JP5523948B2 - Resin molded body and protective plate for display - Google Patents

Description

The present invention relates to a resin molded article having antibacterial and / or antifungal properties, and in particular, a transparent film- or sheet-shaped resin molding having a thickness of 0.2 to 5 mm obtained by curing a photocurable composition. More specifically, it is a resin molding that is excellent in transparency, light resistance, surface hardness, rigidity, antibacterial properties, and antifungal properties, and is particularly useful as a protective plate for displays. It is about the body.

  Conventionally, a protective plate made of glass, plastic, or the like is used on the front surface of a display in order to protect a display device such as a liquid crystal or PDP inside. In particular, a protective plate on the forefront of a portable display device, an outdoor display device, or the like uses a plastic sheet such as polymethyl methacrylate or polycarbonate because mechanical strength such as impact resistance is required. These plastic sheets are required to have not only optical properties such as transparency and light resistance, but also mechanical properties such as surface hardness and rigidity, heat resistance, chemical resistance and solvent resistance. Therefore, the mainstream is a plastic sheet having a hard coat film formed on the surface, a multilayered or thick plastic sheet to ensure rigidity, and the like.

  Here, the protective plate is a plate on the outermost surface of the display, a sheet also serving as a detection function such as a touch panel, an outermost layer film of a card incorporating a display device, and a cover sheet for waterproofing and antifouling. Etc., and is used by being installed on the top of the display device or pasted on the display device.

  On the other hand, in recent years, the protective plate is also required to be clean. In particular, in a display that is touched or approached by an unspecified number of people, there is a strong demand for a protective plate that ensures cleanliness. For example, displays at medical sites, schools, stations, banks, convenience stores, various public facilities, food factories, clothing factories, etc. have antibacterial and antifungal properties, as well as antiviral and antiallergenic functions. There is a need for a protective plate having When a plastic sheet is used as the protective plate, for example, when wrinkles occur, the wrinkles penetrate into the plastic sheet, optical properties such as transparency and hue of the plastic sheet, bending strength, bending elastic modulus, impact strength, Performances such as mechanical properties such as surface hardness are deteriorated, and the display performance of the display is deteriorated as a foreign matter, and further, malfunction of the display device is caused. Nutrient sources such as dust, dirt, food residue, sweat, and oil are likely to adhere to the protective plate, which sometimes leads to explosive growth of the cocoon. In addition, when moisture adheres to the surface of the protective plate due to condensation or the like, bacteria are also likely to propagate.

  In order to solve these problems, a protective sheet in which a thermosetting resin layer having a surface hardness of 2H or more containing fine particles of an inorganic antibacterial agent is formed on a polyester film has been proposed (see, for example, Patent Document 1). ). Moreover, in order to maintain the cleanliness of the touch panel, an input device including an antibacterial-coated protective sheet has been proposed (see, for example, Patent Document 2).

JP 2006-299214 A JP-A-8-185560

  However, even with these disclosed technologies, it is difficult to say that all the performances are satisfied. For example, the protective sheet disclosed in Patent Document 1 requires secondary processing such as coating, and surface hardness. Also, rigidity, chemical resistance and solvent resistance are insufficient. Moreover, since the protective sheet disclosed in Patent Document 2 requires a special transfer function, it must be expensive and is inferior in practicality. Furthermore, in these disclosed technologies, the antiviral and antiallergenic functions are not mentioned, and further improvements are desired.

  Therefore, in the present invention, in such a background, transparency, light resistance, surface hardness, rigidity, chemical resistance / solvent resistance are excellent, and antibacterial properties and / or antifungal properties are also excellent in long-term sustainability. It is an object of the present invention to provide a molded resin product. Furthermore, it is another object of the present invention to provide a resin molded article having both antiviral and antiallergenic functions.

  However, as a result of intensive studies by the present inventors to solve the above-described problems, the photocurable composition [I] containing an antibacterial agent and / or an antifungal agent is cured in a transparent resin molded product. In addition to being excellent in transparency, light resistance, surface hardness, rigidity, chemical resistance and solvent resistance, it is possible to obtain a resin molded article that is further excellent in antibacterial and antifungal properties and in addition to its long-term durability. The present invention has been completed.

That is, the gist of the present invention is a transparent resin molded body having a thickness of 0.2 to 5 mm, which is obtained by curing a photocurable composition [I] containing an antibacterial agent and / or an antifungal agent. It is related with the resin molding characterized by these.
Moreover, in this invention, the protective plate for displays which consists of the said resin molding is also provided.

In the present invention, fungus means bacteria, and sputum means fungi.
In addition, the definition of antibacterial and antifungal properties in industrial products is not clear, and the level of requirements may vary depending on the application, but it shall conform to the guidelines of the Japan Household Appliances Fair Trade Council. That is, the antibacterial and antifungal properties in the present invention have a function of preventing the growth of microorganisms such as bacteria or spiders that have a direct or indirect adverse effect on the human body and adhere to the surface of the protective plate. I will say.

  The antibacterial and antifungal functions of the protective plate are not temporary and must last for a certain period of time. For example, when an antibacterial component or the like is blended in the protective plate, sustained release property of the antibacterial component is required. It should be noted that functions such as antibacterial and antifungal properties do not need to be increased unnecessarily, and excessively high functions should be avoided in view of safety to the human body and environmental load.

  According to the present invention, a display having excellent optical properties and thermomechanical properties, particularly excellent surface hardness and rigidity, excellent antibacterial and / or antifungal functions, and excellent long-term sustainability. It is possible to easily manufacture a resin molded body suitable for a protective plate for use.

Hereinafter, the present invention will be described in detail.
In the present invention, “(meth) acrylate” is a general term for acrylate and methacrylate.

The resin molded body of the present invention is a transparent resin molded body having a thickness of 0.2 to 5 mm, and is obtained by curing a photocurable composition [I] containing an antibacterial agent and / or an antifungal agent. It is what

The resin molded body of the present invention is plate-like, and its thickness directly affects the rigidity when used as a protective plate, and is important to be 0.2 to 5 mm. If the thickness is less than the lower limit, it is easy to deform, it is difficult to maintain the shape of the protective plate, and it is difficult to protect the display device. Conversely, if the upper limit is exceeded, it will be difficult to reduce the weight and thickness of the display device. A preferable range of the thickness is 0.2 to 4 mm, more preferably 0.3 to 3 mm, still more preferably 0.4 to 2 mm, and particularly preferably 0.5 to 1.5 mm.

  The greatest feature of the present invention is that the photocurable composition [I] contains an antibacterial and / or antifungal agent in order to impart an antibacterial and / or antifungal function to the resin molding. .

  In the present invention, the reason for using a resin molded product obtained by curing the photocurable composition [I] is that it is easy to obtain characteristics such as surface hardness, rigidity, solvent resistance / chemical resistance as a protective plate, and antibacterial properties over a long period of time. This is because the property and / or the antifungal property can be maintained. That is, the photocurable composition [I], which is usually liquid at about room temperature, easily dissolves or disperses the antibacterial agent and / or antifungal agent uniformly, and immediately after curing in the photocurable resin. The confined antibacterial agent and / or antifungal agent moves to the surface of the protective plate over time, and exhibits antibacterial and / or antifungal functions over a long period of time. Furthermore, since the photo-curing resin is generally insoluble in water, the antibacterial agent and / or the antifungal agent is not wasted even if used as a protective plate under high humidity.

  As this photocurable composition [I], the composition containing an epoxy-type compound and a (meth) acrylate type compound is mention | raise | lifted, for example. Among these, a photocurability containing a polyfunctional (meth) acrylate compound and a photopolymerization initiator in addition to an antibacterial agent and / or an antifungal agent because a relatively thick resin molded product can be produced with high productivity. Compositions are preferred.

  Many antibacterial agents and / or antifungal agents are unstable when heated for a long time, for example, deteriorate during high temperature melt molding of a thermoplastic resin, or yellow during thermosetting of a thermosetting composition. There is a tendency to do. Antibacterial agents and / or antifungal agents often vaporize during heating, particularly when the molecular weight is small. By using the photocurable composition [I], the antibacterial agent and / or the antifungal agent is reduced without reducing the heating temperature and the heating time, and without causing the blended antibacterial agent and / or the antifungal agent to evaporate or deteriorate. An incorporated resin molded body can be obtained.

  Examples of the polyfunctional (meth) acrylate compound include polyfunctional (meth) acrylate compounds having two or more (meth) acryloyl groups in the molecule.

Examples of the bifunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6- Hexanediol di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether Di (meth) acrylate, diethylene glycol aliphatic di (meth) acrylate compounds such as diglycidyl ether di (meth) acrylate, bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2, 6]} decane = di (meth ) Acrylate, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = di (meth) acrylate, bis (hydroxy) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane = di (meth) acrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] pentadecane = di (meth) acrylate, 2,2-bis [4- (β- (meth) acryloyloxyethoxy) cyclohexyl] propane, 1,3-bis ((meth) acryloyloxymethyl) cyclohexane, 1,3-bis ((meth) acryloyloxyethyloxymethyl) cyclohexane, 1,4-bis ((meth) acryloyloxymethyl) cyclohexane, 1,4-bis ((meth) acryloyloxyethyloxymethyl) cyclohexane, etc. Alicyclic di (meth) acrylate compounds, 2,2-bis [4- (meth) acryloyloxyphenyl] propane, ethylene oxide modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A type di (meta Aromatic di (meth) a such as acrylate Relate-based compounds, and the like.

  Examples of the trifunctional or higher functional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and di Pentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) ) Acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, ethylene oxide modified pentaerythris Aliphatic polyfunctional (meth) acrylates such as alkylene oxide-modified poly (meth) acrylates such as tall tetra (meth) acrylate, 1,3,5-tris ((meth) acryloyloxymethyl) cyclohexane, 1,3, Modified with alicyclic polyfunctional (meth) acrylate such as 5-tris ((meth) acryloyloxyethyloxymethyl) cyclohexane, 1,3,5-tris ((meth) acryloyloxyethyl) benzene, isocyanuric acid ethylene oxide modified And aromatic (meth) acrylate compounds such as triacrylate.

  Furthermore, polyfunctional (meth) acrylate compounds such as epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, and the like can be given.

Among these, from the viewpoint of rigidity, bis (hydroxy) tricyclo [5.2.1.0 ^2,6 ] decane = di (meth) acrylate, bis (hydroxymethyl) tricyclo [5.2.1.0 ^{2 , 6} ] Preferred are alicyclic di (meth) acrylates and alicyclic polyfunctional urethane (meth) acrylates having an alicyclic skeleton such as decane = di (meth) acrylate.

Moreover, the said polyfunctional (meth) acrylate type compound can also be used together 1 type, or 2 or more types.
Furthermore, you may use together the said polyfunctional (meth) acrylate type compound and a monofunctional (meth) acrylate type compound.

  Specific examples of the photopolymerization initiator include acetophenone-based initiators such as 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, and 4-diphenoxydichloroacetophenone, benzophenone Benzophenone initiators such as methyl benzoylbenzoate, 4-phenylbenzophenone and hydro-benzobenzophenone, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6 -A phosphine oxide initiator such as trimethylbenzoyl) phenylphosphine oxide, and the like can be used in combination.

  These photopolymerization initiators are polyfunctional (meth) acrylate compounds (the total of polyfunctional (meth) acrylate compounds and monofunctional (meth) acrylate compounds when using monofunctional (meth) acrylate compounds) It is preferably used in a proportion of usually 0.1 to 10 parts by weight with respect to 100 parts by weight, more preferably 0.2 to 5 parts by weight, and particularly preferably 0.3 to 2 parts by weight. If the amount of the photopolymerization initiator is too small, curing tends not to proceed sufficiently. If the amount is too large, the light transmittance of the resulting resin molded product tends to decrease.

  As the antibacterial agent and antifungal agent used in the present invention, known antibacterial compounds and antifungal compounds can be used. In the present invention, for example, metals (including ions) such as silver, copper, and zinc, metal oxides such as zinc oxide, magnesium oxide, and titanium oxide, sodium percarbonate, sodium hypochlorite, silver phosphate, etc. Metal salts, boric acid compounds such as orthoboric acid, metaboric acid, borax, thiosulfato silver salt, 2- (4-thiazolyl) benzimidazole silver salt, 2-pyridinethiol-1-oxide sodium salt, bis (2-pyridine) Thiol-1-oxide) complex compounds such as zinc salts, and inorganic compounds such as zeolite support, ceramic support, silica gel support, montmorillonite support, quaternary ammonium salt compounds, monocyclic carbonization Hydrogen compounds, phenol compounds, pyridine compounds, alcohol compounds, phosphonium salt compounds, allyl compounds Products, haloallylsulfone compounds, iodopropargyl compounds, N-haloalkylthio compounds, nitrile compounds, 8-oxyquinoline compounds, benzoithiazole compounds, isothiazoline compounds, organotin compounds, triazine compounds , Thiadiazine compounds, anilide compounds, adamantane compounds, dithiocarbamate compounds, brominated indanone compounds, phenol ether compounds, sulfone compounds, pyrrole compounds, imidazole compounds, benzimidazole compounds, benzoic acid compounds , Phenol ether compounds, sulfone compounds, pyrrole compounds, halodiallyl urea compounds, guanidine compounds, fatty acid ester compounds, cyano compounds, aldehyde compounds, amide compounds, iodine Compounds, carboximide compounds, benzoquinone compounds, paraben compounds, tyrosol compounds, and other organic compounds, chitosan, scorpion bamboo extract, Japanese mustard extract, wasabi extract, hiba extract, oyster shell, protamine, polylysine And other natural compounds.

  Among these, organic compounds are preferable in terms of compatibility as the photocurable composition [I]. More preferably, an organic compound having a molecular weight of 100 or more, particularly 120 to 1000, and more preferably 140 to 900 is preferred in that it does not evaporate wastefully during the production process of the resin molded body or during use as a protective plate. The organic compound referred to here is a compound mainly composed of carbon and hydrogen, which may contain oxygen, nitrogen, sulfur, phosphorus, silicon, and / or halogen, and contains a small amount of metal ions. Also good.

Furthermore, the acute oral toxicity LD ₅₀ of the antibacterial agent and / or antifungal agent is preferably 1 g / kg or more in order to avoid adverse effects on the human body. More preferably, it is 1.5 g / kg or more, and particularly preferably 2 g / kg or more. The upper limit is usually 100 g / kg.

  Specific examples of the organic antibacterial agent used in the present invention include 3- (trimethoxysilyl) propyldimethyloctadecylammonium chloride, tetradecyldimethylbenzylammonium chloride, 1-hexadecylpyridinium chloride, hexadecyltrimethylammonium bromide. , Hexadecyltrimethylammonium chloride, N-polyoxyethylene-N, N, N-trimethylammonium chloride, cetyltrimethylammonium chloride, octadecyltrimethylammonium chloride, didecyldimethylammonium chloride, benzalkonium chloride, behenyltrimethylammonium chloride, benzethonium Chloride, 4,4 ′-(tetramethylenedicarbonyldiamino) bis (1-decylpyridinium bromide) Mido), N, N′-hexamethylenebis (4-carbamoyl-1-decylpyridinium salt), 4,4 ′-(p-phthalamido) bis (1-octylpyridinium bromide), 3,3 ′-(m- Quaternary ammonium salt compounds such as phthalamido) bis (1-octylpyridinium iodide), monohydric phenol compounds such as 5-chloro-2- (2,4-dichlorophenoxy) phenol, 2- (3,5- Pyridine compounds such as dimethylpyrazolyl) -4-hydroxy-6-phenylpyridine, alcohol compounds such as 2- (hydroxymethylamino) ethanol and 2- (hydroxymethylamino) -2-methylpropanol, tetradecyltrimethylphosphonium chloride, Phosphonium salt compounds such as didecyldimethylphosphonium chloride, Con acid chlorohexidine compounds and the like.

  Among these, a quaternary ammonium salt compound and a pyridine compound are preferable in terms of light resistance. Particularly preferred are 3- (trimethoxysilyl) propyldimethyloctadecylammonium chloride, tetradecyldimethylbenzylammonium chloride and the like because of their low cost.

  Examples of the bacteria in the present invention include Staphylococcus aureus, MRSA (methicillin-resistant Staphylococcus aureus), Escherichia coli, Pseudomonas aeruginosa, Micrococcus sp., Pediococcus sp., Proteus vulgaris, Pseudomonas aeruginosa, Pseudomonas Pseudomonas putida, alcaligenes, Pseudomonas Pseudoalcaligenes, Pseudomonas cepacia, Alcaligenes defnitrificans, Alcaligenes faecalis, Bacillus subtils, Bacillus cerens, Acinetobacter calcoaceticus, Alcaligenes faecalis, Peptococcus sp., Neisseria sp., Salmonella typhimurium, Vibrio parahaemolyticus, Enterobacter cloacea, Citrobacter freundii, Kiebsiella pneumoniae, Actinomyces Examples include bacteria of the genus and Thiobacillus genus.

  Specific examples of the organic antifungal agent used in the present invention include haloallylsulfone compounds such as 1-[(diiodomethyl) sulfonyl] -4-methylbenzene, 3-iodo-2-propargyl, and the like. Iodopropargyl compounds such as butyl carbamate, N, N-dimethyl-N ′-(fluorodimethylthio) -N′-phenylsulfanide, N, N-dimethyl-N ′-(fluorodichloromethylthio) -N ′ N-haloalkylthio compounds such as phenylsulfamide, nitrile compounds such as 2,3,5,6-tetrachloroisophthalonitrile, 2,4,5,6-tetrachloroisophthalonitrile, 2,3 Pyridine compounds such as 1,5,6-tetrachloro-4- (methylsulfonyl) pyridine, and benzene such as 2- (thiocyanomethylthio) benzothiazole Isothiazoline compounds such as zoithiazole compounds, 2-n-octyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one Compound, p-chloro-m-cresol, alkylene bisphenol sodium, 2,4,4′-trichloro-2′-hydroxydiphenyl ether, o-phenylphenol and other phenol compounds, hexahydro-1,3,5-tri (2- Triazine compounds such as hydroxyethyl) -s-triazine, thiadiazine compounds such as 3,5-dimethyl-tetrahydro-1,3,5,2H-thiadiazine-2-thione, 3,4,5-tribromosartylanilide Anilide compounds such as 1- (3-chloroallyl) -3,5,7-triaza- -Adamantane compounds such as azonia adamantane chloride, dithiocarbide compounds such as tetramethylthiuram disulfide, bis (dimethylthiocarbamoyl) disulfide, bis (diethylthiocarbamoyl) disulfide, 2,2-dibromo-1-indanone, etc. Brominated indanone compounds, benzyl bromoacetate, benzoic acid compounds such as p-hydroxybenzoic acid ester, sulfone compounds such as 3,4,5-tribromosalicylanilide, N- (trichloromethylthio) phthalimide, N-trichloro Phthalimide compounds such as methylthio-4-cyclohexene-1,2-dicarboximide, N-1,1,2,2-tetrachloroethylthiotetrahydrophthalimide, N- (fluorodichloromethylthio) phthalimide Imidazole compounds such as 2- (4-thiazolyl) benzimidazole, 2- (carbomethoxyamino) benzimidazole, benzimidazole carbamate methyl ester, 2-benzimidazole methyl carbamate, halodiallyl urea compounds such as triclocarban, poly Hexamethylene piguanidine hydrochloride, guanidine compounds such as chlorohexidine hydrochloride, propylene glycol monofatty acid ester, fatty acid ester compounds such as glycerin fatty acid ester, amide compounds such as 2,2-dibromo-2-cyanopropionamide, diiodomethyl-p -Iodo compounds such as tolylsulfone, N- (1,1,2,2-tetrachloroethylthio) -4-cyclohexene-1,2-dicarboximide, N- (trichloromethylthio) Carboxyimide based compounds such as 4-cyclohexene-1,2-dicarboximide, benzoquinone-based compounds such as 2,6-dimethoxy -p- benzoquinone, paraben compounds such methylparaben and ethylparaben, and the like.

  Of these, phthalimide compounds and isothiazoline compounds are preferable in terms of light resistance. Particularly preferred are phthalimide compounds in terms of compatibility as the photocurable composition [I].

  In addition, examples of the cocoons in the present invention include Candida albicnas, Aspergillus niger, Aspergillus terrus, Penicillium citrinum, Aspergillus penicilloides, Penicillium funiculosum, Penicillium digitatum, Aureobasidium pullulans, Phomasporium cladosporioides, Cladosporides, Cladosporides, Cladosperia, Aspergillus fumigatus, Aspergillus terreus, Geotrichum sp., Alternaria sp., Alternaria Alternata, Fusarium solani, Nigrospora Oryzae, Pestalotia adusta, Trichoderma T-1, Trichoderma sp., Trichoderma harzianu, Chaetomium pus And fungi belonging to the genus Curvularia, Eurochiumu, Nocardia, Streptomyces, Deccrosphaera, Cochliobolus, Acremonium and the like.

There are many antibacterial compounds having antifungal properties, and many antifungal agents have antibacterial properties. In the present invention, the two are described separately for convenience, but it should be noted that it is difficult to strictly separate them.
In addition, antibacterial and antifungal properties often exhibit deodorant and antiseptic properties as a result, and can be added as an effect of the present invention.
In addition, antibacterial agents and antifungal agents are sometimes referred to as day keeping improvers and preservatives.

The resin molded article of the present invention preferably further contains an antiviral agent or an antiallergen agent.
Specifically, the photocurable composition [I] further contains an antiviral agent or an antiallergen agent, and the photocurable composition [I] is cured to form a resin molded body. .

Examples of the antiviral agent include thiosulfato silver salt, hydroxytyrosol, glutaral, hexachlorophene, chlorohexidine and the like. Among these, hydroxytyrosol is preferable in terms of compatibility as the photocurable composition [I].
In addition, as a virus in this invention, normally, filmless viruses, such as film viruses, such as an AIDS virus, a measles virus, a herpes simplex virus, an influenza virus, and a poliovirus, etc. are mention | raise | lifted.

Examples of the anti-allergen include polyphenol compounds such as polyphenol, polycresol, polymethoxyphenol, polyvinylphenol compounds, polybisphenol A compounds, lignophenol compounds, tannic acid, polytyrosine, and the like. Of these, polyphenol compounds and polyvinyl phenol compounds are preferred in terms of the effect of inactivating allergens. Particularly preferred is a polyvinylphenol compound in terms of compatibility as the photocurable composition [I].
The allergen in the present invention is not particularly limited as long as it causes allergic diseases such as atopic dermatitis, bronchial asthma, and allergic rhinitis, and is generated from mite allergen, cedar pollen allergen, and these allergens. Examples include allergenic substances.

  The content of the antibacterial agent, antifungal agent, antiviral agent, and / or antiallergen agent is 0.01 to 5% by weight, respectively, when the total amount of the photocurable composition [I] is 100% by weight. It is preferable. More preferably, it is 0.05-3 weight%, Most preferably, it is 0.1-1 weight%. If the content of the antibacterial agent, antifungal agent, antiviral agent, and / or antiallergen agent is too small, the antibacterial, antifungal, antiviral, and / or antiallergenic functions of the resin molding are sufficient. On the other hand, if the amount is too large, there is a tendency for the environment and the human body to be adversely affected.

  The photocurable composition [I] used in the present invention is appropriately supplemented with a surfactant or the like for the purpose of uniform dispersion of the antibacterial agent, antifungal agent, antiviral agent, and / or antiallergen agent. It may contain components.

  Furthermore, the photocurable composition [I] used in the present invention may contain a small amount of auxiliary components as long as the object of the present invention is not impaired. For example, thermoplastic resins, polymerization inhibitors, thermal polymerization initiators, chain transfer agents, antioxidants, yellowing inhibitors, ultraviolet absorbers, bluing agents, dyes and pigments, antifoaming agents, leveling agents, thixotropic agents , Flame retardants, thickeners, various fillers and the like.

  A resin molded product is obtained by using the photocurable composition [I] thus obtained, but the resin molded product of the present invention is obtained by placing the photocurable composition [I] on a flat mold, Alternatively, it is manufactured by providing between two flat molds and irradiating with light to cure. Light irradiation may be performed in several stages. In order to accelerate or complete the curing, it is also preferable to heat the resin molded body at the time of light irradiation or after irradiation.

  The material of the mold is not particularly limited as long as at least one of the molds transmits light, and glass, metal, or resin can be used. Among these, a glass or transparent resin mold is preferable in terms of light translucency. When an opaque mold is used, a mold made of a transparent material is used for the mold on the opposite surface, and light is irradiated from the opposite surface side.

As light to be used, light such as far ultraviolet light, ultraviolet light, near ultraviolet light, and infrared light can be used. However, curing by ultraviolet irradiation is advantageous from the viewpoint of curing speed, availability of an irradiation device, price, and the like. As a light source in ultraviolet irradiation, a chemical lamp, a xenon lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, or the like is usually used. Irradiation energy is usually about 0.1 to 10 J / cm ² . Excessive irradiation tends to cause inactivation of antibacterial agents, antifungal agents, antiviral agents, and / or antiallergen agents.

  It is also possible to form fine irregularities on the surface of the resin molding to provide antiglare and water repellent functions and fine irregularities (called anti-Newton ring functions) to avoid interference fringes. It is. In particular, imparting a water-repellent function with fine irregularities is also preferable from the viewpoint of reducing the adhesion of bacteria and sputum. In these cases, a mold having fine irregularities on the surface may be used for at least one mold, and fine irregularities can be formed on the surface of the resin molded body itself.

  The resin molded body of the present invention preferably has a light transmittance of 80% or more from the viewpoint of transparency when used as a protective plate. The light transmittance of the resin molded body is more preferably 85% or more, and particularly preferably 90% or more. In general, the upper limit of the light transmittance is 99%.

  As a method for improving the light transmittance, a method for specifying the component and content of the photocurable composition [I] (for example, using a monomer that does not contain an aromatic ring as a polyfunctional (meth) acrylate, or starting photopolymerization) Adjusting the amount of the agent, etc.), a method for identifying the antibacterial, antifungal, antiviral, and / or antiallergen components and content, a method of blending an antioxidant as an auxiliary component, Examples include a method of controlling the curing conditions (for example, not excessively increasing the amount of light or irradiating with inert gas).

  Furthermore, the resin molded body of the present invention preferably has a pencil hardness of 2H or more from the viewpoint of surface hardness when used as a protective plate, and has a bending elastic modulus of 3 GPa or higher when used as a protective plate. It is preferable in terms of rigidity.

  The pencil hardness of the resin molded body is more preferably 3H or more, and particularly preferably 4H or more. In adjusting the pencil hardness to the above range, a method of appropriately controlling the kind of the above-described photocurable composition [I] and the blending amount of the components can be used. For example, as a polyfunctional (meth) acrylate, a method using a polyfunctional urethane (meth) acrylate compound or a trifunctional or higher functional compound can be used. In general, the upper limit of the pencil hardness of the resin molded body is 8H.

  Further, the flexural modulus of the resin molded body is more preferably 3.5 GPa or more, and particularly preferably 4 GPa or more. In adjusting the bending elastic modulus to the above range, a method of appropriately controlling the kind of the above-described photocurable composition [I] and the blending amount of the components can be mentioned. In addition, the upper limit of the bending elastic modulus of the resin molded body is 10 GPa.

  The resin molded product of the present invention thus obtained has excellent transparency and mechanical strength, and also has excellent antibacterial and antifungal properties, as well as antiviral and antiallergenic properties, and protection for various displays. Very useful as a board.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
In the examples, “parts” and “%” mean weight basis unless otherwise specified.
Each evaluation was performed as follows.

(1) Antibacterial properties Tests were conducted in accordance with JIS Z 2801 on resin moldings 1 day and 2 months after production, and Staphylococcus aureus (E. aureus) and Escherichia coli (E. coli) were evaluated as follows. . As the reference unprocessed film, the film of Comparative Example 1 containing no antibacterial agent, antifungal agent, antiviral agent, or antiallergen agent was used.
○: Antibacterial activity value of 2 or more for any fungus Δ: Antibacterial activity value of 2 or more for any fungus × Less than antibacterial activity value of 2 for any fungus

(2) Antifungal properties
Five types of Aspergillus niger, Penicillium citrinum, Aureobasidium pullulans, Phoma sp., And Cladosporium cladosporioides were each inoculated into potato dextrose (PDA), cultured at 25 ° C for 10 days, and then diluted to 100 times Gulcose Peptone broth (GP ) Was used to prepare a mixed spore solution in which the number of spores of the five types of sputum was 1.0 × 10 ⁶ cfu / ml. By spraying this mixed spore solution on the surface of the resin molded body 1 day and 2 months after the production, culturing at 29 ° C. and 90% RH for 4 weeks, and observing the growth of wrinkles with the naked eye and a microscope, The antifungal property was evaluated as follows.
○ ・ ・ ・ Growth of cocoon hyphae is not allowed.
Δ: The growth of the mycelium of the cocoon is not recognized with the naked eye, but can be confirmed with a microscope.
X: Growth of cocoon mycelium is observed with the naked eye.

(3) Antiallergenicity Dust dust containing mite allergens (Der1 and Der2) is applied to the resin molding, left at 25 ° C. and 75% RH for 24 hours, and “Daniscan” manufactured by Asahi Breweries is used. The presence or absence of color development was observed.
○ ... No color development (no antiallergenicity)
× ... Color development (anti-allergenic)

(4) Light transmittance The total light transmittance (%) of the resin molding was measured using a Nippon Denshoku haze meter “NDH-2000”.

(5) Pencil hardness The pencil hardness of the resin molded product was measured according to JIS K 5600-5-4.

(6) Flexural modulus Using a test piece of a resin molded product of length 25 (mm) × width 10 (mm), an autograph “AG-5kNE” manufactured by Shimadzu Corporation (distance between supporting points 20 mm, 0.5 mm / Minutes), the flexural modulus (GPa) was measured at 25 ° C.

(7) Solvent resistance The resin molded body was immersed in isopropyl alcohol at 25 ° C. for 1 hour and evaluated according to the following evaluation criteria.
○: No change in appearance.
X: Appearance changed.

<Example 1>
98 parts of bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane diacrylate (manufactured by Shin-Nakamura Chemical Co., “A-DCP”), 4 which is a quaternary ammonium salt compound as an antibacterial agent , 4 ′-(tetramethylenedicarbonyldiamino) bis (1-decylpyridinium bromide) (molecular weight 740.70, LD ₅₀ (rat) 2000 mg / kg or more) 1 part, 1-hydroxycyclohexyl phenyl ketone ( One part of “Irgacure 184” manufactured by Ciba Geigy Co., Ltd.) was stirred at 60 ° C. until uniform, to obtain a photocurable composition [I]. This composition [I] was poured into a mold composed of two glass plates facing each other with a silicon plate having a thickness of 1.0 mm as a spacer (23 ° C.), and an illuminance of 100 mW / cm using a metal halide lamp. ^2. After irradiating with ultraviolet rays at a light quantity of 5 J / cm ² , the mold was removed to obtain a resin molded body (A) of 30 cm width × 30 cm length × 1.0 mm thickness.
The obtained resin molding (A) had a light transmittance of 92%, a pencil hardness of 3H, a flexural modulus of 4 GPa, good solvent resistance, and good performance as a protective plate. Antibacterial, antifungal and antiallergenic properties are as shown in Table 2.

<Example 2>
98 parts of bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “A-DCP”), N- (which is a phthalimide compound as an antifungal agent 1 part of fluorodichloromethylthio) phthalimide (molecular weight 280.10, LD ₅₀ (rat) = 2900 mg / kg) (manufactured by Sanai Oil Co., Ltd., “San-Isol 300”), 1-hydroxycyclohexyl phenyl ketone (Ciba Geigy Co., Ltd.) as a photopolymerization initiator A resin molded product (B) having a width of 30 cm, a length of 30 cm and a thickness of 1.0 mm was obtained in the same manner as in Example 1 except that 1 part of “Irgacure 184” manufactured by the company was used.
The obtained resin molding (B) had a light transmittance of 92%, a pencil hardness of 3H, a flexural modulus of 4 GPa, good solvent resistance, and good performance as a protective plate. Antibacterial, antifungal and antiallergenic properties are as shown in Table 2.

<Example 3>
97 parts of bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “A-DCP”), a tetraquaternary ammonium salt compound as an antibacterial agent 1 part of decyldimethylbenzylammonium chloride, 1 part of N- (fluorodichloromethylthio) phthalimide (Sanaisol 300 manufactured by Sanai Oil Co., Ltd.), a phthalimide compound as an antifungal agent, and 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator (Ciba Geigy Co., Ltd., "Irgacure 184") Except having used 1 part, it carried out similarly to Example 1, and obtained the resin molding (C) of width 30cm x length 30cm x thickness 1.0mm.
The obtained resin molding (C) had a light transmittance of 91%, a pencil hardness of 3H, a flexural modulus of 4 GPa, good solvent resistance, and good performance as a protective plate. Antibacterial, antifungal and antiallergenic properties are as shown in Table 2.

<Example 4>
98.8 parts of bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane diacrylate (manufactured by Shin-Nakamura Chemical Co., “A-DCP”), a quaternary ammonium salt compound as an antibacterial agent 0.1 part of a certain tetradecyldimethylbenzylammonium chloride, 0.1 part of N- (fluorodichloromethylthio) phthalimide (San Aisol 300 manufactured by Sanai Oil Co., Ltd.) which is a phthalimide compound as an antifungal agent, and a photopolymerization initiator 1 part of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Geigy Co., Ltd., “Irgacure 184”) was stirred at 60 ° C. until uniform, to obtain a photocurable composition [I]. This composition [I] was poured into a mold composed of two glass plates facing each other with a silicon plate having a thickness of 0.5 mm as a spacer (23 ° C.), and an illuminance of 100 mW / cm using a metal halide lamp. ^2. After irradiating with ultraviolet rays at a light amount of 5 J / cm ² , the mold was removed to obtain a resin molded body (D) having a width of 30 cm × length of 30 cm × thickness of 0.5 mm.
The obtained resin molded product (D) had a light transmittance of 91%, a pencil hardness of 3H, a flexural modulus of 4 GPa, good solvent resistance, and good performance as a protective plate. Antibacterial, antifungal and antiallergenic properties are as shown in Table 2.

<Example 5>
Instead of 97 parts of bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “A-DCP”), bis (hydroxymethyl) tricyclo [5. 2.1.0 ^2,6 ] 60 parts of decane diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “A-DCP”) and hexafunctional alicyclic urethane acrylate (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., “UV7600B”) ) A resin molded product (E) having a width of 30 cm, a length of 30 cm and a thickness of 1.0 mm was obtained in the same manner as in Example 3 except that 37 parts were used.
The obtained resin molded product (E) had a light transmittance of 91%, a pencil hardness of 5H, a bending elastic modulus of 5 GPa, good solvent resistance, and good performance as a protective plate. Antibacterial, antifungal and antiallergenic properties are as shown in Table 2.

<Example 6>
96 parts of bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “A-DCP”), tetra as a quaternary ammonium salt compound as an antibacterial agent 1 part of decyldimethylbenzylammonium chloride, 1 part of N- (fluorodichloromethylthio) phthalimide (“San-Isol 300” manufactured by Sanai Oil Co., Ltd.), a phthalimide compound as an antifungal agent, and 1 part of hydroxytyrosol as an antiviral agent A resin having a width of 30 cm, a length of 30 cm and a thickness of 1.0 mm, in the same manner as in Example 1, except that 1 part of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Geigy Co., Ltd., “Irgacure 184”) is used as a photopolymerization initiator. A molded body (F) was obtained.
The obtained resin molded product (F) had a light transmittance of 91%, a pencil hardness of 3H, a flexural modulus of 4 GPa, good solvent resistance, and good performance as a protective plate. Antibacterial, antifungal and antiallergenic properties are as shown in Table 2.

<Example 7>
94 parts of bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “A-DCP”), tetra as a quaternary ammonium salt compound as an antibacterial agent 1 part decyldimethylbenzylammonium chloride, 1 part N- (fluorodichloromethylthio) phthalimide (manufactured by Sanai Oil Co., Ltd., “San-Isol 300”) as a mildewproofing agent, and poly (4-vinylphenol) as an antiallergenic agent ) 3 parts, 1 part of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Geigy Co., Ltd., “Irgacure 184”) as a photopolymerization initiator in the same manner as in Example 1 except that the width is 30 cm × the length is 30 cm × the thickness is 1. A 0 mm resin molded body (G) was obtained.
The obtained resin molded product (G) had a light transmittance of 90%, a pencil hardness of 2H, a flexural modulus of 4 GPa, good solvent resistance, and good performance as a protective plate. Antibacterial, antifungal and antiallergenic properties are as shown in Table 2.

<Comparative Example 1>
99 parts of bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane diacrylate (manufactured by Shin-Nakamura Chemical Co., "A-DCP"), 1-hydroxycyclohexyl phenyl ketone ( One part of “Irgacure 184” manufactured by Ciba Geigy Co., Ltd.) was stirred until uniform at 60 ° C. to obtain a photocurable composition. Except using this composition, it carried out similarly to Example 1, and obtained the resin molding (H) of width 30cm x length 30cm x thickness 1.0mm.
The obtained resin molding (H) had a light transmittance of 92%, a pencil hardness of 3H, a flexural modulus of 4 GPa, good solvent resistance, and good performance as a protective plate. The antifungal and antiallergenic properties are as shown in Table 2.

  As can be seen from the above evaluation results, the resin moldings obtained by curing the photocurable composition containing an antibacterial agent, an antifungal agent, an antiviral agent, and an antiallergen agent have antibacterial and antifungal properties, respectively. In addition, since it is excellent in antiallergenicity and the like and is made of a photocurable resin, its performance has been maintained for a long period of time.

  The resin molded body of the present invention can be advantageously used for various optical materials and electronic materials. For example, liquid crystal substrates, organic / inorganic EL substrates, PDP substrates, electronic paper substrates, light guide plates, retardation plates, touch panels, optical filters, etc., various display members, storage / recording applications including optical disk substrates, It can be used for energy applications such as thin-film battery substrates and solar cell substrates, optical communication applications such as optical waveguides, functional films and sheets, and various optical films and sheets. In addition to optical materials and electronic materials, it can also be used for, for example, automotive materials, building materials, medical materials, stationery, and the like.

Claims (12)

A transparent resin molded body having a thickness of 0.2 to 5 mm, which is obtained by curing a photocurable composition [I] containing an antibacterial agent and / or an antifungal agent.   The resin molded product according to claim 1, wherein the photocurable composition [I] contains a polyfunctional (meth) acrylate compound and a photopolymerization initiator.   The resin molded product according to claim 2, wherein the polyfunctional (meth) acrylate compound is a compound having an alicyclic skeleton.   The resin molded article according to any one of claims 1 to 3, wherein the antibacterial agent and / or the antifungal agent is an organic compound having a molecular weight of 100 or more. Antibacterial and / or resin molded body according to any one of claims 1 to 4 acute oral toxicity LD ₅₀ for fungicide is characterized in that it is 1 g / kg or more.   6. The antibacterial agent and / or antifungal agent is at least one compound selected from quaternary ammonium compounds, phthalimide compounds, and isothiazoline compounds. The resin molding as described.   The photocurable composition [I] further contains an antiviral agent, and the resin molded article according to any one of claims 1 to 6.   The photocurable composition [I] further contains an anti-allergen agent, and the resin molded article according to any one of claims 1 to 7.   Light transmittance is 80% or more, The resin molding as described in any one of Claims 1-8 characterized by the above-mentioned.   The resin molded body according to any one of claims 1 to 9, wherein the pencil hardness is 2H or more and the flexural modulus is 3 GPa or more.   It uses as a protective plate for displays, The resin molding as described in any one of Claims 1-10 characterized by the above-mentioned.   A protective plate for a display comprising the resin molding according to any one of claims 1 to 11.