Active energy ray-curable composition and resin molding

Abstract

To provide an active energy ray-curable composition and a resin molding which are excellent in durability.SOLUTION: An active energy ray-curable resin composition 10 includes a radical reactive material and a leveling agent, wherein the radical reactive material contains a hydrophobic material 11 and a hydrophilic material 12, the leveling agent is a hydrophobic silicone material containing a radical reaction group, and a non-reactive volatile organic solvent having a boiling point of 200°C or lower in the active energy ray-curable composition 10 is less than 10 mass%.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to an active energy ray-curable composition and a resin molded article. [Background technology]

[0002] Transparent synthetic resins such as polycarbonate (PC) and polymethyl methacrylate (PMMA) are excellent in transparency, moldability, and mechanical properties, and are therefore used in many fields, such as covers for lamps of automobiles and motorcycles, lenses for glasses, covers for optical sensors, and various liquid crystal panels. However, when the surface temperature of a molded product such as a synthetic resin falls below the dew point temperature, moisture in the air condenses into fine droplets, causing fogging. This reduces light transmittance, leading to poor visibility and malfunction of sensors, etc. There is also the problem that scratches or dirt adhere to the surface of a molded product such as a synthetic resin, reducing light transmittance, leading to poor visibility and malfunction of sensors, etc. In order to prevent such problems, a composition is applied to the surface of a molded product such as a synthetic resin to ensure transparency (anti-fogging performance, scratch resistance, etc.).

[0003] For example, Patent Document 1 discloses an active energy ray-curable anti-fog coating composition containing a hydrophilic multifunctional acrylate, a water-soluble leveling agent, and a photopolymerization initiator. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6379690 Summary of the Invention [Problem to be solved by the invention]

[0005] However, active energy ray-curable anti-fog coating compositions containing a hydrophilic polyfunctional acrylate as the main component have poor adhesion to hydrophobic substrates and have problems with durability.

[0006] The present invention has been made in view of the above-mentioned points, and an object of the present invention is to provide an active energy ray-curable composition and a resin molded article having excellent durability. [Means for solving the problem]

[0007] The active energy ray-curable composition of the present invention comprises An active energy ray curable composition having a radical reactive material and a leveling agent, the radical reactive material comprises a hydrophobic material and a hydrophilic material; the leveling agent is a hydrophobic silicone material containing a radical reactive group; The active energy ray-curable composition, wherein the content of a non-reactive volatile organic solvent having a boiling point of 200° C. or less in the active energy ray-curable composition is less than 10 mass %. [Brief description of the drawings]

[0008] [Figure 1] 1 is a conceptual diagram showing a resin molded article of the present invention. [Diagram 2] 1A to 1C are diagrams illustrating a manufacturing process of a resin molded article according to the present invention. [Diagram 3] 1 is a table summarizing the results of comparison between Examples and Comparative Examples of the active energy ray-curable composition of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] An embodiment of the present invention will be described. The active energy ray-curable composition 10 of the present invention contains a radical reactive material, a reactive leveling agent, and a radical generator, and contains less than 10 mass % of a non-reactive volatile organic solvent having a boiling point of 200° C. or less.

[0010] The radical reactive material contains a hydrophobic material 11 and a hydrophilic material 12. Therefore, as shown in Fig. 1, when an active energy ray curable composition 10 is applied to the surface of a hydrophobic substrate 20 (e.g., polycarbonate), the hydrophobic material 11 is disposed on the surface of the substrate 20 since it has properties in common with the substrate 20, and the hydrophilic material 12 is disposed in the surface layer of the active energy ray curable composition 10. Then, a cured film can be formed on the surface of the substrate 20 by curing the active energy ray curable composition 10 by a radical reaction.

[0011] Since the contact surfaces of the active energy ray curable composition 10 and the substrate 20 are both hydrophobic, the adhesion between the active energy ray curable composition 10 and the substrate 20 can be improved. Therefore, the cured film can be prevented from peeling off from the substrate. In addition, since the adhesion between the cured film and the substrate 20 is high, the occurrence of cracks in a low temperature environment can also be prevented. Therefore, a cured film with excellent durability can be formed on the substrate 20.

[0012] Since the hydrophilic material 12 is disposed on the surface of the active energy ray-curable composition 10, the surface of the active energy ray-curable composition 10 has a hydrophilic function. Therefore, the contact angle between the surface of the active energy ray-curable composition 10 and water can be reduced. Thus, moisture diffuses on the surface of the active energy ray-curable composition 10 to form a water film, and the anti-fogging properties of the substrate 20 can be ensured.

[0013] Since the active energy ray curable composition 10 contains less than 10% by mass of a non-reactive volatile organic solvent having a boiling point of 200°C or less, 90% by mass or more of the active energy ray curable composition 10 becomes a cured film on the surface of the substrate 20. In other words, since 90% or more of the active energy ray curable composition 10 becomes an active ingredient, the total amount of the active energy ray curable composition 10 required for application to the surface of the substrate 20 can be reduced. It is more preferable that the active energy ray curable composition 10 contains less than 1% by mass of a non-reactive volatile organic solvent having a boiling point of 200°C or less. In this case, the total amount of the active energy ray curable composition 10 required for application to the surface of the substrate can be further reduced.

[0014] The hydrophobic material 11 is a radical reactive material made of a resin component such as a monomer or oligomer, and has a viscosity of 10 to 100 mPa·s / 25° C. By including the hydrophobic material 11 in the active energy ray curable composition 10, the viscosity of the active energy ray curable composition 10 can be reduced. Therefore, the active energy ray curable composition 10 can be used for coating without being diluted with an organic solvent. Therefore, a thermal drying step is not required in the step of curing the active energy ray curable composition 10 on the surface of the substrate 20, and power consumption during production can be reduced.

[0015] The content of the hydrophobic material 11 is preferably 50% by mass or more and less than 90% by mass with respect to the total amount of the active energy ray curable composition 10. When the content of the hydrophobic material 11 is 50% by mass or more, the active energy ray curable composition 10 can be adjusted to a viscosity suitable for spray coating without diluting it with an organic solvent. The viscosity suitable for spray coating is, for example, less than 30 mPa·s / 25°C.

[0016] As the hydrophobic material 11, aromatic styrene, acrylate-based butyl acrylate, naturally occurring β-pinene, aliphatic 2-phenoxyethyl acrylate, ethoxylated pentaerythritol tetraacrylate, and the like can be used.

[0017] The hydrophilic material 12 is a radical reactive material made of a resin component such as a monomer or oligomer. The content of the hydrophilic material 12 is preferably 1% by mass or more and less than 30% by mass with respect to the total amount of the active energy ray curable composition 10. When the content of the hydrophilic material is less than 1% by mass, sufficient hydrophilic function cannot be ensured on the surface of the cured film, and clouding of the substrate cannot be prevented. In addition, when the content of the hydrophilic material is 30% by mass or more, the compatibility with the reactive leveling agent and / or the radical generator decreases, and the cured film is likely to become cloudy.

[0018] Examples of the hydrophilic material 12 that can be used include copolymer-based styrene-maleic acid amide modified products, amide-based 2-(dimethylamino)ethyl methacrylate, sulfonic acid-based 2-acrylamido-2-methylpropanesulfonic acid (AMPS), and sodium p-styrenesulfonate.

[0019] The reactive leveling agent is a hydrophobic silicone material containing a radical reactive group. The reactive leveling agent spreads on the surface of the substrate immediately after application to the substrate, and can reduce the surface tension. Therefore, the occurrence of defects such as water drip marks and floating spots can be suppressed. In addition, since the reactive leveling agent is hydrophobic, it can be compatible with hydrophobic materials to form a cured film that is not cloudy and has high transparency. Furthermore, since the reactive leveling agent contains a radical reactive group, all of the reactive leveling agent is incorporated into the cured film, and the occurrence of defects caused by the leveling agent can be suppressed.

[0020] The content of the reactive leveling agent is preferably 0.1% or more and less than 0.5% based on the total amount of the active energy ray curable composition 10. If the content of the reactive leveling agent is less than 0.1%, the surface tension cannot be sufficiently reduced. If the content of the reactive leveling agent is 0.5% or more, the cured film may become cloudy.

[0021] The radical generator is an additive that generates highly active radicals when irradiated with ultraviolet light. These radical species undergo decomposition and react with resin components such as monomers and / or oligomers. The reaction product further reacts with another resin component, causing a chain reaction to proceed. Then, the crosslinking reaction proceeds, increasing the molecular weight, curing the radical reactive material and reactive leveling agent, and forming a cured film.

[0022] Examples of the radical generator include ketones such as benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, and 1-hydroxycyclohexyl phenyl ketone; azos such as 2,2'-azobisisobutylnitrile, azobis-2-methylbutyronitrile, and azobisdivaleronitrile; organic peroxides such as t-butylperoxyisobutyrate, t-butylperoxy-2-ethylhexanoate, t-amylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyisopropylcarbonate, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, di-t-butyl peroxide, and di-t-amyl peroxide; and acylphosphine compounds such as 2,6-dimethylbenzoyldiphenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Among these, radical cleavage type radical generators such as 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. are preferred. These radical generators may be used alone or in combination of two or more.

[0023] In addition to the radical generator, the active energy ray-curable composition 10 may contain various additives such as antibacterial agents, antifungal agents, antifoaming agents, antioxidants, antistatic agents, dyes, and polymerization inhibitors.

[0024] Examples of antibacterial agents include captan, carbendazim, quinomethionate, chlorothalonil, clozolinate, cyprodinil, epoxiconazole, famoxadone, fenarimol, fenbuconazole, fenfuram, fenpiclonil, azoxystrobin, benalaxyl, benomyl, bitertanol, fluazinam, fludioxonil, fluorimide, fluquinconazole, flusulfamide, flutolanil, folpet, Hexachlorobenzene, hexaconazole, ipoconazole, iprodione, kresoxim methyl, manzeb, maneb, mepanipyrim, mepronil, metconazole, metiram, phthalide, procymidone, propineb, quintozene, tecnazene, thifluzamide, thiophenate methyl, thiram, tolclofos methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, triforine, etc. can be used. Inorganic antibacterial agents can also be used, for example, silver, copper, zinc, tin, lead, gold, etc. Furthermore, synthetic antibacterial agents can also be used, for example, polyhexamethylene hyguanide, hydrochloride, benzethonium chloride, alkyl polyaminoethyl glycine, benzisothiazoline, etc.

[0025] As the mildewproofing agent, for example, sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof can be used.

[0026] Examples of the defoaming agent that can be used include fatty acid salts, liquid fatty oil sulfates, higher alcohol sulfates, fatty alcohol phosphates, fatty acid amide sulfonates, sulfonates of dibasic fatty acid esters, alkylarylsulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, acrylic polymers, vinyl polymers, and organopolysiloxanes.

[0027] As the antioxidant, for example, a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, etc. can be used. As the phenol-based antioxidant, for example, 2,6-di-tert-butyl-p-cresol, stearyl β-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3',5'-di-tert-butyl-4-hydroxybenzyl)benzene, etc. can be used. As the phosphorus-based antioxidant, for example, tris(2,4-di-tert-butylphenyl)phosphite, diphenyl mono(2-ethylhexyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexylphosphite, distearyl pentaerythritol diphosphite, tri(mononylphenyl)phosphite, etc. can be used. As the sulfur-based antioxidant, for example, dilauryl-3,3'-thiodipropionate, pentaerythritol tetrakis(3-laurylthiopropionate), etc. can be used.

[0028] Examples of the antistatic agent that can be used include various cationic antistatic agents having cationic groups such as primary to tertiary amino groups, quaternary ammonium salts, and pyridinium salts; anionic antistatic agents having anionic groups such as sulfonate groups, sulfate groups, phosphate groups, and phosphonate groups; amphoteric antistatic agents such as amino acid-based and amino sulfate-based; nonionic antistatic agents such as amino alcohol-based, glycerin-based, and polyethylene glycol-based; and polymeric antistatic agents obtained by increasing the molecular weight of the above-mentioned antistatic agents.

[0029] Examples of dyes that can be used include pyrazole azo compounds, anilino azo compounds, triarylmethane compounds, anthraquinone compounds, anthrapyridone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, xanthene compounds, phthalocyanine compounds, benzopyran compounds, indigo compounds, and pyrromethene compounds.

[0030] A polymerization inhibitor may be added to prevent the double bond from reacting. Examples of the polymerization inhibitor include hydroquinone (HQ), hydroquinone monomethyl ether (MEHQ), 2,6-di-t-butyl-4-methylphenol (BHT), t-butylcatechol (TBC), and phenol or naphthol derivatives such as 4-methoxy-1-naphthol, phenothiazine derivatives, and nitrosamine salts.

[0031] A method for producing a resin molded body 30 in which an active energy ray curable composition 10 is cured on the surface of a substrate 20 will be described with reference to FIG. 2. First, the active energy ray curable composition is loaded into a paint gun (S1). Then, the substrate to be coated is fixed to a coating jig (S2). The active energy ray curable composition is applied to the surface of the substrate with a paint gun (S3). The active energy ray curable composition is irradiated with ultraviolet light (S4). The active energy ray curable composition is cured on the surface of the substrate to form a cured film (S5). As described above, a resin molded body 30 in which the active energy ray curable composition 10 is cured on the surface of the substrate 20 can be produced.

[0032] When applying the active energy ray-curable composition 10 to the surface of the substrate 20, the composition may be applied to a part of the surface of the substrate 20, or may be applied to the entire surface of the substrate 20. The method of applying the active energy ray-curable composition 10 is not limited to a coating gun, and an application method using an inkjet or a dispenser may also be used.

[0033] The base material 20 may be made of hydrophobic synthetic resin such as polymethyl methacrylate (PMMA) or hydrophobic material such as glass, in addition to polycarbonate (PC).

[0034] The active energy ray-curable composition 10 can be used as an anti-fog coat or a hard coat. The resin molded body 30 obtained by curing the active energy ray-curable composition on the surface of a substrate can be used as an outer lens (translucent cover) of a vehicle lamp, window glass, a lens of glasses, a cover for the surface of an optical sensor, various liquid crystal panels and front panels of smartphones, tablets, various home appliances, and the like.

[0035] [Variation 1] The active energy ray curable composition of the present embodiment is described below in modified example 1. Modified example 1 of the active energy ray curable composition contains a radical reactive material, a reactive leveling agent, a radical generator, and a polyfunctional monomer, and contains less than 1 mass % of a non-reactive volatile organic solvent having a boiling point of 200° C. or less.

[0036] The polyfunctional monomer is a hydrophobic material with high reactivity. By including the polyfunctional monomer in the active energy ray curable composition, the curing speed of the active energy ray curable composition can be increased. Since both the polyfunctional monomer and the hydrophobic material are hydrophobic, they are compatible and cure simultaneously. On the other hand, since the hydrophilic material is incompatible with them, it cures with a delay. Therefore, the hydrophobic material and the polyfunctional monomer that are compatible with the hydrophobic substrate adhere to the substrate, and the hydrophilic material that cures with a delay can be easily arranged on the outermost surface. Therefore, the content of the hydrophilic material can be reduced, and a thin film of the hydrophilic material can be applied to the surface of the cured film, thereby further improving the anti-fogging property.

[0037] As the polyfunctional monomer, for example, a monomer containing an acrylate or vinyl group can be used. The content of the polyfunctional monomer is preferably 5% or more and less than 20% with respect to the total amount of the active energy ray curable composition. If the content of the polyfunctional monomer is less than 5%, the above-mentioned effects cannot be fully exhibited. On the other hand, if the content of the polyfunctional monomer is 20% or more, the viscosity becomes high, and it becomes difficult to spray coat the composition unless it is diluted with a solvent.

[0038] [Variation 2] The active energy ray curable composition of the present embodiment is described below in modified example 2. Modified example 2 of the active energy ray curable composition contains a radical reactive material, a reactive leveling agent, a radical generator, a polyfunctional monomer, and a thiol material, and contains less than 1 mass % of a non-reactive volatile organic solvent having a boiling point of 200° C. or less.

[0039] By including a thiol material in the active energy ray curable composition, oxygen inhibition can be suppressed by the thiol-ene reaction. The reaction mechanism of the thiol-ene reaction is shown below. First, the initiator is cleaved or energy is transferred by irradiation with ultraviolet light (initiation reaction). Then, electrons are extracted from the thiol material to generate thiyl radicals. The thiyl radicals attack the double bonds of the monomers of the hydrophobic or hydrophilic material. The monomers of the hydrophobic or hydrophilic material having radicals attack the thiol material to generate thiyl radicals. The generated thiyl radicals then attack the double bonds of the monomers of another hydrophobic or hydrophilic material (propagation reaction). In this way, the reaction proceeds in a chain reaction, and the active energy ray curable composition can be efficiently cured. [ka]

[0040] By including a thiol material in the active energy ray curable composition, curing can be promoted by a dark reaction even in the air (oxygen atmosphere). The reaction mechanism in an oxygen atmosphere is shown below. First, oxygen reacts with a monomer to generate a peroxy radical. Then, the peroxy radical abstracts hydrogen from the thiol to generate a thiyl radical. The thiyl radical then undergoes the above-mentioned propagation reaction. Therefore, the active energy curable composition can be cured even in an oxygen atmosphere. [ka]

[0041] By including a thiol material in the active energy ray curable composition, a thioether crosslinked structure is formed, and the flexibility of the cured film can be increased. Therefore, the occurrence of cracks in a low temperature environment can be suppressed, and durability can be further improved. Here, the flexibility of the cured film can be increased because the sulfur atom can rotate or move in the thioether crosslinked structure.

[0042] By including a thiol material in the active energy ray curable composition, it is possible to suppress the curing shrinkage. The curing shrinkage occurs when the double bonds of the radical reactive material are polymerized by radical polymerization, changing into a high molecular weight product connected by single bonds, and the specific gravity increases. However, by including a thiol material, it is possible to reduce the consumption of the double bonds of the radical reactive material. Therefore, the curing shrinkage is suppressed, and the occurrence of defects such as cracks and warping of the cured film can be suppressed.

[0043] The content of the thiol material is preferably 5% or more and less than 20% based on the total amount of the active energy ray-curable composition.

[0044] [Variation 3] The active energy ray curable composition of the present embodiment is described below in modified example 3. The active energy ray curable composition of modified example 3 has a radical reactive material and a reactive leveling agent, and contains less than 1 mass % of a non-reactive volatile organic solvent having a boiling point of 200° C. or less. In other words, the active energy ray curable composition of modified example 3 does not require a radical generator. The active energy ray curable composition is irradiated with an electron beam or deep ultraviolet light to directly excite the radical reactive material, thereby allowing the active energy ray curable composition to be cured without using a radical generator. EXAMPLES

[0045] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0046] Example 1 In a 300 mL separable flask equipped with a stirring blade, 70 parts by mass of styrene (product name: styrene, manufactured by Kanto Chemical Co., Ltd.) as a hydrophobic material, 29.8 parts by mass of styrene maleamic acid modified product as a hydrophilic material, and 0.2 parts by mass of reactive leveling agent (product name: X-22-2404, manufactured by Shin-Etsu Chemical Co., Ltd.) were added. Next, 0.5 parts by mass of radical generator (product name: Omnirad184, manufactured by Sanyo Trading Co., Ltd.) was added. This was stirred at room temperature for 30 minutes to obtain 100 parts by mass of the active energy curing composition of Example 1.

[0047] The styrene-maleamic acid modified product used as the hydrophilic material was obtained by the following process. 50 parts by mass of styrene acid copolymer (product name (trade name): XIRAN manufactured by Tomoe Engineering Co., Ltd.), 25 parts by mass of hexylamine (product name: hexylamine manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.1 parts by mass of pyridine (product name: pyridine manufactured by Wako Pure Chemical Industries, Ltd.) were added to a separable flask equipped with a stirring blade and a cooling tube. After heating at 100°C for 1 hour, the mixture was reprecipitated with 100 parts by mass of isopropyl alcohol and vacuum dried at 40°C to obtain 70 parts by mass of styrene-maleamic acid modified product.

[0048] Example 2 In a 300 mL separable flask equipped with a stirring blade, 70 parts by mass of butyl acrylate (product name: butyl acrylate manufactured by Tokyo Chemical Industry Co., Ltd.) as a hydrophobic material, 19.8 parts by mass of 2-(dimethylamino)ethyl methacrylate as a hydrophilic material, 0.2 parts by mass of a reactive leveling agent (product name: X-22-2445 manufactured by Shin-Etsu Chemical Co., Ltd.), and 10 parts by mass of a multifunctional monomer (product name: DPHA (dipentaerythritol hexaacrylate) manufactured by Tokyo Chemical Industry Co., Ltd.) were added. Next, 0.5 parts by mass of a radical generator (product name: Omnirad184 manufactured by Sanyo Trading Co., Ltd.) was added. This was stirred at room temperature for 30 minutes to obtain 100 parts by mass of the active energy curing composition of Example 2.

[0049] Example 3 In a 300 mL separable flask equipped with a stirring blade, 60 parts by mass of β-pinene (product name: β-pinene manufactured by Tokyo Chemical Industry Co., Ltd.) as a hydrophobic material, 9.8 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid (product name: 2-acrylamido-2-methylpropanesulfonic acid (AMPS) manufactured by Tokyo Chemical Industry Co., Ltd.) as a hydrophilic material, 0.2 parts by mass of a reactive leveling agent (product name: X-22-174ASX manufactured by Shin-Etsu Chemical Co., Ltd.), 15 parts by mass of a multifunctional monomer (product name: DPHA (dipentaerythritol hexaacrylate) manufactured by Tokyo Chemical Industry Co., Ltd.), and 15 parts by mass of a tetrafunctional secondary thiol (product name: Karenz MTPE1 manufactured by Showa Denko K.K.) as a thiol material were added. Next, 0.5 parts by mass of a radical generator (product name: Omnirad184 manufactured by Sanyo Trading Co., Ltd.) was added. This was stirred at room temperature for 30 minutes, yielding 100 parts by mass of the active energy curable composition of Example 3.

[0050] Example 4 In a 300 mL separable flask equipped with a stirring blade, 70 parts by mass of 2-phenoxyethyl acrylate (product name: 2-phenoxyethyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd.) as a hydrophobic material, 9.8 parts by mass of sodium p-styrenesulfonate (product name: Na p-styrenesulfonate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a hydrophilic material, 0.2 parts by mass of a reactive leveling agent (product name: X-22-164, manufactured by Shin-Etsu Chemical Co., Ltd.), 10 parts by mass of a multifunctional monomer (product name: TMPTA (trimethylolpropane triacrylate, manufactured by Tokyo Chemical Industry Co., Ltd.), and 10 parts by mass of a tetrafunctional secondary thiol (product name: Karenz MTPE1, manufactured by Showa Denko K.K.) as a thiol material were added. Next, 0.5 parts by mass of a radical generator (product name: OmniradMBF, manufactured by Sanyo Trading Co., Ltd.) was added. This was stirred at room temperature for 30 minutes to obtain 100 parts by mass of the active energy curing composition of Example 4.

[0051] Example 5 In a 300 mL separable flask equipped with a stirring blade, 70 parts by mass of 2-phenoxyethyl acrylate (product name: 2-phenoxyethyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd.) as a hydrophobic material, 9.8 parts by mass of sodium p-styrenesulfonate (product name: Na p-styrenesulfonate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a hydrophilic material, 0.2 parts by mass of a reactive leveling agent (product name: X-22-164, manufactured by Shin-Etsu Chemical Co., Ltd.), 10 parts by mass of a multifunctional monomer (product name: TMPTA (trimethylolpropane triacrylate, manufactured by Tokyo Chemical Industry Co., Ltd.), and 10 parts by mass of a bifunctional secondary thiol (product name: Karenz MTBD1, manufactured by Showa Denko K.K.) as a thiol material were added. Next, 0.5 parts by mass of a radical generator (product name: OmniradMBF, manufactured by Sanyo Trading Co., Ltd.) was added. This was stirred at room temperature for 30 minutes to obtain 100 parts by mass of the active energy curable composition of Example 5.

[0052] Example 6 In a 300 mL separable flask equipped with a stirring blade, 75 parts by mass of 2-phenoxyethyl acrylate (product name: 2-phenoxyethyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd.) as a hydrophobic material, 9.8 parts by mass of sodium p-styrenesulfonate (product name: Na p-styrenesulfonate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a hydrophilic material, 0.2 parts by mass of a reactive leveling agent (product name: X-22-164, manufactured by Shin-Etsu Chemical Co., Ltd.), 5 parts by mass of a multifunctional monomer (product name: TMPTA (trimethylolpropane triacrylate, manufactured by Tokyo Chemical Industry Co., Ltd.), and 10 parts by mass of a tetrafunctional secondary thiol (product name: Karenz MTPE1, manufactured by Showa Denko K.K.) as a thiol material were added. Next, 0.5 parts by mass of a radical generator (product name: OmniradMBF, manufactured by Sanyo Trading Co., Ltd.) was added. This was stirred at room temperature for 30 minutes to obtain 100 parts by mass of the active energy curing composition of Example 6.

[0053] Example 7 In a 300 mL separable flask equipped with a stirring blade, 52 parts by mass of 2-phenoxyethyl acrylate (product name: 2-phenoxyethyl acrylate, manufactured by Tokyo Chemical Industry Co., Ltd.) as a hydrophobic material, 9.8 parts by mass of sodium p-styrenesulfonate (product name: Na p-styrenesulfonate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a hydrophilic material, 0.2 parts by mass of a reactive leveling agent (product name: X-22-164, manufactured by Shin-Etsu Chemical Co., Ltd.), 20 parts by mass of a multifunctional monomer (product name: TMPTA (trimethylolpropane triacrylate, manufactured by Tokyo Chemical Industry Co., Ltd.), and 18 parts by mass of a tetrafunctional secondary thiol (product name: Karenz MTPE1, manufactured by Showa Denko K.K.) as a thiol material were added. Next, 0.5 parts by mass of a radical generator (product name: OmniradMBF, manufactured by Sanyo Trading Co., Ltd.) was added. This was stirred at room temperature for 30 minutes to obtain 100 parts by mass of the active energy curing composition of Example 7.

[0054] Comparative Example 1 In a 300 mL separable flask equipped with a stirring blade, 99.4 parts by mass of hydrophilic acrylate (product name: PEG400DA, manufactured by Daicel Allnex Co., Ltd.) as a hydrophilic material and 0.1 parts by mass of reactive leveling agent (product name: BYK-381, manufactured by BYK Co., Ltd.) were added. Next, 0.5 parts by mass of radical generator (product name: Omnirad184, manufactured by Sanyo Trading Co., Ltd.) was added. This was stirred at room temperature for 30 minutes to obtain 100 parts by mass of the active energy curable composition of Comparative Example 1.

[0055] (Evaluation of anti-fogging properties) The test pieces, each having the active energy curable composition of Examples 1 to 5 and Comparative Example 1 cured on the surface, were immersed in 40°C warm water for 240 hours. After that, the test pieces were dried at room temperature, and breath was blown onto the test pieces at room temperature. The surface area of ​​the test pieces where fogging occurred was visually checked to evaluate the antifogging properties on a 5-point scale of A to E. The evaluation was carried out as follows: A: no fogging occurred on the test pieces; B: about 10% of the surface area of ​​the test pieces was fogging; C: about 50% of the surface area of ​​the test pieces was fogging; D: about 80% of the surface area of ​​the test pieces was fogging; and E: the entire surface area of ​​the test pieces was fogging. FIG. 3 shows the evaluation results of the antifogging properties of Examples 1 to 5 and Comparative Example 1.

[0056] (Condition evaluation in low temperature environment) The test pieces, the surfaces of which were cured with the active energy curable compositions of Examples 1 to 5 and Comparative Example 1, were left in a freezer at -40°C for 240 hours. The test pieces were then returned to room temperature, and the state of the cured film was visually checked to evaluate the state in a low-temperature environment on a scale of A to E. The evaluation was carried out as follows: A if the cured film had no cracks or cracks; B if the cured film had no cracks but minor cracks; C if the cured film had no cracks but cracks; D if some of the cured film had cracks and cracks; and E if the cured film had large cracks. FIG. 3 shows the results of the evaluation of the state in a low-temperature environment for Examples 1 to 5 and Comparative Example 1.

[0057] (Evaluation of content of non-reactive volatile organic solvents) The active energy curable compositions of Examples 1 to 5 and Comparative Example 1 were subjected to gas chromatography analysis at 200°C to determine the total amount of components not containing a vinyl group or an acryloyl group. The evaluation was as follows: if the total amount was less than 1 mass%, A; if the total amount was 1 mass% or more and less than 10 mass%, B; if the total amount was 10 mass% or more and less than 30 mass%, C; if the total amount was 30 mass% or more and less than 50 mass%, D; and if the total amount was 50 mass% or more, E. The evaluation results of the content of non-reactive volatile organic solvents of Examples 1 to 5 and Comparative Example 1 are summarized in FIG. 3.

[0058] (Evaluation of ejection properties) The viscosity of the active energy curable compositions of Examples 1 to 5 and Comparative Example 1 was measured and evaluated. The viscosity was measured in accordance with JIS K2283 using an E-type viscometer (product name: TVE-22L, manufactured by Toki Sangyo Co., Ltd.). The evaluation was made as follows: A: viscosity is 3 mPa·s or more and less than 30 mPa·s; B: viscosity is 30 mPa·s or more and less than 40 mPa·s; C: viscosity is 40 mPa·s or more and less than 50 mPa·s; D: viscosity is 50 mPa·s or more and less than 80 mPa·s; and E: viscosity is 80 mPa·s or more. FIG. 3 shows the evaluation results of the dischargeability of Examples 1 to 5 and Comparative Example 1.

[0059] As is clear from Fig. 3, according to Examples 1 to 7, which are active energy curable compositions containing a hydrophobic material and a hydrophilic material, it is clear that excellent anti-fogging properties can be ensured and the occurrence of cracks in the cured film in a low temperature environment can be suppressed. It is also clear that the content of non-reactive volatile organic solvents can be reduced and excellent discharge properties can be ensured. Therefore, the ratio of the active ingredient that becomes the cured film is large, the total amount of materials can be reduced, and there is no need to dilute with an organic solvent when spray coating, which reduces power consumption during production.

[0060] From the results of Examples 2 to 7, it is clear that when a polyfunctional monomer is contained, the content of the non-reactive organic solvent is less than 1 mass %, so that the ratio of the active ingredient that becomes the cured film can be further increased, and therefore the total amount of materials can be further reduced.

[0061] From the results of Examples 2 and 4 to 5, it is clear that when the content of the polyfunctional monomer is about 10%, the viscosity is 3 mPa·s or more and less than 30 mPa·s, and therefore better ejection properties can be ensured.

[0062] From the results of Examples 3 to 7, it is clear that when the content of the hydrophilic material was about 9.8%, the cured film had no cracks or only minor cracks when evaluated in a low-temperature environment, which indicates that the occurrence of cracks in a low-temperature environment could be further suppressed.

[0063] From the results of Examples 4, 6 to 7, when the content of the multifunctional monomer is 5 to 20% and the thiol material is a tetrafunctional secondary thiol, it is clear that the test piece did not become cloudy in the evaluation of the anti-fogging property, so that better anti-fogging property can be ensured. In addition, in the evaluation of the state under a low temperature environment, the cured film has no cracks, so that it is clear that the occurrence of cracks under a low temperature environment can be further suppressed.

[0064] In contrast, in Comparative Example 1, which is an active energy curable composition with a hydrophobic material content of 99.4 mass%, the entire surface of the test piece was fogged in the anti-fogging evaluation, and sufficient anti-fogging properties were not ensured. In addition, large cracks were found in the condition evaluation under a low temperature environment, indicating that low-temperature cracks are likely to occur. Furthermore, since the content of non-reactive organic solvent is 50 mass% or more, the proportion of the active ingredient that becomes the cured film is small, and since the viscosity is 80 mPa·s or more, it is clear that spray coating is not possible unless it is diluted with an organic solvent.

[0065] As described above, the active energy ray-curable composition and resin molded article of the present invention can ensure excellent durability. [Explanation of symbols]

[0066] 10. Active energy ray curable composition 11 Hydrophobic materials 12 Hydrophilic materials 20 Base material 30 Resin molding

Claims

1. An active energy ray curable composition having a radical-reactive material and a leveling agent, The radical-reactive material comprises a hydrophobic material, a hydrophilic material, a polyfunctional monomer, and a thiol material. The leveling agent is a hydrophobic silicone material containing radical reactive groups. The amount of non-reactive volatile organic solvent with a boiling point of 200°C or lower in the above-mentioned active energy ray curable composition is less than 10% by mass. The content of the polyfunctional monomer is 5 to 20% by mass. An active energy ray curable composition wherein the thiol material is a tetrafunctional secondary thiol.

2. The active energy ray curable composition according to claim 1, wherein the amount of a nonreactive volatile organic solvent with a boiling point of 200°C or lower in the active energy ray curable composition is less than 1% by mass.

3. The active energy ray curable composition according to claim 1, used as an anti-fogging coating.

4. A resin molded article comprising a cured film obtained by curing an active energy ray curable composition according to any one of claims 1 to 3, and a substrate having the cured film on at least a part of its surface.

5. The resin molded article according to claim 4, wherein the substrate is hydrophobic.

6. A resin molded article according to claim 5, which is an outer lens for a vehicle light fixture.

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