JP2011032394A - Aromatic vinyl-based resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic vinyl-based resin composition that prevents multiplication of fungi, bacteria (including yeast, spore fungi and actinomycetes), etc., has excellent fungicidal property, antimicrobial property, in a case in which contamination such as slime, etc., is attached to a molded product thereof, provides a molded product, a film, etc, having excellent detergent property, namely, antifouling property. <P>SOLUTION: The composition includes [A] a thermoplastic resin (except component [C]) comprising an aromatic vinyl-based resin as a main component, [B] a fungicide and [C] a polymer containing a polyether chain and a polyamide chain. The fungicide [B] contains at least one kind selected from a thiazole group-non-containing benzimidazole-based compound, an organoiodine-based compound, a thiazole-based compound and a haloalkylthio-based compound and the contents of the fungicide [B] and the polymer [C] are 0.01-10 pts. and 1-50 pts. based on 100 pts. of the thermoplastic resin [A]. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an aromatic vinyl-based resin composition that provides a molded article having excellent antifungal, antibacterial and antifouling properties against fungi, bacteria and the like. More specifically, the present invention relates to an aromatic vinyl resin composition having excellent detergency when dirt such as slime adheres to the molded product.

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, a thermoplastic resin composition containing an aromatic vinyl resin such as an ABS resin is used as a material for forming various molded products. However, the thermoplastic resin composition containing an aromatic vinyl resin and a fungicide may not exhibit the fungicide sufficiently.
Therefore, Patent Document 1 was selected from a styrene resin, a polyamide elastomer, a polyester elastomer, a polyalkylene oxide, and a compound or polymer having a molecular weight of 300 to 10,000 having at least one functional group. An antifungal resin composition containing at least one kind and an organic antifungal agent is disclosed.
In addition, Patent Document 2 discloses that a bioresistant drug compounded in a resin includes a nitrile compound, a pyridine compound, a haloalkylthio compound, an organic iodo compound, a thiazole compound, and a benzimidazole compound. There is disclosed a bioresistant molded article which is at least four selected compounds and whose drug content is in the range of 0.05 to 30% by weight with respect to all components constituting the molded article. .

JP-A-7-258506 JP-A-9-157111

Dirt on the surface of the resin molded product is various such as physical dirt, naturally occurring dirt, etc., and water used in places where it comes into contact with washing water, drainage, sewage, etc. in bathrooms, kitchens, toilets, toilets, etc. Mold or the like adhering to components under humid conditions in a rotating member, an air conditioner, a humidifier, an air purifier, or the like may cause slime or the like.
Although the resin composition having antifungal and / or antibacterial properties is widely known, there is a problem that when it is formed into a molded product, the performance deteriorates due to bleeding out of the antifungal agent with time. there were. As described above, when dirt such as slime adheres to the molded product, there is a problem that the detergency is insufficient or decreases with time.
The purpose of the present invention is to control the growth of fungi, bacteria (including yeasts, spore fungi, actinomycetes), etc., and is excellent in antifungal and fungicidal properties. In other words, it is an object to provide an aromatic vinyl-based resin composition that gives a molded article, a film, and the like excellent in detergency, that is, antifouling property.

As a result of intensive investigations, the present inventors give a fungicide containing a specific component and appropriate hydrophilicity to a thermoplastic resin mainly composed of an aromatic vinyl resin in order to solve the above-mentioned problems. It has been found that a composition containing a specific amount of a specific polymer gives a molded article excellent in antifungal property, antibacterial property and antifouling property (cleaning property), and the present invention has been completed. .
That is, the present invention is shown below.
1. [A] Thermoplastic resin mainly composed of aromatic vinyl resin (excluding [C] below), [B] Antifungal agent, [C] Polymer having polyether chain and polyamide chain An aromatic vinyl-based resin composition comprising:
The antifungal agent [B] includes a thiazole group-free benzimidazole compound, and at least one selected from the group consisting of an organic iodine compound, a thiazole compound, and a haloalkylthio compound,
The content of the antifungal agent [B] and the polymer [C] is 0.01 to 10 parts by mass and 1 to 50 parts by mass, respectively, with respect to 100 parts by mass of the thermoplastic resin [A]. An aromatic vinyl resin composition characterized by that.
2. The ratio of the content of the thiazole group-free benzimidazole compound and the total content of at least one selected from the group consisting of organic iodine compounds, thiazole compounds and haloalkylthio compounds is 2. The aromatic vinyl resin composition according to 1 above, which is 80 to 99.99 mass% and 0.01 to 20 mass%, respectively, when the total is 100 mass%.
3. 2. The fungicide [B] according to the above 1, comprising a thiazole group-free benzimidazole compound and at least two selected from the group consisting of an organic iodo compound, a thiazole compound and a haloalkylthio compound. Aromatic vinyl resin composition.
4). The ratio of the content of the thiazole group-free benzimidazole compound and the total of at least two contents selected from the group consisting of organic iodine compounds, thiazole compounds and haloalkylthio compounds is 4. The aromatic vinyl resin composition according to 3 above, which is 80 to 99.99 mass% and 0.01 to 20 mass%, respectively, when the total is 100 mass%.
5). The aromatic vinyl resin composition according to any one of 1 to 4 above, wherein the thiazole group-free benzimidazole compound is a benzimidazole carbamic acid derivative.
6). Any one of 1 to 5 above, wherein the polymer [C] is a polyether ester amide derived from a polyamide having carboxyl groups at both ends and a polyoxyalkylene ether and / or polyalkylene glycol of bisphenols. The aromatic vinyl resin composition according to Item.
7). A molded article formed by molding the aromatic vinyl resin composition according to any one of 1 to 6 above.

  According to the aromatic vinyl resin composition of the present invention, the growth of fungi, bacteria (including yeast, spore fungus, actinomycetes) and the like is controlled, and furthermore, it is excellent in antifungal, antibacterial and antifouling properties. , Molded articles (including solids and foams) having excellent sustainability of these effects can be obtained. In particular, in bathrooms, kitchens, toilets, washrooms, etc., water components used in places that come in contact with washing water, drainage, sewage, etc., components under humid conditions in air conditioners, humidifiers, air purifiers, etc. In this case, the slime and the like adhering to these can be easily washed. In addition, the molded article obtained using the aromatic vinyl resin composition of the present invention is less likely to cause the bleed out of the fungicide, and thus does not cause a decrease in the above effects and a decrease in surface appearance. . Therefore, a molded article, a film and the like produced using the aromatic vinyl resin composition of the present invention are suitable for applications requiring antifungal, antibacterial and antifouling properties (cleanability). As a molded article, for example, in bathroom utensils, kitchen utensils, air conditioners, humidifiers, air purifiers, etc., it is suitable as a watering member that tends to cause slime on its surface.

  The present invention will be described in detail below. In this specification, “(co) polymerization” means homopolymerization and copolymerization. Further, “(meth) acryl” means acryl and methacryl, and “(meth) acrylate” means acrylate and methacrylate.

  The aromatic vinyl resin composition of the present invention has a thermoplastic resin [A] (excluding [C] below), [B] an antifungal agent, [C] a polyether chain and a polyamide chain. The antifungal agent [B] is selected from the group consisting of thiazole group-free benzimidazole compounds, organic iodo compounds, thiazole compounds and haloalkylthio compounds. The content of the antifungal agent [B] and the polymer [C] is 0.01 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin [A]. And 1 to 50 parts by mass.

  The thermoplastic resin [A] is mainly composed of an aromatic vinyl resin, and may be a thermoplastic resin composed only of an aromatic vinyl resin, or an aromatic vinyl resin and an aromatic vinyl. It may be a combination (alloy resin or the like) with other thermoplastic resins other than the base resin. In the latter case, the content of the aromatic vinyl-based resin is preferably 30 to 99% by mass when the thermoplastic resin [A] is 100% by mass from the viewpoint of molding processability, mechanical properties, and the like. More preferably, it is 40-97 mass%, More preferably, it is 50-95 mass%.

  The aromatic vinyl resin is not particularly limited as long as it includes a structural unit derived from an aromatic vinyl compound. For example, aromatic vinyl rubber reinforced resin such as ABS resin, ASA resin, AES resin, etc .; polystyrene And aromatic vinyl (co) polymers such as acrylonitrile / styrene copolymer, styrene / maleic anhydride copolymer, and styrene / (meth) acrylic acid ester copolymer. These may be used alone or in combination of two or more. The aromatic vinyl resin is preferably an aromatic vinyl rubber reinforced resin.

  The aromatic vinyl rubber-reinforced resin polymerizes a vinyl monomer (a2) containing an aromatic vinyl compound in the presence of a rubbery polymer (hereinafter referred to as “rubbery polymer (a1)”). A rubber-reinforced vinyl resin (hereinafter referred to as “rubber-reinforced vinyl resin (A1)”) obtained as described above, or a vinyl-based monomer containing the rubber-reinforced vinyl resin (A1) and an aromatic vinyl compound. It is a combination (mixture) with a (co) polymer (hereinafter referred to as “(co) polymer (A2)”) containing a structural unit derived from the body.

  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.

  A resin containing a 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, as the rubbery polymer (a), a rubber-reinforced vinyl resin (A1) obtained when an ethylene / α-olefin copolymer and / or an ethylene / α-olefin / non-conjugated diene copolymer is used. The resin containing 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 in combination.
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 thereof include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, vinyl toluene, β-methyl styrene, ethyl styrene, p-tert-butyl styrene, vinyl xylene, vinyl naphthalene, 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 acid, 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, vinyl compounds 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.

  In the present invention, the vinyl monomer (a2) preferably contains an aromatic vinyl compound and a vinyl cyanide compound, and the total use amount thereof is molding processability, chemical resistance, dimensional stability, molding appearance. From the viewpoint of properties and the like, the amount is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the total amount of the vinyl monomer (a2). In addition, the use ratio of the aromatic vinyl compound and the vinyl cyanide compound is preferably respectively, from the viewpoint of molding processability, chemical resistance, dimensional stability, molding appearance, etc., when these totals are 100% by mass. Is 5 to 95 mass% and 5 to 95 mass%, more preferably 50 to 95 mass% and 5 to 50 mass%, still more preferably 60 to 95 mass% and 5 to 40 mass%.

Preferred examples of the rubber-reinforced vinyl resin (A1) include the following (1) to (3).
(1) Rubber-reinforced vinyl resin (2) rubber obtained by polymerizing vinyl monomer (a2) comprising an aromatic vinyl compound and a vinyl cyanide compound in the presence of rubber polymer (a1) Rubber-reinforced vinyl resin obtained by polymerizing vinyl monomer (a2) composed of an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid ester compound in the presence of a porous polymer (a1) (3) A rubber-reinforced vinyl resin obtained by polymerizing a vinyl monomer (a2) comprising an aromatic vinyl compound, a vinyl cyanide compound and a maleimide compound in the presence of the rubbery polymer (a1).

  The rubber-reinforced vinyl resin (A1) can be produced by polymerizing the vinyl monomer (a2) in the presence of the rubbery polymer (a1). As a polymerization method, emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a combination of these can be used.

  In the production of the rubber-reinforced vinyl resin (A1), the rubber polymer (a1) and the vinyl monomer (a2) are used in the reaction system in the total amount of the rubber polymer (a1). In the presence, the vinyl monomer (a2) may be added all at once to initiate the polymerization, or the polymerization may be carried out separately or continuously. Further, in the presence or absence of a part of the rubber polymer (a1), the vinyl monomer (a2) may be added all at once to initiate polymerization, or may be divided or continuously. May be added. At this time, the remainder of the rubber-like polymer (a1) may be added all at once during the reaction, divided or continuously.

  When the rubber-reinforced vinyl resin (A1) is produced by emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water and the like are used.

As the polymerization initiator, a redox in which an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, or the like and a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation are combined. System initiators; persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, tert-butyl peroxylaurate, and tert-butyl peroxymonocarbonate. These can be used alone or in combination of two or more. Moreover, the usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinylic monomer (a2) whole quantity.
The polymerization initiator can be added to the reaction system all at once or continuously.

Examples of the chain transfer agent include octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan, and other mercaptans; Examples include α-methylstyrene dimers. These can be used alone or in combination of two or more. The amount of the chain transfer agent used is usually 0.05 to 2.0 mass% with respect to the total amount of the vinyl monomer (a2).
The chain transfer agent can be added to the reaction system all at once or continuously.

  Examples of the emulsifier include anionic surfactants and nonionic surfactants. Anionic surfactants include higher alcohol sulfates; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylates, aliphatic phosphates, etc. Is mentioned. Examples of nonionic surfactants include polyethylene glycol alkyl ester compounds and alkyl ether compounds. These can be used alone or in combination of two or more. The usage-amount of the said emulsifier is 0.3-5.0 mass% normally with respect to the said vinylic monomer (a2) whole quantity.

Emulsion polymerization can be carried out under known conditions depending on the type of vinyl monomer (a2), polymerization initiator, and the like. The latex obtained by this emulsion polymerization is usually purified by coagulation with a coagulant to form a polymer component in powder form, and then washing and drying the polymer component. Examples of the coagulant include inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid.
In the case where two or more kinds of rubber-reinforced aromatic vinyl resins are contained in the aromatic vinyl resin, the resins may be mixed after being isolated from each latex. There are methods such as coagulating a mixture of latexes each containing a resin.

  Known methods can be applied to the method for producing a rubber-reinforced aromatic vinyl resin by solution polymerization, bulk polymerization, and bulk-suspension polymerization.

The graft ratio of the rubber-reinforced vinyl resin (A1) is preferably 30 to 150% by mass, more preferably 50 to 120% by mass, from the viewpoints of moldability and the surface appearance and impact resistance of the obtained molded product. It is. If the graft ratio of the rubber-reinforced vinyl resin (A1) is too small, the surface appearance and impact resistance of the aromatic vinyl 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 ratio (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). Medium (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, the processability of the aromatic vinyl resin composition of the present invention is excellent, and the resulting molded article is also excellent in impact resistance.
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 adjusting the polymerization temperature and the like.

  As described above, when the aromatic vinyl resin is an aromatic vinyl rubber reinforced resin, even if the aromatic vinyl rubber reinforced resin is only the rubber reinforced vinyl resin (A1). Alternatively, it may be a combination of a rubber-reinforced vinyl resin (A1) and a (co) polymer (A2) containing a structural unit derived from a vinyl monomer containing an aromatic vinyl compound. The vinyl monomer forming the (co) polymer (A2) includes an aromatic vinyl compound, and further includes a vinyl cyanide compound, a (meth) acrylic ester compound, a maleimide compound, an acid anhydride, and One or more selected from compounds having a functional group can be used in combination. 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. Also good. Two or more of these polymers may be contained.

Examples of the (co) polymer (A2) include the following (4) 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.
(4) One or more (co) polymers obtained by polymerizing only aromatic vinyl 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 may be used alone or in combination of two or more.

  Accordingly, specific examples of the (co) polymer (A2) include polystyrene, acrylonitrile / styrene copolymer, acrylonitrile / α-methylstyrene copolymer, styrene / methyl methacrylate copolymer, acrylonitrile / styrene / methacrylic. Examples thereof include an acid methyl copolymer, an acrylonitrile / styrene / N-phenylmaleimide copolymer, 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] (30 in methyl ethyl ketone) of a soluble component by acetone of the above aromatic vinyl rubber reinforced resin (however, acetonitrile is used when the rubbery polymer (a1) is an acrylic rubber). (Measured at ° 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, the aromatic vinyl rubber-reinforced resin was obtained by polymerization of a rubber-reinforced vinyl resin (A1) and a vinyl monomer when the rubber-reinforced vinyl resin (A1) alone was used ( In any case of comprising the (co) polymer (A2), the content of the rubbery polymer (a1) in the aromatic vinyl 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 aromatic vinyl 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. .

As described above, the thermoplastic resin [A] according to the present invention may be a combination of an aromatic vinyl resin and another thermoplastic resin.
Other thermoplastic resins include polyester resins; olefin resins; polycarbonate resins; polyamide resins; polyarylate resins; polyacetal resins; polyvinyl chloride resins such as polyvinyl chloride, ethylene / vinyl chloride polymers, and polyvinylidene chloride. Acrylic resins such as (co) polymers using one or more (meth) acrylic acid esters such as polymethyl methacrylate (PMMA); polyphenylene ether; polyphenylene sulfide; polytetrafluoroethylene, polyvinylidene fluoride, etc. Fluorine resins; Imide resins such as polyimide, polyamideimide, and polyetherimide; Ketone resins such as polyetherketone and polyetheretherketone; Sulfone resins such as polysulfone and polyethersulfone; Urethane resins; Polyacetic acid Alkylsulfonyl; polyethylene oxide, polyvinyl alcohol, polyvinyl ethers, polyvinyl butyral, phenoxy resin, a photosensitive resin; liquid crystal polymers; biodegradable plastic and the like. These can be used alone or in combination of two or more.
Of the above thermoplastic resins, polyester resins, olefin resins, polycarbonate resins, and polyamide resins that form an aromatic vinyl rubber-reinforced resin and an alloy resin are preferable.

  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 olefin-based resin is not particularly limited as long as it is a polymer including a monomer unit composed of an α-olefin having 2 or more carbon atoms. A preferable olefin resin is a polymer containing a monomer unit composed of an α-olefin having 2 to 10 carbon atoms. Therefore, a (co) polymer mainly containing one or more monomer units 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 copolymers are preferable, and polymers containing 50% by mass or more of propylene units with respect to all monomer units, that is, polypropylene and ethylene / propylene copolymers are more preferable. 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.
Moreover, the molecular weight of the olefin resin is not particularly limited, but from the viewpoint of moldability, the melt flow rate (based on JIS K7210) is preferably 0.01 to 500 g / 10 min, which corresponds to each value. Those having a molecular weight 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 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.

  The polycarbonate resin can also be used as an alloy in combination with 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.

  Examples of the thermoplastic resin [A] include an aromatic vinyl rubber reinforced resin, an alloy resin composed of an aromatic vinyl rubber reinforced resin and a polyester resin, and an alloy composed of an aromatic vinyl rubber reinforced resin and an olefin resin. Resin, alloy resin composed of aromatic vinyl rubber reinforced resin and polyester resin, alloy resin composed of aromatic vinyl rubber reinforced resin and polycarbonate resin, and aromatic vinyl rubber reinforced resin and polyamide resin. An alloy resin is preferable.

  When the thermoplastic resin [A] contains an alloy resin, a compatibilizing agent can be used as necessary in order to increase the compatibility between the aromatic vinyl resin and the other thermoplastic resin. The compatibilizer is not particularly limited, and a known compatibilizer can be used.

Next, the fungicide [B] will be described. In addition, this antifungal agent [B] is a component which also has actions, such as a fungicide and an antibacterial agent.
This antifungal agent [B] has a benzimidazole ring, does not have a thiazole group, does not contain a thiazole group-containing benzimidazole compound (hereinafter also referred to as “component (b1)”), and an organic iodine compound. And at least one selected from the group consisting of thiazole compounds and haloalkylthio compounds. If necessary, other compounds described later can be included.

  Examples of the component (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, the component (b1) is preferably a benzimidazole carbamic acid derivative.

〔式中、Ｒ^１及びＲ^２は、同一又は異なって、水素原子、置換基を有してもよい炭化水素基若しくは他の有機基であり、Ｒ^３は、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基若しくは他の有機基であり、Ｒ^４は、炭化水素基である。〕 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.

〔式中、Ｒ^１及びＲ^２は、同一又は異なって、水素原子、置換基を有してもよい炭化水素基若しくは他の有機基であり、Ｒ^３は、水素原子、置換基を有してもよいアルキル基、又は、置換基を有してもよいアリール基であり、Ｒは、有機基である。〕 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 component (b1) according to the present invention, methyl 1H-2-benzimidazolecarbamate and methyl 1-butylcarbamoyl-2-benzimidazolecarbamate are preferable, and in particular, methyl 1H-2-benzimidazolecarbamate is particularly preferable. preferable.

The organic iodine compound (hereinafter also referred to as “component (b2)”) is an organic compound having an iodine atom. However, haloalkylthio compounds are excluded.
Examples of the component (b2) include iodosulfonyl compounds and iodinated unsaturated aliphatic compounds. 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 component (b2) according to the present invention, diiodomethyl-p-tolylsulfone is particularly preferable.

The thiazole-based compound (hereinafter also referred to as “component (b3)”) is a compound having a thiazole group.
Examples of the component (b3) include thiazole group-containing benzimidazole derivatives, isothiazoline-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.

〔式中、Ｒ^１及びＲ^２は、同一又は異なって、水素原子、ハロゲン原子、アミノ基、スルホン酸（塩）基、ニトロ基、ヒドロキシル基、置換基を有してもよい炭化水素基、他の有機基であり、Ｒ^３は、水素原子、置換基を有してもよいアルキル基、又は、置換基を有してもよいアリール基であり、Ｒ^５は、アルキレン基である。また、ｍは０又は１である。〕 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. ]

左側の化合物は、２−（４−チアゾリル）−１Ｈ−ベンズイミダゾールである。

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

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

〔式中、Ｒ^６及びＲ^７は、同一又は異なって、水素原子、ハロゲン原子若しくは置換基を有してもよい炭化水素基であり、Ｒ^８は、置換基を有してもよい炭化水素基である。〕 The isothiazoline-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 etc. are mentioned. These can be used alone or in combination of two or more.

〔式中、Ｒ^９及びＲ^１０は、同一又は異なって、水素原子、ハロゲン原子、ニトロ基、カルボキシル基、シアノ基若しくは置換基を有してもよい炭化水素基であり、Ｒは、水素原子又は有機基である。〕 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.

〔式中、Ｒ^９及びＲ^１０は、同一又は異なって、水素原子若しくは置換基を有してもよい炭化水素基であり、Ｒは、−ＳＭ（Ｍは、Ｎａ、Ｚｎ等の金属原子である）又は有機基である。〕

〔式中、Ｒ^９、Ｒ^１０及びＲ^１１は、同一又は異なって、水素原子若しくは置換基を有してもよい炭化水素基であり、Ｒ^１２は、Ｒ^１３は、同一又は異なって、有機基である。〕 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, and R represents —SM (M represents a metal atom such as Na, Zn, etc. 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 component (b3), 2- (4-thiazolyl) -1H-benzimidazole is particularly preferable.

The haloalkylthio compound (hereinafter also referred to as “component (b4)”) is a compound having a —S—C—X bond (X: halogen atom).
Examples of the component (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 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 component (b4) according to the present invention, N, N-dimethyl-N′-phenyl-N ′-(fluorodichloromethylthio) sulfamide is particularly preferred.

  The antifungal agent [B] according to the present invention contains the component (b1) and at least one selected from the components (b2), (b3) and (b4). At this time, the ratio of the content of the component (b1) and the total of at least one content selected from the group consisting of the components (b2), (b3) and (b4) is the sum of both. When it is 100% by mass, preferably 80 to 99.99% by mass and 0.01 to 20% by mass, more preferably 85 to 99.97% by mass and 0.03 to 15% by mass, and still more preferably. They are 88-99.85 mass% and 0.15-12 mass%, Most preferably, they are 91-99.7 mass% and 0.3-9 mass%. When combined at the above ratio, the composition of the present invention controls fungal and bacterial growth, and is more excellent in sustainability such as fungicidal and antifungal properties.

Specific examples when the component (b1) and at least one selected from the components (b2), (b3) and (b4) are combined are shown below.
(1) Combination of thiazole group-free benzimidazole compound and organic iodo compound (2) Combination of thiazole group-free benzimidazole compound and thiazole compound (3) Thiazole group-free benzimidazole compound and haloalkylthio Combination of compounds (4) Combination of thiazole group-free benzimidazole compound, organic iodo compound and thiazole compound (5) Combination of thiazole group-free benzimidazole compound, organic iodo compound and haloalkylthio compound (6 ) Combination of thiazole group-free benzimidazole compound, thiazole compound and haloalkylthio compound (7) Thiazole group-free benzimidazole compound, organic iodo compound, thiazole The combination of compounds and haloalkylthio compounds

  In the said antifungal agent [B], when it is a combination of the component (b1) and one kind selected from the components (b2), (b3) and (b4), examples thereof are the above (1) to ( 3) It is as follows. In this case, the ratio of the content of the component (b1) and the content of one kind selected from the group consisting of the component (b2), the component (b3) and the component (b4) is the sum of both. When it is 100% by mass, preferably 80 to 99.99% by mass and 0.01 to 20% by mass, more preferably 85 to 99.97% by mass and 0.03 to 15% by mass, and still more preferably. They are 88-99.85 mass% and 0.15-12 mass%, Most preferably, they are 91-99.7 mass% and 0.3-9 mass%. When the antifungal agent [B] is combined at this ratio, the fungi and bacteria are prevented from growing and the sustainability such as fungicidal and antifungal properties is further improved.

  In the present invention, fungi, bacteria (including yeast, spore bacteria, actinomycetes) and the like is controlled, and further, it is excellent in fungicidal and antifungal properties, and particularly excellent in the sustainability of these effects. The fungicide [B] is a combination of the component (b1) and at least two selected from the components (b2), (b3) and (b4), that is, the above-described embodiments (4) to (7). preferable. In this case, the ratio of the content of the component (b1) and the content of two kinds selected from the group consisting of the component (b2), the component (b3) and the component (b4) is the sum of both. When it is 100% by mass, preferably 80 to 99.99% by mass and 0.01 to 20% by mass, more preferably 85 to 99.97% by mass and 0.03 to 15% by mass, and still more preferably. They are 88-99.85 mass% and 0.15-12 mass%, Most preferably, they are 91-99.7 mass% and 0.3-9 mass%.

As described above, the antifungal agent [B] may further contain other compounds in addition to the essential components. Examples of other compounds include organic bromine compounds.
The organic bromide compound is an organic compound having a bromine atom. However, haloalkylthio compounds are excluded.
Examples of the organic bromide compound include 2,2-dibromo-3-nitrilopropionamide, 2,2-dibromo-4-nitrilobutanamide, 1,2-dibromo-2,4-dicyanobutane, and 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, 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, Bromoacetate, 1,2-dibromopropionaldehyde, N-bromoacetamide, hexabromodimethylsulfone, bromomethylthiocyanate, 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, Examples include 6-tribromophenol and 1-bromo-3-ethoxycarbonyloxy-1,2-diiodo-1-propene. These can be used alone or in combination of two or more. When the said antifungal agent [B] contains these organic bromide compounds, it is excellent in antibacterial properties against spore bacteria such as Bacillus genus and Clostridium genus and wood rot fungi.
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 antifungal agent [B] contains an organic bromide compound, the content of the organic bromide compound is preferably 0.01 to 3 parts by mass when the component (b1) is 100 parts by mass. More preferably, it is 0.02-2.5 mass part, More preferably, it is 0.03-2 mass part. When the organic bromide compound is contained in the above-described ratio, excellent resistance to fungi, bacteria, algae, wood decay fungi, marine organisms, and the like can be obtained in the obtained molded article and the like.

The antifungal agent [B] can further contain other antibacterial agents. Examples of 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 2-pyridinethiol-1-oxide sodium. 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 fungicide [B] may be a powder or a powder mixture, or a composition dispersed or dissolved in water, an organic solvent, or a mixed medium thereof. The antifungal agent [B] can be used as a mixture containing a predetermined amount of additives to be described later in addition to the above powder mixture and a composition dispersed or dissolved in a medium. 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 aromatic vinyl resin composition of the present invention, the content of the antifungal agent [B] is 0.01 to 10 parts by mass with respect to 100 parts by mass of the thermoplastic resin [A], preferably 0.05-8 mass parts, More preferably, it is 0.08-5 mass parts, Most preferably, it is 0.1-3 mass parts. When the content of the antifungal agent [B] is in the above range, the obtained molded article or the like controls the growth of fungi and bacteria, and further has excellent antifungal and antifungal properties and sustains these effects. Excellent in properties. In addition, when there is too much content of the said antifungal agent [B], the external appearance property of the molded article etc. which are obtained will fall, and when there is too little content, antifungal and fungicidal properties will become inadequate.

  Next, the polymer [C] is a polymer having a polyether chain and a polyamide chain. By containing this polymer [C], the aromatic vinyl resin composition of the present invention can impart appropriate hydrophilicity to the resulting molded product, and dirt such as slime adheres to the surface. In this case, cleaning with water or the like can be facilitated.

  The structure of the polyether chain and the polyamide chain contained in the polymer [C] is not particularly limited, but is usually a polymer having a structure in which the polyether chain and the polyamide chain are linearly bonded. Examples of the polymer [C] include polyether amide and polyether ester amide. These may be used alone or in combination. In the present invention, polyether ester amide is preferred because of its excellent wettability with water and compatibility with aromatic vinyl resins and the like.

  Examples of the polyether ester amide include polyether ester amides derived from polyamides having carboxyl groups at both ends and polyoxyalkylene ethers and / or polyalkylene glycols of bisphenols.

  As the polyamide having carboxyl groups at both ends used for the formation of the polyether ester amide, (1) a dicarboxylic acid having 4 to 20 carbon atoms is used as a molecular weight regulator, and in the presence of the dicarboxylic acid, carbon A polyamide obtained by ring-opening polymerization of a lactam having 6 to 12 or more (caprolactam, enantolactam, laurolactam, undecanolactam, etc.), (2) an aminocarboxylic acid having 6 to 12 or more carbon atoms (ω) A polyamide obtained by polycondensation of aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, 12-aminododecanoic acid, etc.), (3) a dicarboxylic acid having 4 to 20 carbon atoms (adipic acid, azelaic acid, Sebacic acid, undecanedioic acid, terephthalic acid, isophthalic acid, sodium 3-sulfoisophthalate, etc.) Prime numbers 4-12 or more diamines (hexamethylenediamine, heptamethylene diamine) polyamides obtained by the polycondensation and the like. Of these, the polyamides (1) and (2) are preferred, the polyamide (1) is particularly preferred, and the polyamide obtained from caprolactam is particularly preferred.

The polyoxyalkylene ethers of bisphenols used for forming the polyether ester amide can be obtained, for example, by adding alkylene oxides having 2 to 4 carbon atoms to bisphenols.
Examples of bisphenols include bisphenol A, bisphenol F, bisphenol S, 4,4′-dihydroxydiphenyl-2,2-butane, and the like. Of these, bisphenol A is preferred.
Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, 1,2- or 1,4-butylene oxide. These may be used alone or in combination of two or more. Of these, ethylene oxide is preferred.

  Polyalkylene glycols used for forming the polyether ester amide include polyethylene glycol, polypropylene glycol, polybutylene glycol, polyhexamethylene glycol, ethylene oxide and propylene oxide block or random copolymer, ethylene oxide and tetrahydrofuran block or And a random copolymer. These may be used alone or in combination of two or more. Of these, polyethylene glycol is preferred.

  The number average molecular weights (Mn) of the polyamides having carboxyl groups at both ends, the polyoxyalkylene ethers of the bisphenols and the polyalkylene glycols are usually 200 to 5,000, preferably 500 to 3, respectively. 000, more preferably 1,000 to 3,000. When Mn is less than 200, the heat resistance of the resulting polyether ester amide tends to decrease. On the other hand, when Mn exceeds 5,000, the reactivity is lowered, so that a great amount of time tends to be required during the production of the polyetheresteramide.

The polyether ester amide can be produced, for example, by heating a polyamide having carboxyl groups at both ends and a polyoxyalkylene ether and / or polyalkylene glycol of bisphenols under reduced pressure.
At this time, since the total use amount of the polyoxyalkylene ether of the bisphenols and / or the polyalkylene glycol exhibits the effect of containing the polymer [C], the polyamide having carboxyl groups at both ends is used. When the total of the polyoxyalkylene ether of bisphenols and polyalkylene glycol is 100% by mass, it is usually 20 to 80% by mass.
Moreover, the use ratio of the polyoxyalkylene ether of the bisphenols and the polyalkylene glycol is preferably 5 to 100% by mass and 0 to 95% by mass, respectively, when the total of these is 100% by mass. More preferably, they are 50-100 mass% and 0-50 mass%.

  As the above polyether ester amide, it has excellent wettability with water and is excellent in compatibility with aromatic vinyl resins and the like. From the polyamides having carboxyl groups at both ends and polyoxyalkylene ethers of bisphenols Derived polyetheresteramides are preferred.

In the aromatic vinyl resin composition, Mn of the polymer [C] is preferably more than 10,000 and 100,000 or less, and more preferably 12,000, because appropriate dispersibility is obtained. -80,000, more preferably 15,000-60,000.
Moreover, the said polymer [C] is a solid normally, and a softening point is 100 to 250 degreeC normally.

  In the aromatic vinyl resin composition of the present invention, the content of the polymer [C] is 1 to 50 parts by mass, preferably 5 to 45 parts per 100 parts by mass of the thermoplastic resin [A]. Part by mass, more preferably 10 to 40 parts by mass. When the content of the polymer [C] is in the above range, the resulting molded article or the like controls the growth of fungi, bacteria (including yeast, spore fungus, actinomycetes) and the like, and has fungicidal and fungicidal properties. Excellent in cleaning and cleaning properties, and excellent in sustainability of these effects. In addition, if the content of the polymer [C] is too large, the heat resistance, mechanical properties and the like of the obtained molded product are reduced, and if the content is too small, the cleaning property against dirt such as slime is insufficient. Become.

  The aromatic vinyl resin composition of the present invention comprises an antioxidant, a plasticizer, an ultraviolet absorber, a weathering agent, a light resistance agent, an anti-aging agent, an antistatic agent, a lubricant, a crystal nucleating agent, a filler, a flame retardant, and a foam. Additives such as agents, spreading agents, extenders, excipients, curing agents, coloring agents, fragrances, dispersants, leveling agents, antifoaming agents, matting agents, and antifreezing agents can be contained.

  The aromatic vinyl-based resin composition of the present invention is usually solid at ordinary temperature, and can be produced by supplying each component or a mixture thereof to an extruder, a Banbury mixer, a kneader, a continuous kneader, and kneading. it can. 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.

  In the production of the composition, the antifungal agent [B] comprising a part of the thermoplastic resin [A] and the antifungal agent [B] is used in a high concentration (for example, 3 to 50% by mass). ) Contained in the master batch resin (S1) and the remainder of the thermoplastic resin [A] and the polymer [C], the master batch not containing the fungicide [B] (S2) A method of preparing and kneading both can be applied. In this case, the dispersibility of the fungicide [B] in the composition can be further improved.

A molded article can be obtained by using the aromatic vinyl resin composition of the present invention. Moreover, using the raw material composition formed by dividing the thermoplastic resin [A], the fungicide [B], the polymer [C] and the like contained in the aromatic vinyl resin composition of the present invention into two or more. A molded product can also be obtained.
The molded article of the present invention may have a uniform composition over the whole, or the concentration of the antifungal agent [B] or the polymer [C] may be changed in a predetermined direction. And the specific site | part which desires the effect of this invention may be formed with the aromatic vinyl-type resin composition of this 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 an aromatic vinyl 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, It can be produced by a known method such as foam molding, melt spinning, dry spinning, wet spinning. Further, as described above, when the effect of the present invention is expressed at a desired site, the aromatic vinyl resin composition can be produced so as to be unevenly distributed at that site. Further, as a constituent of the aromatic vinyl resin composition of the present invention, a plurality of compositions having different proportions of the fungicide [B] and the polymer [C] are used, for example, these are supplied stepwise. Can also be manufactured.

  In the present invention, in addition to the molded article formed by the aromatic vinyl resin composition, a laminate comprising a resin layer containing the aromatic vinyl resin composition on the surface of an article or layer made of another material ( Composite articles, laminated films, laminated sheets, etc.); a laminate comprising two or more resin layers containing the aromatic vinyl resin composition; the aromatic vinyl resin composition on the surface of an article made of another material; Can be made into a laminate (composite article, laminated film, laminated sheet, etc.) provided with a film formed by using as a paint or the like. The molded article of the present invention is suitable for use in a place where bacteria, organisms, etc. are generated or proliferate during use, transportation or storage of the product, and the product adheres to or propagates.

A molded product formed by molding the aromatic vinyl resin composition of the present invention has resistance to fungi, bacteria, and the like.
Examples of the fungus include those shown in Table 3.
Examples of the bacteria include yeast, spore bacteria, actinomycetes, Escherichia coli, Pseudomonas aeruginosa, Bacillus subtilis, Staphylococcus aureus, and the like. aerogenes, Lactobacillus bulgericus, Micrococcus glamaticus, Paecilomyces lilacinus, Pseudomonas aeruginosa, Pseudononasflureseus, Proteus vulgariculus, Proteus vulgaricus acea, Rhizoctonia solani, Streptomyces aureofaciene, Staphylococcus aureus, Staphylococcus faecalis, Salmonella arizonae, Saccharomyces cerevisiae, Saccharomyces rouxii, Streptoverticillium reticulum, Salmonella paratyphi, and the like.

  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. Thermoplastic resin [A]
ABS resin (trade name “Techno ABS 350”, manufactured by Techno Polymer Co., Ltd.) was used as the resin (A1).
As the resin (A2), ABS / PC alloy (trade name “Excelloy CK20”, manufactured by Techno Polymer Co., Ltd.) was used.
AS resin (trade name “SANREX SAN-R”, manufactured by Techno Polymer Co., Ltd.) was used as the resin (A3).

1-2. Component of fungicide [B] The following 1H-2-benzimidazole carbamate methyl was used as the thiazole group-free benzimidazole compound (b1).

The following diiodomethyl-p-tolylsulfone was used as the organic iodo compound (b2).

  As the thiazole-based compound (b3), 2- (4-thiazolyl) -1H-benzimidazole was used.

The following N, N-dimethyl-N′-phenyl-N ′-(fluorodichloromethylthio) sulfamide was used as the haloalkylthio compound (b4).

1-3. Polymer [C]
A polyether ester amide block polymer (trade name “Pelestat M-140”, manufactured by Sanyo Chemical Industries, Ltd.) was used.

2. Preparation of antifungal agent [B] The above components (b1) to (b4) are supplied to the V-type mixer at the ratios shown in Table 1, mixed at room temperature for 30 minutes, and the antifungal agent (B1) to (B7) was obtained.

3. Preparation and Evaluation of Aromatic Vinyl Resin Composition Examples 1 to 11 and Comparative Example 1-3
The thermoplastic resin [A], the fungicide [B] and the polymer [C] are supplied to a Henschel mixer in the proportions shown in Table 2, mixed at room temperature, and then single screw extrusion manufactured by Nakatani Machinery Co., Ltd. Using a machine “NVC50” (model name), the mixture was melt-kneaded to obtain pellets (aromatic vinyl resin composition). In addition, the cylinder temperature at the time of melt-kneading was 200 degreeC-230 degreeC.

  The following evaluation was performed about the pellet obtained above. The test piece for evaluation was prepared by using an injection molding machine “J35AD” (model name) manufactured by Nippon Steel Works, which was set so that the melting temperature of the resin would be 180 ° C. to 240 ° C. after the pellets were sufficiently dried. 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.

3-1. Evaluation of resistance to fungi Using each test piece made of the above aromatic vinyl resin composition and the test bacteria (71 fungi) shown in Table 3, the apizza method based on the following conditions, that is, disposed on the medium The surface of the test piece was sprayed with a test bacterial solution and cultured for 14 days, and the degree of bacterial growth after 14 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 4.
<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.

  As is apparent from Table 4, Examples 1 to 11 are excellent in resistance to fungi.

3-2. Detergency evaluation One test piece was sequentially subjected to the following treatment, and the surface of the test piece after <2>, <3>, <5>, <6>, <8> and <9> was visually observed. The cleaning property was evaluated according to the criteria described below. The results are shown in Table 5.
<1> Application of glue Application of a paste for stationery (trade name “NA-150”, manufactured by Yamato Co., Ltd.) to the surface of a test piece made of the aromatic vinyl resin composition is 0.5 mm thick. did.
<2> Cultivation The test piece was placed on the medium prepared in 3-1, and the mixed spore solution prepared in 3-1 was sprayed on the surface of the glue film in the test piece. Thereafter, this was cultured for 28 days. The culture conditions were a circulator with a temperature / humidity thermostat, temperature 28 ° C. to 30 ° C., and relative humidity 85% or more.
<3> Cleaning Place the test piece with glue film vertically, and from a distance of about 20 cm, discharge water at a water temperature of 23 ° C. using a hand shower at a water power of 10 liters per minute and wash for 30 seconds. As a result, the entire paste was washed away.
<4> Application of glue The above-mentioned paste for stationery was applied to the surface of the test piece washed in <3> so as to have a thickness of 0.5 mm.
<5> Culture The test piece was placed on the medium prepared in 3-1, and the mixed spore solution prepared in 3-1 was sprayed on the surface of the glue film in the test piece. Thereafter, this was cultured for 28 days. The culture conditions were a circulator with a temperature / humidity thermostat, temperature 28 ° C. to 30 ° C., and relative humidity 85% or more.
<6> Cleaning Place the test piece with glue film vertically, and from a distance of about 20 cm, discharge water at a water temperature of 23 ° C. using a hand shower at a water force of 10 liters per minute and wash for 30 seconds. As a result, the entire paste was washed away.
<7> Application of glue The above-mentioned paste for stationery was applied to the surface of the test piece washed in <6> so as to have a thickness of 0.5 mm.
<8> Culture A test piece was placed on the medium prepared in 3-1, and the mixed spore solution prepared in 3-1, was sprayed on the surface of the glue film in the test piece. Thereafter, this was cultured for 28 days. The culture conditions were a circulator with a temperature / humidity thermostat, temperature 28 ° C. to 30 ° C., and relative humidity 85% or more.
<9> Cleaning Place the test piece with glue film vertically, and from a distance of about 20 cm, discharge water with a water temperature of 23 ° C. using a hand shower at a water power of 10 liters per minute and wash for 30 seconds. As a result, the entire paste was washed away.

(Criteria)
A: No fungal growth was observed.
○: Fungal growth was less than 10% of the surface area of the test piece surface.
(Triangle | delta): The adhesion area of fungi was 10% or more and less than 80%.
X: The adhesion area of fungi was 80% or more.

Table 5 shows the following.
The comparative example 1 is an example using the composition which does not contain a polymer [C], and the sustainability of antifungal property, antibacterial property, and washing | cleaning property was not enough. Comparative Example 2 is an example using a composition that does not contain the fungicide [B], and did not exhibit any fungicide, antibacterial properties, and detergency. Comparative Example 3 is an example in which only the thiazole group-free benzimidazole compound (b1) is used as the antifungal agent [B], and the sustainability of the antifungal, fungicidal and detergency properties is not sufficient. There wasn't.
On the other hand, Examples 1 to 11 are examples containing a thermoplastic resin [A], an antifungal agent [B] and a polymer [C] at a predetermined ratio, and include a specific antifungal agent [B]. No fungal growth was observed, and by containing the polymer [C], it could be easily washed with water and the sustainability was exhibited.

Articles having molded articles or films formed using the aromatic vinyl-based resin composition of the present invention have fungi, organisms, etc. generated or proliferated during use, transportation or storage of these products, It is suitable for use in places where it adheres to or propagates to products. In particular, it is useful as an article used in a place where it comes into contact with drainage, sewage, etc., an article used under high humidity conditions, etc.
Specific fields include daily necessities, sports / leisure supplies, civil engineering materials, agricultural and forestry materials, fishery materials, industrial materials, materials for public institutions, transportation-related materials, low-power products, textile products, etc. It is done.
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 grass, building interior materials, building 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.
Weak electricity-related products include refrigerators, washing machines, vacuum cleaners, fans, dryers, air conditioners, humidifiers, air purifiers, telephones, electric kettles, rice cookers, dishwashers, dish dryers, microwave ovens, mixers, A VTR, a television, a clock, a stereo, a tape recorder, an OA device, and the like can be given, and a housing, a handle, a tray, a partition, a vent, a water vent, and the like can be used.
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.

Claims (7)

[A] Thermoplastic resin mainly composed of aromatic vinyl resin (excluding [C] below), [B] Antifungal agent, [C] Polymer having polyether chain and polyamide chain An aromatic vinyl-based resin composition comprising:
The antifungal agent [B] includes a thiazole group-free benzimidazole compound, and at least one selected from the group consisting of an organic iodine compound, a thiazole compound, and a haloalkylthio compound,
The content of the antifungal agent [B] and the polymer [C] is 0.01 to 10 parts by mass and 1 to 50 parts by mass, respectively, with respect to 100 parts by mass of the thermoplastic resin [A]. An aromatic vinyl resin composition characterized by that.   The ratio of the content of the thiazole group-free benzimidazole compound and the total content of at least one selected from the group consisting of organic iodine compounds, thiazole compounds and haloalkylthio compounds is The aromatic vinyl-based resin composition according to claim 1, which is 80 to 99.99 mass% and 0.01 to 20 mass%, respectively, when the total is 100 mass%.   The antifungal agent [B] comprises a thiazole group-free benzimidazole compound and at least two selected from the group consisting of organic iodo compounds, thiazole compounds and haloalkylthio compounds. Aromatic vinyl resin composition.   The ratio of the content of the thiazole group-free benzimidazole compound and the total of at least two contents selected from the group consisting of organic iodine compounds, thiazole compounds and haloalkylthio compounds is The aromatic vinyl resin composition according to claim 3, which is 80 to 99.99 mass% and 0.01 to 20 mass%, respectively, when the total is 100 mass%.   The aromatic vinyl resin composition according to any one of claims 1 to 4, wherein the thiazole group-free benzimidazole compound is a benzimidazole carbamic acid derivative.   The polymer [C] is a polyether ester amide derived from a polyamide having carboxyl groups at both ends and a polyoxyalkylene ether and / or polyalkylene glycol of bisphenols. 2. The aromatic vinyl resin composition according to item 1.   The molded article formed by shape | molding the aromatic vinyl-type resin composition of any one of Claims 1-6.