymers such as copolymers, styrene / maleic anhydride copolymers, (meth) acrylic acid esters / styrene copolymers; Olefin resins such as polyethylene and polypropylene; Polyester resins; Polyamide resins Polycarbonate resin; Polyarylate resin; Polyacetal resin; Vinyl chloride resin such as polyvinyl chloride, ethylene / vinyl chloride polymer, and polyvinylidene chloride; One kind of (meth) acrylic acid ester such as polymethyl methacrylate (PMMA) Acrylic resins such as (co) polymers using the above; polyphenyle Ethers; Polyphenylene sulfide; Fluorine resins such as polytetrafluoroethylene and polyvinylidene fluoride; Imide resins such as polyimide, polyamideimide and polyetherimide; Ketone resins such as polyetherketone and polyetheretherketone; Polysulfone and polyether Examples include sulfone resins such as sulfones; urethane resins; polyvinyl acetate; polyethylene oxide; polyvinyl alcohol; polyvinyl ether; polyvinyl butyral; phenoxy resins; These can be used alone or in combination of two or more.
Among the above thermoplastic resins, those suitable for forming a molded product include: rubber reinforced resin; polyester resin; olefin resin; polyamide resin; alloy of polyester resin and polycarbonate resin; polyester resin, rubber reinforced resin and Examples include polycarbonate resin alloys.

The rubber-reinforced resin is obtained by polymerizing a vinyl monomer (a2) containing an aromatic vinyl compound in the presence of a rubbery polymer (hereinafter referred to as “rubbery polymer (a1)”). Rubber reinforced vinyl resin (hereinafter referred to as “rubber reinforced vinyl resin (A1)”) or the rubber reinforced vinyl resin (A1) and a structural unit derived from a vinyl monomer ) A polymer (hereinafter referred to as “(co) polymer (A2)”).

The rubbery polymer (a1) may be a homopolymer or a copolymer as long as it is rubbery at room temperature, but it may be a diene polymer (diene rubber polymer). And non-diene polymers (non-diene rubber polymers) are preferred. Further, the rubber polymer (a1) may be a crosslinked polymer or a non-crosslinked polymer. These can be used alone or in combination of two or more.

Examples of the diene polymers include homopolymers such as polybutadiene, polyisoprene, and polychloroprene; styrene / butadiene copolymers, styrene / butadiene / styrene copolymers, acrylonitrile / butadiene copolymers, and acrylonitrile / styrene / butadiene copolymers. Styrene / butadiene copolymer rubber such as polymer; styrene / isoprene copolymer, styrene / isoprene copolymer rubber such as styrene / isoprene / styrene copolymer, acrylonitrile / styrene / isoprene copolymer; natural rubber Etc. These copolymers may be block copolymers or random copolymers. These copolymers may be hydrogenated (however, the hydrogenation rate is less than 50%). The said diene polymer can be used individually by 1 type or in combination of 2 or more types.

Examples of the non-diene polymer include ethylene units and ethylene / α-olefin copolymer rubbers including units composed of α-olefins having 3 or more carbon atoms; urethane rubbers; acrylic rubbers; silicone rubbers; Examples include silicone / acrylic IPN rubbers; polymers obtained by hydrogenating (co) polymers containing units composed of conjugated diene compounds. These copolymers may be block copolymers or random copolymers. These copolymers may be hydrogenated (however, the hydrogenation rate is 50% or more). The said non-diene polymer can be used individually by 1 type or in combination of 2 or more types.

The resin containing the rubber-reinforced vinyl resin (A1) obtained when a diene polymer is used as the rubber polymer (a1) is generally referred to as “ABS resin”. Further, a resin containing a rubber-reinforced vinyl resin (A1) obtained when ethylene / α-olefin and / or ethylene / α-olefin / non-conjugated diene copolymer is used as the rubbery polymer (a). Is generally referred to as “AES resin”. Furthermore, a resin containing a rubber-reinforced vinyl resin (A1) obtained when an acrylic rubber is used as the rubber polymer (a) is generally referred to as an “ASA resin”.

The vinyl monomer (a2) used for forming the rubber-reinforced vinyl resin (A1) may be an aromatic vinyl compound alone, or an aromatic vinyl compound and, for example, a vinyl cyanide compound, (meth) A compound that can be copolymerized with an aromatic vinyl compound, such as an acrylate compound, a maleimide compound, or an acid anhydride, can be used alone or in combination of two or more.
Therefore, the vinyl monomer (a2) is one or more aromatic vinyl compounds, or one or more aromatic vinyl compounds and one or more compounds copolymerizable with the aromatic vinyl compounds. A monomer in combination with can be used.

The aromatic vinyl compound is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. Examples include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinyltoluene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinylxylene, vinylnaphthalene, monochlorostyrene, dichloromethane. Examples thereof include styrene, monobromostyrene, dibromostyrene, and fluorostyrene. These can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferred.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.
Examples of the (meth) acrylic acid ester compound include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, methyl acrylate, acrylic Examples include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and the like. These can be used alone or in combination of two or more.

Examples of the maleimide compounds include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide and the like. Can be mentioned. These can be used alone or in combination of two or more. In addition, as another method for introducing a unit composed of a maleimide compound, for example, a method in which maleic anhydride is copolymerized and then imidized may be used.
Examples of the acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These can be used alone or in combination of two or more.

In addition to the above compounds, a vinyl compound having a functional group such as a hydroxyl group, an amino group, an epoxy group, an amide group, a carboxyl group, or an oxazoline group can be used as necessary. For example, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxystyrene, N, N-dimethylaminomethyl methacrylate, N, N-dimethylaminomethyl acrylate, N, N-diethyl-p-aminomethylstyrene Glycidyl methacrylate, glycidyl acrylate, 3,4-oxycyclohexyl methacrylate, 3,4-oxycyclohexyl acrylate, vinyl glycidyl ether, methallyl glycidyl ether, allyl glycidyl ether, methacrylamide, acrylamide, methacrylic acid, acrylic acid And vinyl oxazoline. These can be used alone or in combination of two or more.

As described above, when the component [A] is a rubber reinforced resin, the rubber reinforced resin may be only the rubber reinforced vinyl resin (A1), or the rubber reinforced vinyl resin (A1). And a (co) polymer (A2) obtained by polymerization of a vinyl monomer. Examples of the vinyl monomer include compounds used for forming the rubber-reinforced vinyl resin (A1), that is, aromatic vinyl compounds, cyanide vinyl compounds, (meth) acrylic acid ester compounds, maleimide compounds, acids. One or more selected from an anhydride and a compound having a functional group can be used. Therefore, the (co) polymer (A2) is a polymer obtained by polymerizing components having exactly the same composition as the vinyl monomer (a2) used for forming the rubber-reinforced vinyl resin (A1). It may be a polymer obtained by polymerizing the same type of monomer with different compositions, or a polymer obtained by polymerizing different types of monomers with different compositions It may be. Two or more of these polymers may be contained.

The graft ratio of the rubber-reinforced vinyl resin (A1) is preferably 30 to 150% by mass, more preferably 50 to 120% by mass. If the graft ratio of the rubber-reinforced vinyl resin (A1) is too small, the surface appearance and impact resistance of the antifungal resin composition of the present invention and a molded product containing it may be lowered. On the other hand, if the graft ratio is too large, the molding processability is poor.
Here, the graft ratio means x gram of rubber component in 1 gram of the rubber reinforced vinyl resin (A1), 1 gram of the rubber reinforced vinyl resin (A1) with acetone (however, the rubbery polymer (a1)). Is an acrylic rubber, acetonitrile is used.) When the insoluble content when dissolved in y-gram is obtained, the value is obtained by the following formula.
Graft rate (mass%) = {(y−x) / x} × 100

In addition, the intrinsic viscosity [η] (methyl ethyl ketone) of the soluble component of acetone of the rubber-reinforced vinyl resin (A1) (however, acetonitrile is used when the rubbery polymer (a1) is an acrylic rubber). (Measured at 30 ° C.) is preferably 0.2 to 1 dl / g, more preferably 0.3 to 0.8 dl / g. By setting it as this range, it is excellent in the moldability of the antifungal resin composition of this invention, and is excellent also in the impact resistance of the obtained molded article.
The graft ratio and intrinsic viscosity [η] are the types and amounts of a polymerization initiator, a chain transfer agent, an emulsifier, a solvent, etc., when the rubber-reinforced vinyl resin (A1) is produced. It can be easily controlled by changing the polymerization temperature or the like.

Examples of the (co) polymer (A2) include the following (3) to (8). In addition, the compound used for formation of the said rubber reinforced vinyl-type resin (A1) can be applied to each monomer, and a preferable compound is also the same.
(3) One or more (co) polymers obtained by polymerizing only aromatic vinyl compounds.
(4) One or more (co) polymers obtained by polymerizing only (meth) acrylic acid ester compounds.
(5) One or more types of copolymers obtained by polymerizing an aromatic vinyl compound and a vinyl cyanide compound.
(6) One or more kinds of copolymers obtained by polymerizing an aromatic vinyl compound and a (meth) acrylic acid ester compound.
(7) One or more types of copolymers obtained by polymerizing aromatic vinyl compounds, vinyl cyanide compounds and other compounds.
(8) One or more types of copolymers obtained by polymerizing an aromatic vinyl compound and other compounds excluding the vinyl cyanide compound.
These can be used alone or in combination of two or more.

Accordingly, specific examples of the (co) polymer (A2) include acrylonitrile / styrene copolymer, acrylonitrile / α-methylstyrene copolymer, acrylonitrile / styrene / methyl methacrylate copolymer, styrene / methyl methacrylate. Examples include copolymers, acrylonitrile / styrene / N-phenylmaleimide copolymers, and the like.

The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the (co) polymer (A2) is preferably 0.2 to 0.8 dl / g. When the intrinsic viscosity [η] is within the above range, the physical property balance between molding processability and impact resistance is excellent. The intrinsic viscosity [η] of the (co) polymer (A2) can be controlled by adjusting the production conditions, as in the case of the rubber-reinforced vinyl resin (A1).

Intrinsic viscosity [η] of a soluble component by acetone of the above rubber-reinforced resin (provided that acetonitrile is used when the rubbery polymer (a1) is an acrylic rubber) (measured in methyl ethyl ketone at 30 ° C.) Is preferably 0.2 to 0.8 dl / g. When the intrinsic viscosity [η] is within the above range, the physical property balance between molding processability and impact resistance is excellent.

Here, when the rubber-reinforced resin is a rubber-reinforced vinyl resin (A1), and a (co) polymer obtained by polymerization of a rubber-reinforced vinyl resin (A1) and a vinyl monomer ( In any case of the mixture comprising A2), the content of the rubbery polymer (a1) in the antifungal resin composition of the present invention is preferably 5 to 30% by mass. When the content of the rubbery polymer (a1) is in the above range, the antifungal resin composition of the present invention and the molded product containing the same are excellent in impact resistance, surface appearance, rigidity, heat resistance and the like.

The olefin resin is not particularly limited as long as it is a polymer containing a monomer unit composed of an α-olefin having 2 or more carbon atoms. A preferred olefin resin is a polymer containing a monomer unit composed of an α-olefin having 2 to 10 carbon atoms. Accordingly, a (co) polymer mainly containing at least one monomer unit composed of an α-olefin having 2 to 10 carbon atoms; one or more monomer units composed of an α-olefin having 2 to 10 carbon atoms; And a copolymer mainly containing at least one monomer unit composed of a compound copolymerizable with the α-olefin. These can be used alone or in combination of two or more.

Examples of the olefin resin include polyethylene, polypropylene, ethylene / propylene copolymer, polybutene-1, and ethylene / butene-1 copolymer. Among these, polyethylene, polypropylene, and propylene / ethylene copolymer are preferable, and a polymer including propylene units with respect to all monomer units of 50% by mass or more, that is, polypropylene and ethylene / propylene copolymers are more preferable. . The ethylene / propylene copolymer includes a random copolymer and a block copolymer, and a random copolymer is particularly preferable.

The olefin resin may be crystalline or amorphous. Preferably, it has a crystallinity of 20% or more by X-ray diffraction at room temperature.
The melting point (based on JIS K7121) of the olefin resin is preferably 40 ° C. or higher.
The molecular weight of the olefin resin is not particularly limited, but from the viewpoint of moldability, the melt flow rate (according to JIS K7210; hereinafter also referred to as “MFR”) is preferably 0.01 to 500 g / 10 min. And those having a molecular weight corresponding to each value are preferred.

As the olefin resin, ionomer, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, cyclic olefin copolymer, chlorinated polyethylene, and the like can be used.

The polyester resin is not particularly limited as long as it has an ester bond in the main chain of the molecule, and may be a saturated polyester resin or an unsaturated polyester resin. Of these, saturated polyester resins are preferred. Further, it may be a homopolymerized polyester or a copolyester. Further, it may be a crystalline resin or an amorphous resin.

Examples of the polyester resins include polyalkylene terephthalates such as polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), polyhexamethylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, and polyneopentyl terephthalate. , Homopolymerized polyesters such as polyalkylene naphthalates such as polyethylene isophthalate, polyethylene naphthalate, polybutylene naphthalate, polyhexamethylene naphthalate, copolymer polyesters mainly containing alkylene terephthalate units and / or alkylene naphthalate units, liquid crystals Examples include polyester. Of these, polybutylene terephthalate is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

The polycarbonate resin is not particularly limited as long as it has a carbonate bond in the main chain, and may be an aromatic polycarbonate or an aliphatic polycarbonate. Moreover, you may use combining these. In the present invention, an aromatic polycarbonate is preferable from the viewpoint of impact resistance, heat resistance, and the like. The polycarbonate resin may have a terminal modified with an R—CO— group or an R′—O—CO— group (R and R ′ each represents an organic group). This polycarbonate resin can be used individually by 1 type or in combination of 2 or more types.

The viscosity average molecular weight of the polycarbonate resin is preferably 12,000 to 40,000 when converted from the solution viscosity measured at a temperature of 20 ° C. using methylene chloride as a solvent. When this viscosity average molecular weight is in the above range, the molding processability is excellent, and the resulting molded article is excellent in impact resistance, toughness and chemical resistance.
The polycarbonate resin may be used by mixing two or more polycarbonate resins having different viscosity average molecular weights as long as the overall viscosity average molecular weight falls within the above range.

As described above, the polycarbonate resin can be used as an alloy in combination with a polyester resin, or a rubber-reinforced resin and a polyester resin.

The polyamide-based resin is not particularly limited as long as it is a resin having an acid amide bond (—CO—NH—) in the main chain.
Examples of the polyamide-based resin include nylon 4, 6, 7, 8, 11, 12, 6.6, 6.9, 6.10, 6.11, 6.12, 6T, 6 / 6.6, 6 / 12, 6 / 6T, 6T / 6I and the like.
In addition, the terminal of a polyamide-type resin may be sealed with carboxylic acid, amine, etc. Examples of the carboxylic acid include aliphatic monocarboxylic acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Examples of the amine include aliphatic primary amines such as hexylamine, octylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, and behenylamine.
The said polyamide-type resin can be used individually by 1 type or in combination of 2 or more types.

Moreover, when the said component [A] is curable resin, as this curable resin, if it contains the polymer and / or precursor which produce | generate cured resin by itself or with a hardening | curing agent etc. , Not particularly limited, acrylic resin, epoxy resin, phenolic resin, unsaturated polyester resin, alkyd resin, melamine resin, urethane resin, urea resin, silicone resin, polysulfide resin, polyimide resin, bismaleimide / triazine resin , Furan resin, xylene resin, guanamine resin, dicyclopentadiene resin and the like. These can be used alone or in combination of two or more.

In addition, the antifungal resin composition of the present invention can be used as a paint, an adhesive, a sealing agent, etc. as well as forming a molded product. Suitable resins in these cases include acrylic resins, polyvinyl acetate, polyvinyl alcohol, vinyl chloride resins, urethane resins, urea resins and the like.

Next, component [B] is demonstrated.
The component [B] is a composition containing a benzimidazole compound (b1), an organic iodo compound (b2), a thiazole compound (b3), and a haloalkylthio compound (b4) in a predetermined ratio. . This component [B] may contain other components as required.

The benzimidazole compound (b1) is a compound having a benzimidazole ring and having no thiazole group and —S—C—X bond (X: halogen atom).
Examples of the benzimidazole compound (b1) include benzimidazole carbamic acid derivatives, thiobenzimidazole derivatives, sulfonyl group-containing benzimidazole derivatives, and the like. These can be used alone or in combination. In the present invention, a benzimidazole carbamic acid derivative is preferable.

The benzimidazole carbamic acid derivative is preferably a compound represented by the following general formula (1).

[In the formula, R ¹ and R ² are the same or different and are a hydrogen atom, a hydrocarbon group which may have a substituent, or other organic group, and R ³ has a hydrogen atom, a substituent. An alkyl group that may be substituted, an aryl group that may have a substituent, or another organic group, and R ⁴ is a hydrocarbon group. ]
Examples of the compound represented by the general formula (1) include methyl 1H-2-benzimidazolecarbamate, methyl 1-butylcarbamoyl-2-benzimidazolecarbamate, methyl 6-benzoyl-1H-2-benzimidazolecarbamate , 6- (2-thiophenecarbonyl) -1H-2-benzimidazole carbamate methyl and the like. These can be used alone or in combination of two or more.

The thiobenzimidazole derivative is preferably a compound represented by the following general formula (2).

[In the formula, R ¹ and R ² are the same or different and are a hydrogen atom, a hydrocarbon group which may have a substituent, or other organic group, and R ³ has a hydrogen atom, a substituent. An alkyl group that may be substituted, or an aryl group that may have a substituent, and R is an organic group. ]

Examples of the sulfonyl group-containing benzimidazole derivative include 1-dimethylaminosulfonyl-2-cyano-4-bromo-6-trifluoromethylbenzimidazole. These can be used alone or in combination of two or more.

As the benzimidazole compound (b1) according to the present invention, methyl 1H-2-benzimidazolecarbamate and methyl 1-butylcarbamoyl-2-benzimidazolecarbamate are preferable, and in particular, 1H-2-benzimidazolecarbamic acid. Methyl is particularly preferred.

The content of the benzimidazole compound (b1) contained in the component [B] is 85 when the total of the components (b1), (b2), (b3) and (b4) is 100% by mass. To 99.97% by mass, preferably 88 to 99.7% by mass, and more preferably 91.5 to 99.5% by mass. When the content of the benzimidazole compound (b1) is within the above range, the fungi, bacteria, wood decay fungi, algae and marine organisms are controlled to grow. It is excellent in deodorization and antiseptic properties and excellent in sustainability of these effects.

The organic iodine compound (b2) is an organic compound having an iodine atom, and is a compound having no thiazole group and —S—C—X (X: halogen atom). In addition, a chlorine atom may be included.
Examples of the organic iodo compound (b2) include an iodosulfonyl compound and an iodinated unsaturated aliphatic compound. These can be used alone or in combination. In the present invention, iodosulfonyl compounds are preferred.

The iodosulfonyl compound is preferably an iodosulfonylbenzene derivative, and examples thereof include diiodomethyl-p-tolylsulfone (also referred to as 1-diiodomethylsulfonyl 4-methylbenzene) and 1-diiodomethylsulfonyl 4-chlorobenzene. These can be used alone or in combination of two or more. Of these, diiodomethyl-p-tolylsulfone is preferred.
Examples of the iodinated unsaturated aliphatic compound include 3-iodo-2-propargylbutylcarbamic acid, 4-chlorophenyl-3-iodopropargyl formal, 3-ethoxycarbonyloxy-1-bromo-1,2-diiodo- Examples include 1-propene and 2,3,3-triiodoallyl alcohol. These can be used alone or in combination of two or more.

As the organic iodo compound (b2) according to the present invention, diiodomethyl-p-tolylsulfone is particularly preferable.

The content of the organic iodine compound (b2) contained in the component [B] is 0 when the total of the components (b1), (b2), (b3) and (b4) is 100% by mass. 0.01 to 5% by mass, preferably 0.03 to 4% by mass, more preferably 0.05 to 3% by mass. When the content of the organic iodine compound (b2) is within the above range, the growth of fungi, bacteria, wood decay fungi, algae and marine organisms is controlled, and further, fungicidal, fungicidal, antialgal, It is excellent in deodorization and antiseptic properties and excellent in sustainability of these effects.

The thiazole-based compound (b3) is a compound having a thiazole group and having no —SC—X (X: halogen atom).
Examples of the thiazole-based compound (b3) include thiazole group-containing benzimidazole derivatives, isothiazolin-3-one derivatives, 1,2-benzisothiazolin-3-one derivatives, benzthiazole derivatives, and isothiazole derivatives. These can be used alone or in combination of two or more. In the present invention, thiazole group-containing benzimidazole derivatives are preferred.

The thiazole group-containing benzimidazole derivative is preferably a compound represented by the following general formula (3).

[Wherein, R ¹ and R ² are the same or different and each represents a hydrogen atom, a halogen atom, an amino group, a sulfonic acid (salt) group, a nitro group, a hydroxyl group, a hydrocarbon group which may have a substituent, It is another organic group, R ³ is a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ⁵ is an alkylene group. M is 0 or 1. ]

Examples of the compound represented by the general formula (3) are shown below.

The compound on the left is 2- (4-thiazolyl) -1H-benzimidazole.

The isothiazolin-3-one derivative is preferably a compound represented by the following general formula (4).

[Wherein R ⁶ and R ⁷ are the same or different and are a hydrogen atom, a halogen atom or a hydrocarbon group which may have a substituent, and R ⁸ represents a hydrocarbon which may have a substituent. It is a group. ]

Examples of the compound represented by the general formula (4) include 2-methyl-4-isothiazolin-3-one, 2- (n-octyl) -4-isothiazolin-3-one, and 5-chloro-2-methyl- 4-isothiazolin-3-one, 4,5-dichloro-2-cyclohexyl-4-isothiazolin-3-one, 2-methyl-5-phenyl-4-isothiazolin-3-one, 2-hydroxymethyl-4-isothiazoline -3-one and the like. These can be used alone or in combination of two or more.

The 1,2-benzisothiazolin-3-one derivative is preferably a compound represented by the following general formula (5).

[Wherein R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom, a halogen atom, a nitro group, a carboxyl group, a cyano group or a hydrocarbon group which may have a substituent, and R represents a hydrogen atom Or it is an organic group. ]

Examples of the compound represented by the general formula (5) include the following.

The benzthiazole derivative is preferably a compound represented by the following general formulas (6) and (7).

[In the formula, R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom or a hydrocarbon group which may have a substituent; R represents —SM (M represents a metal atom such as Na or Zn; Or an organic group. ]

^Wherein, R ^{9, R 10} and ^{R 11} are the same or different, a hydrogen atom or a substituent hydrocarbon group which may have ^{a, R 12 is, R 13} are the same or different, organic It is a group. ]

Examples of the compound represented by the general formula (6) include 2- (4-thiocyanomethylthio) benzthiazole, 2-mercaptobenzthiazole sodium, and 2-mercaptobenzthiazole zinc. These can be used alone or in combination of two or more.

As the thiazole compound (b3), 2- (4-thiazolyl) -1H-benzimidazole is particularly preferable.

The content of the thiazole compound (b3) contained in the component [B] is 0. When the sum of the components (b1), (b2), (b3) and (b4) is 100% by mass. The content is from 01 to 5% by mass, preferably from 0.03 to 4% by mass, and more preferably from 0.05 to 3% by mass. When the content of the thiazole compound (b3) is within the above range, the growth of fungi, bacteria, wood rot fungi, algae and marine organisms is controlled, and further, the fungicidal, fungicidal, antialgal, and deodorant properties are controlled. It has excellent properties and antiseptic properties and is excellent in sustainability of these effects.

The haloalkylthio compound (b4) is a haloalkylthio compound and is usually a compound having a —S—C—X bond (X: halogen atom).
Examples of the haloalkylthio compound (b4) include haloalkylthiosulfamide derivatives, haloalkylthiophthalimide derivatives, haloalkylthiotetrahydrophthalimide derivatives, and the like. These can be used alone or in combination. In the present invention, haloalkylthiosulfamide derivatives are preferred.

Examples of the haloalkylthiosulfamide derivatives include N-trichloromethylthio-N- (phenyl) methylsulfamide, N-trichloromethylthio-N- (4-chlorophenyl) methylsulfamide, N- (1-fluoro-1 , 1,2,2-tetrachloroethylthio) -N- (phenyl) methylsulfamide, N- (1,1-difluoro-1,2,2-trichloroethylthio) -N- (phenyl) methylsulfamide N, N-dimethyl-N′-phenyl-N ′-(fluorodichloromethylthio) sulfamide, N, N-dimethyl-N ′-(p-tolyl) -N ′-(fluorodichloromethylthio) sulfamide, and the like. . These can be used alone or in combination of two or more. Of the above haloalkylthiosulfamide derivatives, N, N-dimethyl-N′-phenyl-N ′-(fluorodichloromethylthio) sulfamide is preferred.
Examples of the haloalkylthiophthalimide derivatives include N-fluorodichloromethylthiophthalimide and N-trichloromethylthiophthalimide. These can be used alone or in combination of two or more.
Examples of the haloalkylthiotetrahydrophthalimide derivative include N-1,1,2,2-tetrachloroethylthiotetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide and the like. These can be used alone or in combination of two or more.

As the haloalkylthio compound (b4) according to the present invention, N, N-dimethyl-N′-phenyl-N ′-(fluorodichloromethylthio) sulfamide is particularly preferable.

The content of the haloalkylthio compound (b4) contained in the component [B] is 0 when the total of the components (b1), (b2), (b3) and (b4) is 100% by mass. 0.01 to 5% by mass, preferably 0.03 to 4% by mass, more preferably 0.05 to 2.5% by mass. When the content of the haloalkylthio compound (b4) is in the above range, the fungi, bacteria, wood decay fungi, algae and marine organisms are controlled, and further, fungicidal, fungicidal, antialgal, It is excellent in deodorization and antiseptic properties and excellent in sustainability of these effects.

The said component [B] may consist of said component (b1), (b2), (b3) and (b4), and contains the other component which has an antifungal action and / or an antibacterial action It may be. In the latter case, the ratio of the total amount of the components (b1), (b2), (b3) and (b4) to the component [B] is usually It is 90 to 100% by mass, preferably 95 to 100% by mass.

The component [B] may further contain an organic bromide compound (b5). When this component (b5) is contained, it is excellent in antibacterial properties against spore bacteria such as Bacillus genus, Clostridium genus and the like, and wood decay fungi.
Examples of the component (b5) include 2,2-dibromo-3-nitrilopropionamide, 2,2-dibromo-4-nitrilobutanamide, 1,2-dibromo-2,4-dicyanobutane, 2-bromo-2 Nitrile group (cyan group) -containing compounds such as bromomethylglutaronitrile; 2-bromo-2-nitro-1,3-propanediol, 2-bromo-2-nitro-1,3-butanediol, 3-bromo Alcoholic hydroxyl group-containing compounds such as -3-nitro-2,4-pentanediol and 2,2-dibromo-2-nitroethanol; α-bromocinnamaldehyde, 2,2-dibromoacetophenone, 2,2-dibromo-4 '-Hydroxyacetophenone, 2-bromo-4'-hydroxyacetophenone, bis-1,4-bromoacetoxy-2-butene, benzyl Bromoacetate, 1,2-dibromopropionaldehyde, N-bromoacetamide, hexabromodimethylsulfone, bromomethyl thiocyanate, ω-bromooxyiminoacetophenone, bromoacetic acid ethylthiophenyl ester, 5-bromo-5-nitro-1,3 -Dioxane, 5-bromosalicylanilide, 3,4-dibromosalicylanilide, 3,4 ', 5-tribromosalicylanilide, 3,5-dibromosalicylic acid, 3,5-dibromosalicylaldehyde, 2,4,6- And tribromophenol, 1-bromo-3-ethoxycarbonyloxy-1,2-diiodo-1-propene, and the like. These can be used alone or in combination of two or more. Of the above compounds, nitrile groups such as 2,2-dibromo-3-nitrilopropionamide, 2,2-dibromo-2-nitroethanol, 1,2-dibromo-2,4-dicyanobutane (cyanide) are preferred. Group) containing compounds; alcoholic hydroxyl group containing compounds such as 2-bromo-2-nitro-1,3-propanediol; bis-1,4-bromoacetoxy-2-butene and hexabromodimethylsulfone, more preferably 2- Bromo-2-nitro-1,3-propanediol and 1,2-dibromo-2,4-dicyanobutane, particularly preferably 2-bromo-2-nitro-1,3-propanediol.

When the component [B] includes the component (b5), the content of the component (b5) is 100 parts by mass of the total of the components (b1), (b2), (b3), and (b4). In this case, the amount is preferably 0.01 to 3 parts by mass, more preferably 0.02 to 2.5 parts by mass, and still more preferably 0.03 to 2 parts by mass. When component [B] containing this component (b5) in the above proportion is used, excellent resistance to fungi, bacteria, algae, wood decay fungi, marine organisms, etc. is obtained in the obtained molded article, film, etc. Can do. In particular, the component (b1) is methyl 1H-2-benzimidazole carbamate, the component (b2) is an iodosulfonylbenzene derivative, the component (b3) is a benzimidazole derivative having a thiazole group, In the case where component (b4) is a haloalkylthiosulfamide derivative, the conventional content of components (b1), (b2), (b3), (b4) and (b5) is adjusted to the following proportions. Spore fungi such as Bacillus cereus, Clostridium botulinum, Clostridium perfringens (Clostridial perfringens), and Sugihiratake, which were difficult to achieve with the fungicide composition Bamboo, Pycnoporus cinnabarinus, Namidatake, Watagusaretake, the resistance to wood-rotting fungi such as Fomitopsis palustris excellent. That is, when the total of components (b1), (b2), (b3) and (b4) is 100% by mass, the content of each component is preferably 94.5-99.2% by mass, 0.1-2% by mass, 0.1-2% by mass and 0.1-1.5% by mass, more preferably 95.8-99% by mass, 0.35-1.5% by mass, 0.35 -1.5% by mass and 0.3-1.2% by mass. The content of component (b5) is preferably 0.03 to 1.5 parts by mass when the total of components (b1), (b2), (b3) and (b4) is 100 parts by mass, More preferably, it is 0.05 to 0.8 part by mass.

Still other antibacterial agents include organic antibacterial agents, inorganic antibacterial agents, and organic / inorganic antibacterial agents.
Examples of organic antibacterial agents include nitrile compounds such as 2,4,5,6-tetrachloroisophthalonitrile and 5-chloro-2,4,6-trifluoroisophthalonitrile; 2,3,5,6- Examples thereof include pyridine compounds such as tetrachloro-4-methylsulfonylpyridine and sodium 2-pyridinethiol-1-oxide. These can be used alone or in combination of two or more.
Examples of the inorganic antibacterial agents include silver antibacterial agents such as silver ion retention type and silver complex salt retention type; titanium oxide antibacterial agents; copper antibacterial agents; zinc oxide antibacterial agents. These can be used alone or in combination of two or more.

The component [B] may be a powder mixture containing the components (b1), (b2), (b3), (b4), etc., and is dispersed in water, an organic solvent, or a mixed medium thereof. Alternatively, it may be a dissolved composition. In addition to the above powder mixture and the composition dispersed or dissolved in the medium, this component [B] can be used as a mixture containing a predetermined amount of additives to be described later. The mixing method may be a conventionally known method, and may be either a dry method or a wet method. Examples of the mixing device include a rocking mill, a tumbler mixer, a drum mixer, a mixing shaker, a rocking shaker, a V-type mixer, and a W-type mixer.

In the antifungal resin composition of the present invention, the content of the component [B] is 0.01 to 10 parts by mass, preferably 0.05 to 8 parts, relative to 100 parts by mass of the component [A]. Part by mass, more preferably 0.08 to 5 parts by mass, particularly preferably 0.1 to 3 parts by mass. When the content of this component [B] is in the above range, the resulting molded article, film, etc., control the growth of fungi, bacteria, wood decay fungi, algae and marine organisms, and further, fungicidal, antibacterial It has excellent properties, anti-algae properties, deodorization properties and antiseptic properties, and is excellent in sustainability of these effects. In addition, when there is too much content of the said component [B], the external appearance properties, such as a molded product obtained, will fall.

Further, the antifungal resin composition of the present invention comprises an antioxidant, a plasticizer, an ultraviolet absorber, a weathering (light) agent, an antistatic agent, a lubricant, a crystal nucleating agent, a filler, a flame retardant, a foaming agent, a spreading agent. You may contain additives, such as an adhesive agent, an extender, an excipient | filler, a hardening | curing agent, a coloring agent, a fragrance | flavor, a dispersing agent, a leveling agent, an antifoamer, a matting agent, and an antifreezing agent.

The properties of the antifungal resin composition of the present invention are not particularly limited, and depending on the purpose, application, etc., a solid (pellet, powder mixture), liquid, a dispersion liquid in which raw material components are dispersed in a medium, a raw material It can be set as the solution etc. in which a component is melt | dissolved in a medium.

The antifungal resin composition of the present invention is preferably a solid and a molding material. In this case, the antifungal resin composition of the present invention can be produced by supplying the raw material components or a mixture thereof to various extruders, Banbury mixers, kneaders, continuous kneaders and the like and kneading them. A preferable production method is a method using an extruder, and among them, a method using a multi-screw extruder, and a method combining an extruder, a Banbury mixer, a continuous kneader and the like are preferable. Furthermore, when the raw material components are kneaded, the entire amount may be kneaded in a lump or may be kneaded while being divided and blended in multiple stages.

A molded article can be obtained using the antifungal resin composition of the present invention. Moreover, a molded article can also be obtained using the raw material composition formed by dividing the components [A] and [B] contained in the antifungal resin composition of the present invention into two or more. That is, the molded article of the present invention contains the above-mentioned antifungal resin composition of the present invention.
The molded product of the present invention may have a uniform composition throughout, or the concentration of the component [B] may vary in a predetermined direction, and the effect of the present invention is desired. The specific part to be formed may be formed by the antifungal resin composition of the present invention.

In the molded article of the present invention, the form thereof is not particularly limited, and is a predetermined shape body (film, fiber, tube, etc.) such as a plate shape, a linear shape, a ring shape, a net shape, a cylindrical shape, a semi-cylindrical shape, or a deformed shape. be able to. These may be either solid or foam. In addition, the molded product of the present invention may include a through hole, a groove, a concave portion, a convex portion, and the like at an arbitrary place.

The molded product of the present invention uses a mold-resistant resin composition having a uniform composition such as pellets, injection molding, (co) extrusion molding (sheet molding, film molding), profile extrusion molding, press molding, vacuum molding, foaming. It can be produced by a known method such as molding, melt spinning, dry spinning, or wet spinning. In addition, as described above, when the effect of the present invention is expressed at a desired site, the antifungal resin composition can be produced so as to be unevenly distributed at the site. Moreover, the composition in which the content rate of component [B] in an antifungal resin composition differs can also be manufactured by supplying in steps, for example.

When the molded article of the present invention is a housing or the like, the component [A] and [B] are mixed in advance at a high concentration (for example, 3 to 50% by mass). When preparing the master batch resin (S1) and the master batch (S2) composed of the remainder of the component [A] not containing the component [B], and (co) extrusion molding or injection molding, By supplying the master batch (S2), the dispersibility of the component [B] can be further improved.

In the present invention, in addition to the molded article formed from the antifungal resin composition of the present invention, a resin layer containing the antifungal resin composition of the present invention is provided on the surface of an article or layer made of another material. Laminate provided (composite article, laminate film, laminate sheet, etc.); laminate comprising two or more resin layers containing the antifungal resin composition of the present invention; The antifungal resin composition of the invention may be a laminate (composite article, laminated film, laminated sheet, etc.) provided with a film formed by using it as a paint or the like.

When the antifungal resin composition of the present invention is a paint, an adhesive, a sealing agent, or the like, the components [A] and [B] and additives used as necessary are added with water and / or It can be produced by dispersing or dissolving in a medium composed of an organic solvent. The paint is applied (brush coating, spraying, dipping), roll, flow, curtain, knife coating on the surface of a predetermined shape made of resin, metal, wood, paper, fiber, mortar, plaster, decorative gypsum board, etc. , Spin coating, printing, etc.), drying, etc., a film or the like can be formed.

The molded article of the present invention, or an article having a film or the like formed of the antifungal resin composition of the present invention generates or proliferates bacteria, organisms, etc. during use, transportation or storage of these products. However, it is suitable for use in a place where it adheres to or breeds a product.

The fungicide composition of the present invention contains a benzimidazole compound (b1), an organic iodine compound (b2), a thiazole compound (b3), and a haloalkylthio compound (b4), and each component. When the total content is 100% by mass, 85 to 99.97% by mass, 0.01 to 5% by mass, 0.01 to 5% by mass, and 0.01 to 5%, respectively. It is characterized by mass%.
The antifungal agent composition of the present invention can further contain an organic bromide compound (b5).
The description in said component [B] is applied about the compound of said component (b1), (b2), (b3), (b4) and (b5), a content rate, etc.

The antifungal composition of the present invention may further contain other antibacterial agents and the like as long as the effects of the present invention are not impaired. Examples of other antibacterial agents include organic antibacterial agents, inorganic antibacterial agents, and organic / inorganic antibacterial agents.
In addition, the antifungal composition of the present invention includes additives such as a dispersant, a spreading agent, a fragrance, an antioxidant, a bulking agent, an excipient, a colorant, and an antifreezing agent, depending on the purpose and application. It may contain.

The fungicide composition of the present invention may be a powder mixture (I) containing the above components (b1), (b2), (b3), (b4), etc., water, an organic solvent, or The composition (II) may be dispersed or dissolved in these mixed media.
The antifungal composition of the present invention can be obtained by mixing predetermined amounts of the above components (b1), (b2), (b3), (b4) and the like. The mixing method may be a conventionally known method, and may be either a dry method or a wet method. Examples of the mixing device include a rocking mill, a tumbler mixer, a drum mixer, a mixing shaker, a rocking shaker, a V-type mixer, and a W-type mixer.
When the antifungal composition of the present invention is the above powder mixture (I), it is suitable for molding materials prepared by blending with resin or the like; antiseptics; antifouling agents and the like. Using this molding material, it is also possible to make a molded product; a laminated product formed by laminating thin bodies. In addition, when the fungicide composition of the present invention is the composition (II), it is used as a paint or the like, and imparts antifungal properties to its surface by coating or spraying on a resin molded product, fiber or the like. be able to.

The fungicide composition of the present invention is suitable for use in a place where fungi, organisms, etc. are generated or proliferate during use, transportation or storage of the product, and adhere to or breed on the product.

The antifungal agent composition of the present invention, the antifungal resin composition of the present invention containing the same, and the molded product obtained using this resin composition are resistant to fungi, bacteria, wood decay fungi, algae, marine organisms, etc. And has resistance.
Examples of the fungus include those shown in Table 5.
Examples of the bacteria include yeast, spore bacteria, actinomycetes, Escherichia coli, Pseudomonas aeruginosa, Bacillus subtilis, Staphylococcus aureus, and specific examples include Bacillus cereus, Bacillus subtilis, Clostridium botulinum, Clostridium perfringens, Escherichia coli, , Lactobacillus bulgericus, Micrococcus glamaticus, Paecilomyces lilacinus, Pseudomonas aeruginosa, Pseudomonas flureseus, Proteus vulgaris, Proteus vulgariz a, Rhizoctonia solani, Streptomyces aureofaciene, Staphylococcus aureus, Staphylococcus faecalis, Salmonella arizonae, Saccharomyces cerevisiae, Saccharomyces rouxii, Streptoverticillium reticulum, is a Salmonella paratyphi and the like.
Examples of the wood-rotting fungi include Sugihiratake, Kawaratake, Statake, Namidatake, Watakusaretake, Ouzuratake and the like.
Examples of algae include those shown in Table 7.
Examples of marine organisms include mussels, oysters, hydroworms, barnacles, sea anemones, mussels, and seaweeds.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded. In the following, parts and% are: Unless otherwise noted, it is based on mass.

1. Raw material components The components used in the production of the resin composition are shown below.
1-1. Ingredient [A]
ABS resin (trade name “Techno ABS 350”, manufactured by Techno Polymer Co., Ltd.) was used as the resin (A1).
As the resin (A2), an ABS resin (trade name “Techno ABS 810”, manufactured by Techno Polymer Co., Ltd.) was used.
As the resin (A3), AES resin (trade name “Techno AES W210”, manufactured by Techno Polymer Co., Ltd.) was used.
As the resin (A4), AS resin (trade name “Sunrex SAN-R”, manufactured by Techno Polymer Co., Ltd.) was used.
As the resin (A5), a polystyrene resin (trade name “PSJ polystyrene GPPS679”, manufactured by PS Japan Ltd.) was used.
As the resin (A6), ABS / PC alloy (trade name “Excelloy CK20”, manufactured by Techno Polymer Co., Ltd.) was used.
As the resin (A7), a polycarbonate resin (trade name “NOVAREX 7022A”, manufactured by Mitsubishi Engineering Plastics) was used.
As the resin (A8), a polypropylene resin (trade name “NOVATEC PPBC6C”, manufactured by Nippon Polypro Co., Ltd.) was used.
As the resin (A9), a polyethylene resin (trade name “NOVATEC LDLF122”, manufactured by Nippon Polyethylene Co., Ltd.) was used.
Further, polybutylene terephthalate resin (trade name “Novaduran 5010R5”, manufactured by Mitsubishi Engineering Plastics) was used as the resin (A10).

1-2. Ingredient [B]
The following compounds (b11) and (b12) were used as the benzimidazole compound (b1).
(B11) Methyl 1H-2-benzimidazolecarbamate

(B12) Methyl 1-butylcarbamoyl-2-benzimidazolecarbamate

The following compounds (b21) and (b22) were used as the organic iodine compound (b2).
(B21) Diiodomethyl-p-tolylsulfone

(B22) 1-Diiodomethylsulfonyl-4-chlorobenzene As the thiazole compound (b3), the following compounds (b31) and (b32) were used.
(B31) 2- (4-thiazolyl) -1H-benzimidazole (b32) 2- (n-octyl) -4-isothiazolin-3-one

The following compounds (b41) and (b42) were used as the haloalkylthio compounds (b4).
(B41) N, N-dimethyl-N′-phenyl-N ′-(fluorodichloromethylthio) sulfamide

(B42) N-fluorodichloromethylthiophthalimide

The following compounds (b51) and (b52) were used as the organic bromide compound (b5).
(B51) 2-Bromo-2-nitro-1,3-propanediol (b52) 1,2-dibromo-2,4-dicyanobutane Other compounds (b6) include the following compounds (b61) and ( b62) was used.
(B61) 2,4,5,6-tetrachloroisophthalonitrile (b62) 2,3,5,6-tetrachloro-4-methylsulfonylpyridine

2. Preparation of fungicides composition and evaluation thereof Examples 1-1 to 1-10 and Comparative Examples 1-1 to 1-9
The above components (b1) to (b6) were supplied to a V-type mixer at the ratios shown in Tables 1 and 2, and mixed at room temperature for 30 minutes to obtain antifungal compositions B1 to B19.

Each composition was evaluated as follows.
2-1. Growth inhibitory minimum concentration Based on the test method described in “Koji Inspection Manual Color Chart” (published by Techno System) supervised by Kosuke Takatori, fungi, fungi, bacteria, algae, wood decay fungi and Each culture temperature, humidity, and medium in marine organisms were selected and the minimum growth inhibition concentration was measured. The unit of the numbers in the table is ppm. “-” Means that there was no effect.

2-2. Evaluation of Resistance to Fungi Examples 1-1 and 1-3 and Comparative Examples were made so that the content was 0.5% in polybutylene terephthalate resin (trade name “Novaduran 5010R5”, manufactured by Mitsubishi Engineering Plastics). Using each test piece comprising the antifungal composition of 1-2 and 1-6 and the test fungus (71 fungi) shown in Table 5, the apizza method based on the following conditions, that is, on the medium After spraying the test bacterial solution on the surface of the test piece disposed in the plate, the cells were cultured for 60 days, and the degree of bacterial growth after 14 days, 28 days, 48 days and 60 days was observed. Judgment criteria are “1” when the bacteria do not grow at all, “2” when the growth of the bacteria is 10% or less on the upper surface area of the test piece, and when 30% or less exceeding 10% Was “3”, “4” when 30% and 60% or less, and “5” when 60%. The results are shown in Table 6.
<Medium>
0.7 g KH ₂ PO ₄ , 0.7 g K ₂ HPO ₄ , 0.7 g MgSO ₄ .7H ₂ O, 1.0 g NH ₄ NO ₃ , 0.005 g NaCl, 0 .002 g of FeSO ₄ .7H ₂ O, 0.002 g of ZnSO ₄ .7H ₂ O, 0.001 g of MnSO ₄ .7H ₂ O, and 15 g of agar are added to 1,000 ml of pure water. And heated at 121 ° C. for 20 minutes to dissolve. Thereafter, an aqueous 0.01 N NaOH solution was added to adjust the pH to 6.0 to 6.5 to obtain an inorganic salt agar medium.
<Test bacterial solution>
(1) Mixed spore solution An aqueous solution obtained by removing agar from the medium was added to the spore, and the mixture was adjusted to 10 ⁶ ± 200,000 per milliliter and mixed in equal amounts.
(2) Wetting liquid A 0.05 g / liter sodium laurate aqueous solution was used.
<Culture conditions>
Using a circulator with a temperature / humidity thermostat, the temperature was 28 ° C. to 30 ° C., the relative humidity was 85% or more, and the cells were cultured for 60 days.

2-3. Sustainability evaluation for algae Each test piece in the above section 2-2, a test bacterial solution containing the test bacteria (71 fungi) shown in Table 5, and a test bacterial solution containing the algae (27 species) shown in Table 7 Was used to evaluate the sustainability of algae. That is, the test bacterial solution in the above section 2-2 is sprayed on the surface of the test piece disposed on the medium, and then the test bacterial solution containing algae (27 species) is sprayed under the following conditions: The cells were cultured for 28 days, and the degree of algae generation after 7 days, 14 days, 21 days and 28 days was observed. Judgment criteria are “1” when there is no growth of algae, “2” when growth of algae is 10% or less on the surface area of the upper surface of the test piece, and when 20% or less exceeding 10% Is “3”, 20% is 30% or less and “4”, and 30% is “5”. The results are shown in Table 8.
<Medium>
1.25 g KNO ₃ , 1.25 g MgSO ₄ .7H ₂ O, 1.25 g NaCl, 0.05 g FeSO ₄ .4H ₂ O, 0.1 g CaCl ₂ , 0.35 g K ₃ HPO ₄ and 15 g of agar were added to 1,000 ml of pure water and heated at 121 ° C. for 15 minutes to be dissolved. Thereafter, the pH was adjusted to 5.8 to obtain a Detmer agar medium.
<Culture conditions>
The cells were cultured in an incubator at a temperature of 27 ° C. ± 5 ° C. and a relative humidity of 95% ± 5% for 60 days. During the cultivation, the light was irradiated with 1,500 Lux (positive fluorescent lamp) for 8 hours per day, and the remaining 16 hours were unirradiated, and repeated for 28 days.

2-4. Real net test for marine organisms The fungicidal compositions of Examples 1-3 and Comparative Examples 1-7 were added to an acrylic paint having a solid content of 80% so that the content was 1% and 4%. Two suspensions were prepared by stirring. Thereafter, a net for fishing net made of nylon 6 (expanded into a 60 cm square by a wire) was immersed and fixed in the suspension to form a fungicidal layer on the surface of the net. Next, this net was suspended at a position 6 m below the sea level for 6 months, and the presence of marine organisms was observed every month. In addition, as Comparative Example 1-10, evaluation was also made on a net without the antifungal agent composition attached thereto. Judgment criteria are “-” when there is no marine organism attached to the surface of the fungicide layer, “+” when the marine organism adheres to the surface area of the net string of 10% or less, and “+” 10%. The case of exceeding 50% or less was designated as “++”, and the case of exceeding 50% was designated as “++++”. The results are shown in Table 9.

2-5. Evaluation Results Comparative Example 1-1 is an example in which the content ratio of the component (b1) is small outside the scope of the present invention, that is, an example in which the content ratio of the components (b2) to (b4) is large and has an antifungal property. Few fungi were exhibited. In addition, even the fungi exhibiting the effect had a high growth inhibition minimum concentration.
Comparative Example 1-2 is an example consisting of only component (b1), and there were few fungi exhibiting antifungal properties. In addition, even the fungi exhibiting the effect had a high growth inhibition minimum concentration. And the resistance with respect to a fungus and the sustainability of the effect with respect to algae were not enough.
Comparative Example 1-3 is an example not containing the components (b3) and (b4), and there were few fungi exhibiting antifungal properties. In addition, even the fungi exhibiting the effect had a high growth inhibition minimum concentration.
Comparative Example 1-4 is an example not containing the components (b2) and (b4), and there were few fungi exhibiting antifungal properties. In addition, even the fungi exhibiting the effect had a high growth inhibition minimum concentration.
Comparative Example 1-5 is an example not containing the components (b2) and (b3), and there were few fungi exhibiting fungicidal properties. In addition, even the fungi exhibiting the effect had a high growth inhibition minimum concentration.
In Comparative Example 1-6, the composition of Example 2 in JP-A-8-92012, that is, the content of component (b1) is large outside the scope of the present invention, and the content of components (b2) to (b4) is high. This is a few examples, and there were few fungi exhibiting antifungal properties. In addition, even the fungi exhibiting the effect had a high growth inhibition minimum concentration. And the resistance with respect to a fungus and the sustainability of the effect with respect to algae were not enough.
Comparative Examples 1-7 to 1-9 are all examples in which the content of component (b1) is small outside the scope of the present invention, that is, the content of components (b2) to (b4) is large. There were few fungi exhibiting antifungal properties. In addition, even the fungi exhibiting the effect had a high growth inhibition minimum concentration. In Comparative Example 1-7, a sufficient effect was not obtained in the real net test for marine organisms.
Since Comparative Example 1-10 did not contain the fungicide composition, no effect was obtained in the real net test for marine organisms.
On the other hand, each of Examples 1-1 to 1-10 is an example containing components (b1) to (b4) in a predetermined range, and includes fungi, bacteria (including yeast, spore fungus, actinomycetes), Controls the growth of wood-rotting fungi, algae and marine organisms, and the decay of wood, and also has excellent antifungal, antibacterial, algal, anti-odor and antiseptic properties, and excellent sustainability of these effects. I understand. It should be noted that 0.5 parts of the compositions of Examples 1-1 to 1-10 and 99.5 parts of polybutylene terephthalate resin (trade name “Novaduran 5010R5”, manufactured by Mitsubishi Engineering Plastics) were melt-kneaded at 250 ° C. Then, when the surface appearance of the molded product obtained by injection molding was observed, no bleed-out of the fungicide composition was observed.

3. Preparation and Evaluation of Antifungal Resin Composition Examples 2-1 to 2-31 and Comparative Examples 2-1 to 2-21
The above components [A] (A1 to A10) and the components [B] (B1, B3, B4, B5, B12, B16, B17 and B18) shown in Table 1 or Table 2 are used in Tables 10 to 14 The mixture is supplied to a Henschel mixer at the ratio described in the above, mixed at room temperature, melt-kneaded using a single-screw extruder “NVC50” (model name) manufactured by Nakatani Machinery Co., Ltd., and pellets (antifungal resin composition) did. The cylinder temperature during melt kneading is 200 ° C. to 230 ° C. when the component [A] is (A1) to (A6), and 230 ° C. to 260 ° C. when it is (A7). In the case of (A8) and (A9), it was set to 180 ° C. to 210 ° C., and in the case of (A10), it was set to 230 ° C. to 260 ° C.

The following evaluation was performed on the pellets obtained above. Test specimens for evaluation were prepared using an injection molding machine “35AD” (model name) manufactured by Nippon Steel Works, in which the pellets were sufficiently dried and the resin melting temperature was set to 180 ° C. to 240 ° C. It was obtained by cutting a flat molded product having a length of 80 mm, a width of 55 mm, and a thickness of 2.4 mm. The size is 30 mm in length, 30 mm in width, and 2.4 mm in thickness. In Comparative Example 2-5, the following evaluation was stopped because the antifungal agent composition bleeded out from the surface of the flat plate-shaped molded article, resulting in poor appearance.

3-1. Evaluation of resistance to fungi Using each test piece made of the above-mentioned fungicidal resin composition and the test bacteria (71 fungi) shown in Table 5, the apizza method based on the following conditions, that is, disposed on the medium: The surface of the test piece was sprayed with the test bacterial solution and cultured for 60 days, and the degree of bacterial growth after 14 days, 28 days, 48 days and 60 days was observed. Judgment criteria are “1” when the bacteria do not grow at all, “2” when the growth of the bacteria is 10% or less on the upper surface area of the test piece, and when 30% or less exceeding 10% Was “3”, “4” when 30% and 60% or less, and “5” when 60%. The results are shown in Table 15 and Table 16.
<Medium>
0.7 g KH ₂ PO ₄ , 0.7 g K ₂ HPO ₄ , 0.7 g MgSO ₄ .7H ₂ O, 1.0 g NH ₄ NO ₃ , 0.005 g NaCl, 0 .002 g of FeSO ₄ .7H ₂ O, 0.002 g of ZnSO ₄ .7H ₂ O, 0.001 g of MnSO ₄ .7H ₂ O, and 15 g of agar are added to 1,000 ml of pure water. And heated at 121 ° C. for 20 minutes to dissolve. Thereafter, an aqueous 0.01 N NaOH solution was added to adjust the pH to 6.0 to 6.5 to obtain an inorganic salt agar medium.
<Test bacterial solution>
(1) Mixed spore solution An aqueous solution obtained by removing agar from the medium was added to the spore, and the mixture was adjusted to 10 ⁶ ± 200,000 per milliliter and mixed in equal amounts.
(2) Wetting liquid A 0.05 g / liter sodium laurate aqueous solution was used.
<Culture conditions>
Using a circulator with a temperature / humidity thermostat, the temperature was 28 ° C. to 30 ° C., the relative humidity was 85% or more, and the cells were cultured for 60 days.

3-2. Sustainability evaluation for algae Each test piece in the above section 3-1, and a test bacterial solution containing the test bacteria (71 fungi) shown in Table 5, and a test bacterial solution containing the algae (27 species) shown in Table 7 Was used to evaluate the sustainability of algae. That is, the test bacterial solution in the above section 3-1 is sprayed on the surface of the test piece disposed on the medium, and then the test bacterial solution containing algae (27 species) is sprayed under the following conditions: The cells were cultured for 28 days, and the degree of algae generation after 7 days, 14 days, 21 days and 28 days was observed. Judgment criteria are “1” when there is no growth of algae, “2” when growth of algae is 10% or less on the surface area of the upper surface of the test piece, and when 20% or less exceeding 10% Is “3”, 20% is 30% or less and “4”, and 30% is “5”. The results are shown in Table 17.
<Medium>
1.25 g KNO ₃ , 1.25 g MgSO ₄ .7H ₂ O, 1.25 g NaCl, 0.05 g FeSO ₄ .4H ₂ O, 0.1 g CaCl ₂ , 0.35 g K ₃ HPO ₄ and 15 g of agar were added to 1,000 ml of pure water and heated at 121 ° C. for 15 minutes to be dissolved. Thereafter, the pH was adjusted to 5.8 to obtain a Detmer agar medium.
<Culture conditions>
The cells were cultured in an incubator at a temperature of 27 ° C. ± 5 ° C. and a relative humidity of 95% ± 5% for 60 days. During the cultivation, the light was irradiated with 1,500 Lux (positive fluorescent lamp) for 8 hours per day, and the remaining 16 hours were unirradiated, and repeated for 28 days.

3-3. Real net test on marine organisms Examples 2-32 and 2-33 and Comparative Examples 2-22 to 2-24
The fungicidal compositions B3 and B17 were added to a paint containing an acrylic resin having a solid content of 80% so that the content would be 1% and 4%, respectively, and stirred to obtain two types of suspensions. A suspension was prepared. Thereafter, a net for fishing net made of nylon 6 (expanded into a 60 cm square by a wire) was immersed and fixed in the suspension to form a fungicidal layer on the surface of the net. Next, this net was suspended at a position 6 m below the sea level for 6 months, and the presence of marine organisms was observed every month. Further, as Comparative Example 2-24, an actual net test was conducted using an acrylic paint not containing the antifungal agent composition [B]. Judgment criteria are “-” when there is no marine organism attached to the surface of the fungicide layer, “+” when the marine organism adheres to the surface area of the net string of 10% or less, and “+” 10%. The case of exceeding 50% or less was designated as “++”, and the case of exceeding 50% was designated as “++++”. The results are shown in Table 18.

3-4. Evaluation Results Comparative Examples 2-1, 2-6, 2-14 and 2-18 are examples containing no component [B], and the resistance to fungi was poor (see Tables 15 and 16).
Comparative Examples 2-2 and 2-7 are examples containing the fungicide composition B12 consisting only of the component (b1), and the resistance to fungi and the sustainability of the effect on algae were not sufficient ( Table 15 and Table 17).
In Comparative Examples 2-3, 2-8, 2-10, 2-15, 2-17 and 2-19, the composition of Example 2 in JP-A-8-92012, that is, the content of component (b1) is This is an example using the fungicide composition B16 which is outside the scope of the present invention and has a low content of components (b2), (b3) and (b4), and exhibits antifungal properties as described above. There are few fungi (see Table 4). Moreover, in these comparative examples, resistance to fungi and persistence of the effect on algae were not sufficient (Table 10, Table 11, Table 12, Table 13, Table 14, Table 15, Table 16, and Table 17). reference).
Comparative Examples 2-4, 2-9, 2-11, 2-12, 2-20 and 2-21 use the antifungal agent composition B17 in which the content of component (b1) is small outside the scope of the present invention. The resistance to fungi and the persistence of the effect on algae were not sufficient (see Table 10, Table 11, Table 12, Table 14, Table 15, Table 16, and Table 17).
Comparative Examples 2-13 and 2-16 are examples using the fungicide composition B18 in which the content of the component (b1) is small outside the scope of the present invention, and the resistance to fungi and the effect on algae are Persistence was not sufficient (see Table 12, Table 13, Table 16, and Table 17).
Further, in the real net test for marine organisms, Comparative Examples 2-22 and 2-23 are examples using a paint containing the antifungal agent composition B17 in which the content ratio of the component (b1) is small outside the scope of the present invention. Yes, marine life repellent was not enough. Comparative Example 2-24 was an example containing no component [B], and the repellent properties of marine organisms were not sufficient (see Table 18).
On the other hand, Examples 2-1 to 2-33 are examples using the components (b1) to (b4) or the component [B] containing the components (b1) to (b5) in a predetermined ratio. Controls fungi, bacteria (including yeast, spore fungus, actinomycetes), wood decay fungi, algae and marine life, and wood decay, and also has fungicidal, fungicidal, antialgal, deodorant and It turns out that it is excellent in antisepticity and is excellent in the sustainability of these effects. When the surface appearance of the molded products obtained by injection molding of the compositions of Examples 2-1 to 2-31 was observed, no bleed-out of the fungicide composition was observed.

The molded article of the present invention, or an article having a film or the like formed of the antifungal resin composition of the present invention generates or proliferates bacteria, organisms, etc. during use, transportation or storage of these products. However, it is suitable for use in a place where it adheres to or breeds a product.
Specific fields include weak electricity-related products, daily necessities, sports / leisure products, building and civil engineering materials, agricultural and forestry materials, fishery materials, industrial materials, materials for public institutions, transportation-related materials, textile products, etc. It is done.
Weak electricity-related products include refrigerators, washing machines, vacuum cleaners, fans, dryers, air conditioners, telephones, electric kettles, rice cookers, dishwashers, dish dryers, microwave ovens, mixers, VTRs, TVs, watches, stereos , Tape recorders, OA devices, etc., and can be a housing, a handle, a tray, or the like.
Living items include bathroom items, kitchen items (triangular corners, chopping boards, balls, lanterns, etc.), laundry items, cleaning items (brushes, etc.), rugs, interior items, stationery items (fountain pens, mechanical pencils, ballpoint pens, etc.), curtains , Towels, bedding, beds, rain gear, garbage baskets, flower vases, gardening tools, flower pots, cushions, bags, flags, etc.
Examples of sports / leisure goods include sports equipment, sports clothing, protectors, gloves, shoe materials, saddle materials, grip taping materials, pool equipment, park equipment, beach equipment, shading materials, tents, ropes, boat yacht equipment, etc. .
Examples of building civil engineering materials include tents, curing sheets, curing meshes, antifouling membrane materials, canvases, roofing materials, artificial turf, building interior materials, interior material reinforcing fibers, paint reinforcing fibers, and wall soil reinforcing fibers.
Agricultural and forestry materials include water tanks, cocoons, agricultural hoses, agricultural films, greenhouse equipment, cold cocoons, hydroponics materials, insect nets, and the like.
Examples of fishery materials include fishing nets, aquaculture equipment, mooring ropes, fenders, sea anchors, and floating bodies.
Industrial materials include water pipes, hoses, conveyor belts, land nets, land ropes, filters, felts, various containers, packaging materials, drainage side gutters, water treatment materials, food processing plant materials, control devices, and home appliances. And buttons such as computers, operation instruments, optical instruments, various medical instruments, water evaporation materials, and the like.
As materials for public institutions and traffic-related materials, interior and exterior materials for automobiles, door handles, hanging leather, buttons for operating vending machines, escalator handles, guide ropes, road signs, materials for advertisement signs, interiors for hospitals and nursing homes Goods materials, interior materials and the like.
As textile products, textile products include woven knitted fabrics, fabrics, spunbonds, felts, synthetic paper intermediate products, and further processed clothing (outer clothes, work clothes, underwear, socks, hats, etc.) and knitted clothing. , Industrial sewing products, strings, tapes, ropes, ribbons and the like.
The processed product is also used for the purpose of giving the effect of the present invention to nearby articles. For example, a product can be arranged for the purpose of preventing the invasion of bacteria and fungi, or a mesh product can be arranged for the purpose of reducing the invasion of flying bacteria.

The fungicide composition of the present invention is also suitable for use in a place where bacteria, organisms, etc. are generated or proliferate during use, transportation or storage of the product, and adhere to or propagate the product. For example, it can be used in the fields of paper / pulp industry, chemical industry, high-tech industry, livestock industry, fishery industry, agriculture, forestry, etc., specifically, fiber, wood / building materials, leather, adhesive, metal Processing oil, rubber, plastic film, cooling water, electrical equipment, optical equipment, air conditioner, ship bottom, fishing nets, fishing supplies, pharmaceuticals, agricultural chemicals, water, cosmetics / toiletries, sanitary goods, household goods, sports equipment , Leisure equipment, school supplies, toys, food storage, hospitals, facilities installed in nursing homes, and the like.

Claims (9)

1. [A] resin;
   [B] When the total of the following compounds (b1), (b2), (b3) and (b4) is 100% by mass, (b1) benzimidazole compound 85 to 99.97% by mass, (b2) organic An antifungal composition comprising 0.01 to 5% by mass of an iodo compound, 0.01 to 5% by mass of (b3) thiazole compound and 0.01 to 5% by mass of (b4) a haloalkylthio compound;
   And the antifungal agent composition [B] is 0.01 to 10 parts by mass with respect to 100 parts by mass of the resin [A]. .
2. The antifungal resin composition according to claim 1, wherein the benzimidazole compound (b1) is a benzimidazole carbamic acid derivative.
3. The fungicidal resin composition according to claim 2, wherein the benzimidazole carbamate derivative is at least one selected from methyl 1H-2-benzimidazole carbamate and methyl 1-butylcarbamoyl-2-benzimidazole carbamate. .
4. The organic iodo compound (b2) is an iodosulfonylbenzene derivative, the thiazole compound (b3) is a benzimidazole derivative having a thiazole group, and the haloalkylthio compound (b4) is a haloalkylthiosulfamide derivative. The antifungal resin composition according to claim 1.
5. The antifungal composition [B] further contains an organic bromide compound (b5), and the content of the organic bromide compound (b5) is determined based on the compounds (b1), (b2), and (b3). And the antifungal resin composition according to claim 1, which is 0.01 to 3 parts by mass when the total of (b4) is 100 parts by mass.
6. 6. The fungicides according to claim 5, wherein the organic bromide compound is at least one selected from 2-bromo-2-nitro-1,3-propanediol and 1,2-dibromo-2,4-dicyanobutane. Resin composition.
7. A molded product comprising the antifungal resin composition according to claim 1.
8. It contains a benzimidazole compound (b1), an organic iodo compound (b2), a thiazole compound (b3), and a haloalkylthio compound (b4), and the content of each component is 100 in total. When the mass percentage is 85% to 99.97% by mass, 0.01% to 5% by mass, 0.01% to 5% by mass, and 0.01% to 5% by mass, respectively, Fungi composition.
9. Furthermore, it contains an organic bromide compound (b5), and the content of the organic bromide compound (b5) is such that the benzimidazole compound (b1), the organic iodine compound (b2), and the thiazole compound (b3). ) And the haloalkylthio-based compound (b4) are 0.01 to 3 parts by mass, based on 100 parts by mass.