JP6679848B2 - Active energy ray curable resin composition and molded product using the same - Google Patents

Description

  The present invention relates to an active energy ray-curable resin composition and a molded article using the same.

  Thermoplastic resins can be thermoformed relatively easily and are therefore used as materials for molded articles. However, if an attempt is made to increase the heat-resistant deformation temperature of the molded body, the temperature required for thermoforming also increases, and it is difficult to achieve both moldability and heat resistance.

  On the other hand, as a method for improving the heat resistance, scratch resistance and strength of the thermoplastic resin, a method of introducing a crosslinked structure can be mentioned. However, since the fluidity necessary for thermoforming is lost after introducing the crosslinked structure, the thermoplastic resin having the crosslinked structure introduced at a certain ratio or more cannot be thermoformed. Therefore, at the time of molding, molding can be performed at a relatively low temperature, and if the heat resistance, scratch resistance, and strength can be improved by post-treatment after molding, the moldability and the above-mentioned functions can be made compatible.

  Examples of the post-treatment include crosslinking between polymer molecules. For the crosslinking, for example, silane crosslinking is used. For example, as described in Patent Documents 1 to 3, a polyolefin-based polymer, a resin composition obtained by melt-kneading a silanol catalyst, and a silane crosslinkable polyolefin are kneaded to obtain a molded article by extrusion molding. Then, a method of contacting with water and then crosslinking is mentioned.

JP, 2004-098635, A JP-A-2000-212291 JP, 2006-131720, A

  However, the methods described in Patent Documents 1 to 3 require contact with water, and cannot be used in a system in which materials that dislike water are mixed. Moreover, since the curing reaction is slow, it cannot be processed in a short time.

  It is an object of the present invention to provide an active energy ray-curable resin composition and a molded product thereof which can provide a molded product having excellent thermoformability, heat resistance, scratch resistance, surface hardness and transparency. .

  The present invention includes the following [1] to [5].

[1] An active energy ray-curable resin composition containing an acrylic polymer (A), a polyfunctional acrylate (B), and a photopolymerization initiator (C),
The acrylic polymer (A) contains 75% by mass or more of methyl methacrylate as a monomer unit,
An active energy ray-curable resin composition in which the mass ratio ((A) :( B)) of the acrylic polymer (A) and the polyfunctional acrylate (B) is 75:25 to 90:10.

  [2] The photopolymerization initiator (C) is 2- [2-oxo-2-phenylacetoxy-ethoxy] -ethyl = oxyphenylacetate and 2- (2-hydroxyethoxy) -ethyl = oxyethylacetate. And / or containing 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one. 1] The active energy ray-curable resin composition described in 1).

  [3] The active energy ray-curable resin composition according to [1] or [2], wherein the polyfunctional acrylate (B) has a mass average molecular weight of 260 or more.

  [4] A molded article obtained by thermoforming the active energy ray-curable resin composition according to any one of [1] to [3], which is curable by irradiation with active energy rays.

  [5] A molded product which is a cured product of the active energy ray-curable resin composition according to any one of [1] to [3].

  ADVANTAGE OF THE INVENTION According to this invention, the active energy ray curable resin composition which can provide a thermoformed moldability, and also the heat resistant, the abrasion resistance, the surface hardness, and the transparency excellent in a molded object, and its molded object are provided.

  Hereinafter, a mode for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail, but the present invention is not limited to the following description, and various modifications are possible within the scope of the gist thereof. It can be modified and implemented.

  In addition, below, the monomer component before superposition | polymerization is called "-monomer", and "monomer" may be abbreviate | omitted. In addition, the constitutional units constituting the polymer are referred to as "-monomer units". Further, (meth) acrylate represents methacrylate or acrylate.

[Active energy ray curable resin composition]
The active energy ray-curable resin composition according to the present invention contains an acrylic polymer (A), a polyfunctional acrylate (B), and a photopolymerization initiator (C), and optionally other components (D). including. By irradiating the active energy ray-curable resin composition with an active energy ray, a polymerization reaction proceeds and is cured.

[Acrylic polymer (A)]
The acrylic polymer (A) is a non-polymerizable component and enables the active energy ray-curable resin composition to be handled as a solid even in an uncured state. Specific solid forms include pellets, powders, granules, films, sheets, fibers, blocks, strips and the like. If it can be handled in the form of pellets, powder, granules, etc. in the uncured state, it is advantageous in terms of transportation and storage as a raw material for a molded body used for thermoforming. In addition, not only can it be wound or stacked in the shape of a film, sheet, or fiber in the uncured state, but also processing such as cutting or cutting can be performed.

  Since the uncured active energy ray-curable resin composition is treated as a solid at room temperature, the glass transition point of the acrylic polymer (A) is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, even more preferably 90 ° C. or higher. . On the other hand, if the molding temperature when thermoforming the uncured active energy ray-curable resin composition is too high, or if the temperature when preparing the active energy ray-curable resin composition is too high, polyfunctional The glass transition point of the acrylic polymer (A) is preferably 180 ° C. or lower, more preferably 150 ° C. or lower, even more preferably 120 ° C. or lower, because it may lead to abnormal polymerization of the acrylate (B). The glass transition point is a value measured by a differential scanning calorimeter (DSC).

  Since the uncured active energy ray-curable resin composition is irradiated with active energy rays to be cured, the acrylic polymer (A) is preferably transparent. In particular, since it is assumed that a photopolymerization initiator having a sensitivity in the wavelength range of 250 to 550 nm and a light source that emits light in the ultraviolet / visible range are combined, the acrylic polymer (A) is used in the wavelength range of 250 to 550 nm. It is preferable to have high transmittance. Further, in order for the molded product made of the active energy ray-curable resin composition and the cured product thereof to have an excellent appearance of transparency, it is important to maintain high transparency in the visible light region, and a wavelength of 380 to 380 is required. It preferably has a high transmittance in the region of 780 nm.

  The acrylic polymer (A) contains 75% by mass or more of methyl methacrylate as a monomer unit. Since the acrylic polymer (A) contains 75% by mass or more of methyl methacrylate as a monomer unit, high transmittance in a wavelength range of 250 to 780 nm, a glass transition point of 30 ° C. or higher and 180 ° C. or lower, cost advantage Etc. can be given to the active energy ray-curable resin composition. The acrylic polymer (A) preferably contains 80% by mass or more of methyl methacrylate as a monomer unit, more preferably 85% by mass or more, and further preferably 90% by mass or more. The upper limit of the ratio of methyl methacrylate as a monomer unit in the acrylic polymer (A) is not particularly limited, but is preferably 99.5% by mass or less, and more preferably 99% by mass or less.

  The acrylic polymer (A) can contain a polymerizable monomer other than methyl methacrylate as a monomer unit. The polymerizable monomer contained in the acrylic polymer (A) as a copolymerization component with methyl methacrylate is not particularly limited as long as it has a copolymerizability with methyl methacrylate. Examples of the polymerizable monomer include methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-. Butyl (meth) acrylate, linear alkyl (meth) acrylate, branched alkyl (meth) acrylate, unsaturated alkyl (meth) acrylate, saturated alkyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, synthetic lauryl (C12-C13) (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, beheni Alkyl (meth) acrylates such as (meth) acrylate, oleyl (meth) acrylate, myristyl (meth) acrylate, 2-ethylhexyl (meth) acrylate; cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, Tetrahydrofurfuryl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl Having a ring structure such as (meth) acrylate, nonylphenol (meth) acrylate, phenyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate (Meth) acrylate; (meth) acrylate having a polyalkylene glycol chain such as methoxy polyethylene glycol mono (meth) acrylate, alkoxylated alkyl (meth) acrylate, alkoxylated phenyl (meth) acrylate; 1,4-butanediol di (meth) ) Polyfunctional (meth) acrylates such as acrylates, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate; aromatic vinyls such as styrene and α-methylstyrene; (meth) acrylic acid; A (meth) acrylate having an amino group such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth (Meth) acrylate having a hydroxyl group such as acrylate and hydroxypropyl (meth) acrylate; acrylamide derivative such as (meth) acryloylmorpholine and N, N-dimethyl (meth) acrylamide; 2-vinylpyridine, 4-vinylpyridine, N- Vinylpyrrolidone, N-vinylformamide, vinyl acetate, 1,2,2,6,6-pentamethyl-4-piperidyl = (meth) acrylate, 2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di) acrylic acid -Tertiary pentylphenyl) ethyl] -4,6-di-tertiary pen Ruphenyl, 3- (2H-1,2,3-benzotriazol-2-yl) -4-hydroxyphenethyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8 , (8), 8-Tridecafluorooctyl (meth) acrylate and the like containing (meth) acrylate containing fluorine. These may be used alone or in combination of two or more.

  Among these, it is preferable to use one or more kinds of acrylates as the polymerizable monomer. By copolymerizing methyl methacrylate and acrylate, the depolymerization reaction (zipper cleavage) of polymethacrylate can be prevented. Examples of the acrylate include methyl acrylate, n-propyl acrylate, n-butyl acrylate, i-butyl acrylate and the like. Among these, it is preferable to use methyl acrylate from the viewpoint of heat resistance and cost. These may be used alone or in combination of two or more.

  The acrylic polymer (A) preferably contains 0 to 20% by mass of an acrylate as a monomer unit, more preferably 0.5 to 10% by mass, and further preferably 1 to 5% by mass. When the content of the acrylate as a monomer unit satisfies the above range, the acrylic polymer (A) can exhibit sufficient heat resistance, weather resistance, thermal decomposition resistance, transparency, mechanical properties and the like. .

  The mass average molecular weight (Mw) of the acrylic polymer (A) is preferably 50,000 to 200,000, and more preferably 70,000 to 150,000. When the Mw satisfies the above range, the acrylic polymer (A) can exhibit sufficient heat resistance, weather resistance, thermal decomposition resistance, transparency, mechanical properties, fluidity, moldability and the like. The number average molecular weight (Mn) of the acrylic polymer (A) is preferably 25,000 to 200,000, more preferably 35,000 to 150,000. When Mn satisfies the above range, the acrylic polymer (A) can exhibit sufficient heat resistance, weather resistance, thermal decomposition resistance, transparency, mechanical properties, fluidity, moldability and the like. Note that Mw and Mn are values measured by the method described below.

  As a method for producing the acrylic polymer (A), known methods such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method and a precipitation polymerization method can be used. Among these methods, the bulk polymerization method and the suspension polymerization method are preferable, and the bulk polymerization method is more preferable. The bulk polymerization method is a method suitable for mass production among polymerization methods for obtaining various acrylic resins, and is advantageous in terms of production speed (production amount), production cost, and the like.

  In the present invention, the mass ratio ((A) :( B)) of the acrylic polymer (A) and the polyfunctional acrylate (B) is 75:25 to 90:10, and 77:23 to 88:12. Is preferred, and 80:20 to 85:15 is more preferred. When the proportion of the acrylic polymer (A) is 75% by mass or more, the handleability as a solid becomes good even when the active energy ray-curable resin composition is in an uncured state. Further, when the proportion of the acrylic polymer (A) is 90% by mass or less, the effect of the polyfunctional acrylate (B) described below is sufficiently exhibited.

[Polyfunctional acrylate (B)]
The polyfunctional acrylate (B) is a polymerizable component, and polymerization proceeds by irradiation with an active energy ray to form a crosslinked structure. Further, the polyfunctional acrylate (B) functions as a plasticizer of the active energy ray-curable resin composition before irradiation with the active energy ray, and lowers the molding temperature during thermoforming. As a result of intensive studies, the present inventor has found that acrylate is superior to methacrylate in preventing yellowing and gelation during thermoforming. The polyfunctional acrylate (B) is a bifunctional or higher functional acrylate for forming a crosslinked structure, and is preferably a trifunctional or higher functional acrylate.

  The polyfunctional acrylate (B) preferably has low volatility. Specifically, it is preferable that the volatile amount of the polyfunctional acrylate (B) is small when preparing an uncured active energy ray-curable resin composition or during thermoforming. Therefore, it is preferable that the polyfunctional acrylate (B) has a large mass average molecular weight (Mw). The mass average molecular weight (Mw) of the polyfunctional acrylate (B) is preferably 260 or more, more preferably 360 or more, still more preferably 460 or more. Although the upper limit of Mw of the polyfunctional acrylate (B) is not particularly limited, it can be set to, for example, 50,000 or less. In addition, when Mw is 3000 or less, the molecular weight calculated from the structural formula is used, and when Mw exceeds 3000, the value measured by the method described below is used.

  Examples of the polyfunctional acrylate (B) include, as bifunctional acrylates, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, 1,12-dodecanediol diacrylate, tetraethylene glycol diacrylate and polyethylene. Glycol diacrylate, ethoxylated bisphenol A diacrylate, propoxylated bisphenol A diacrylate, alkoxylated bisphenol A diacrylate, cyclohexanedimethanol diacrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, dioxane glycol diacrylate, alkoxylation Hexanediol diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, trisethylene Rodecane dimethanol diacrylate, alkoxylated neopentyl glycol diacrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, tris (2-hydroxyethyl) isocyanurate diacrylate; bifunctional urethane acrylate And bifunctional epoxy acrylate, and other polymers having an average of two acryloyl groups in the same molecule.

  Trifunctional or higher functional acrylates include trimethylolpropane triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, alkoxylated trimethylolpropane triacrylate. , Pentaerythritol (tri) tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol (penta) hexaacrylate, ethoxylated dipentaerythritol hexaacrylate, ε-caprolactone modified tris (acryloxyethyl) isocyanate Nurate, trifunctional or higher urethane acrylate, trifunctional or higher epoxy acrylate Rate, polyglycerin polyethylene oxide polyacrylate, tripentaerythritol polyacrylate, a super-functional acrylic pendant polymer which is a cationic polymer of 2- (2-vinyloxyethoxy) ethyl acrylate, and an average of 3 acryloyl groups in the same molecule. Examples thereof include polymers having two or more. These may be used alone or in combination of two or more.

  Among these, the molded product produced by irradiating the active energy ray-curable resin composition with the active energy ray has good heat resistance, scratch resistance, surface hardness, weather resistance, transparency, and low volatility. The polyfunctional acrylate (B) is trimethylol propane triacrylate, ditrimethylol propane tetraacrylate, pentaerythritol, since it has good compatibility with the acrylic polymer (A) and is advantageous in terms of cost. (Tri) tetraacrylate, dipentaerythritol (penta) hexaacrylate, tripentaerythritol polyacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, and their alkoxylated and caprolactone modified products are preferable.

  As described above, in the present invention, the mass ratio ((A) :( B)) of the acrylic polymer (A) and the polyfunctional acrylate (B) is 75:25 to 90:10, and 77: 23-88: 12 is preferable, and 80: 20-85: 15 is more preferable. Since the ratio of the polyfunctional acrylate (B) is 10% by mass or more, the molded product, which is a cured product of the active energy ray-curable resin composition, has a favorable crosslinked structure formed by irradiation with active energy rays. Heat resistance, scratch resistance, and surface hardness are given, and the thermoforming temperature can be suppressed to a sufficiently low level. In addition, since the ratio of the polyfunctional acrylate (B) is 25% by mass or less, the active energy ray-curable resin composition can be handled as a solid even in an uncured state, and a molded product before curing is excellent. Dimensional stability can be realized. Further, the curing shrinkage at the time of irradiation with active energy rays can be suppressed to a sufficiently low level.

[Photopolymerization initiator (C)]
The photopolymerization initiator (C) is a compound that is cleaved by irradiation with an active energy ray to generate a radical that initiates a polymerization reaction. As the active energy rays, ultraviolet rays and visible rays are preferable from the viewpoint of device cost and productivity.

  Examples of the photopolymerization initiator (C) that generates radicals by ultraviolet rays include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methylorthobenzoylbenzoate, 4-phenylbenzophenone, and t. -Butylanthraquinone, 2-ethylanthraquinone, thioxanthones (2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, etc.), acetophenones (diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane) -1-one, benzyl dimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-di Tylamino-1- (4-morpholinophenyl) -butanone, 2- [2-oxo-2-phenylacetoxy-ethoxy] -ethyl oxyphenyl acetate and 2- (2-hydroxyethoxy) -ethyl oxyethyl acetate , 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one, etc.), benzoin ethers ( Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.), acylphosphine oxides (2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4 -Trimethylpentylphosphine Sid, bis (2,4,6-trimethylbenzoyl) - phenyl phosphine oxide, etc.), methylbenzoyl formate, 1,7-bis acridinyl heptane, 9-phenyl acridine, and the like.

  Among these, 2- [2-oxo-2-phenylacetoxy-ethoxy] -ethyl = oxyphenylacetate and 2- (2-hydroxyethoxy) -ethyl = oxy, because of their low volatility and high radical generating ability. Using a mixture with ethyl acetate, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one. Is preferred.

  Further, when the molded product is thick and requires deep-curing, or when the molded product needs to have a function of absorbing ultraviolet rays, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, which is an acylphosphine oxide, is used. It is preferable to use bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

  These photopolymerization initiators (C) may be used alone or in combination of two or more. When these photopolymerization initiators (C) are used in combination, it is preferable to use two or more kinds having different absorption wavelengths in combination. If necessary, a thermal polymerization initiator such as a persulfate (potassium persulfate, ammonium persulfate, etc.), a peroxide (benzoyl peroxide, etc.), an azo-based initiator or the like may be used in combination.

  The content of the photopolymerization initiator (C) is 0.01 with respect to a total of 100 parts by mass of the acrylic polymer (A) and the polyfunctional acrylate (B) contained in the active energy ray-curable resin composition. -10 mass parts is preferable, 0.1-5 mass parts is more preferable, and 0.2-3 mass parts is still more preferable. When the content of the photopolymerization initiator (C) is 0.01 parts by mass or more, curing of the active energy ray-curable resin composition is sufficiently advanced, and the molded product after irradiation with active energy rays has sufficient heat resistance. , Scratch resistance, and surface hardness. When the content of the photopolymerization initiator (C) is 10 parts by mass or less, the unreacted photopolymerization initiator (C) does not remain in the molded body after curing, and the molded body after curing has sufficient heat resistance. It has scratch resistance, surface hardness, no coloring, and high weather resistance.

[Other ingredients (D)]
The other component (D) is a component added as necessary, and is a component other than the acrylic polymer (A), the polyfunctional acrylate (B) and the photopolymerization initiator (C). Other components (D) include flame retardants, flame retardant aids, plasticizers, surfactants, release agents, slip agents, lubricants, light stabilizers, ultraviolet absorbers, fillers, adhesion promoters, Colorants, pigments, dyes, reinforcing agents, inorganic fillers, mica powder, impact resistance improvers, polymerization inhibitors, antioxidants, heat stabilizers, pH adjusters, fluidity improvers, antistatic agents, conductivity imparting Agents, stress relaxation agents, crystallization accelerators, hydrolysis inhibitors, compatibilizers, nucleating agents, sensitizers, defoamers, coupling agents, antibacterial / antifungal agents, rust preventives and the like. These may be used alone or in combination of two or more. The active energy ray-curable resin composition may contain a trace amount of an organic solvent as the other component (D).

  Examples of the polymerization inhibitor include hydroquinone (HQ) and hydroquinone monomethyl ether (MEHQ) as hydroquinone-based polymerization inhibitors. Examples of the phenol-based polymerization inhibitor include 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), catechol, picric acid, tert-butylcatechol, 2,6-di-tert-butyl-p- Cresol (BHT), 4,4′-thiobis [ethylene (oxy) (carbonyl) (ethylene)] bis [2,6-bis (1,1-dimethylethyl) phenol] and the like can be mentioned. Examples of the phenothiazine-based polymerization inhibitor include phenothiazine, bis (α-methylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, and bis (α, α-dimethylbenzyl) phenothiazine. These may be used alone or in combination of two or more. Among the polymerization inhibitors listed here, a phenolic polymerization inhibitor such as BHT can also be used as an antioxidant.

  Examples of antioxidants include hindered phenol-based, benzimidazole-based, phosphorus-based, sulfur-based, hindered amine-based antioxidants, and hindered phenol-based antioxidants are preferable.

  Examples of the hindered phenol-based antioxidants include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and neodiethylenebis [3- (3,5-diester). -T-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,3 ′, 3 ″, 5,5 ′, 5 '' -Hexa-t-butyl-a, a ', a' '-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propione ], Hexamethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,3,5-Tris (3,5-di-t-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris [(4-t-butyl-3-hydroxy-2,6-xylin) methyl ] -1,3,5-Triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-t-butyl-4- (4,6-bis (octylthio) -1,3 , 5-triazin-2-ylamine) phenol and the like. These may be used alone or in combination of two or more. Of these, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] is preferred because it has low volatility and a large effect as an antioxidant.

  Examples of phosphorus-based antioxidants include tris (2,4-di-t-butylphenyl) phosphite and bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl). Ethyl ester phosphorous acid, tetrakis (2,4-di-t-butylphenyl) (1,1-biphenyl) -4,4′-diylbisphosphonite, bis (2,4-di-t-butylphenyl) ) Pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol-diphosphite, tetrakis (2,4) -T-butylphenyl) (1,1-biphenyl) -4,4'-diylbisphosphonite, di-t-butyl-m-cresyl-phosphonite And the like. These may be used alone or in combination of two or more.

  Examples of the ultraviolet absorber include benzotriazole compounds, benzotriazine compounds, benzoate compounds, benzophenone compounds, oxybenzophenone compounds, phenol compounds, oxazole compounds, malonate compounds, cyanoacrylate compounds, Examples thereof include lactone compounds, salicylate compounds, benzoxazinone compounds, and the like. Among these, benzotriazole compounds and benzotriazine compounds are preferable. These may be used alone or in combination of two or more.

  Examples of the light stabilizer include hindered amine-based antioxidants. Examples of the primary antioxidant that is a hindered amine-based radical scavenger include, for example, commercially available products, Chimassorb 2020FDL, Chimassorb 944FDL, Tinuvin 622SF, Uvinul 5050H, Tinuvin 144, Tinuvin 765SFin, 40inu FF70, Tinuvin 750, Tinuvin 750, Tinuvin 750u, Tinuvin 750u, Tinuvin 750u, Tinuvin 750u, Tinuvin 750u, Tinuvin 750u. Manufactured) and the like. These may be used alone or in combination of two or more.

  Examples of the release agent and slip agent include fatty acids, fatty acid amides, organic phosphoric acid compounds, phosphoric acid ester compounds, acidic phosphoric acid ester compounds, fluorine-containing compounds, silicone compounds, compounds having a long-chain alkyl group, paraffin, Waxes, oils and fats, long-chain alkyl alcohols and the like can be mentioned. These may be used alone or in combination of two or more.

[Method for preparing active energy ray curable resin composition]
In order to obtain the active energy ray-curable resin composition in a uniform state, it is necessary to mix the solid acrylic polymer (A) and the polyfunctional acrylate (B). Therefore, examples of the method of preparing the active energy ray-curable resin composition include a method of using a volatile component and a method of heating and kneading.

(Method using volatile components)
The method of using a volatile component is a method of using a volatile component such as a solvent for handling the acrylic polymer (A) in a liquid state. For example, after the acrylic polymer (A) and the volatile component are mixed to obtain a syrup-like liquid, a polyfunctional acrylate (B), a photopolymerization initiator (C), and other components as necessary. A uniform syrup-like liquid is obtained by adding (D) and mixing. Then, the volatile components are removed to obtain a solid, uncured active energy ray-curable resin composition.

  Examples of the volatile component include a solvent and a low molecular weight polymerizable component. Examples of the solvent include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diisobutyl ketone (DIBK), cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and isophorone, toluene, xylene, Hydrocarbons such as normal hexane, cyclohexane, methylcyclohexane, normal heptane, naphtha, terpene, petroleum benzine, d-limonene, isoparaffins, ethylbenzene, xylene, benzene, methanol, ethanol, isopropyl alcohol, normal propyl alcohol, isobutanol, Alcohols such as 1-butanol and 2-butanol, acetic acid esters such as methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate and amyl acetate, etc. Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mononormal butyl ether, ethylene glycol monotertiary butyl ether, cellosolves such as 2-methoxymethyl acetate and 2-ethoxyethyl acetate, glycol ethers, ethers such as tetrahydrofuran and diethyl ether. , Chlorohydrocarbons such as dichloromethane, trichloroethylene, tetrachloroethylene, carbon tetrachloride, 1,1,1-trichloroethane, 1,2-dichloropropane, nitrogen-containing solvents such as N, N-dimethylformamide (DMF), γ- Examples include butyrolactone and ethyl lactate. These may be used alone or in combination of two or more.

  Examples of the low molecular weight polymerizable component include a monofunctional polymerizable component having a molecular weight of less than 260. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, Examples thereof include styrene and α-methylstyrene. These may be used alone or in combination of two or more.

  Since the acrylic polymer (A) is handled as a liquid, the acrylic polymer (A) can be produced by a bulk polymerization method to control the polymerization rate. For example, a monomer that is a raw material of the acrylic polymer (A) is polymerized by a bulk polymerization method to produce a syrup-shaped liquid having a polymerization rate of about 20 to 80%. A polyfunctional acrylate (B), a photopolymerization initiator (C), and optionally other component (D) are added to the syrup-like liquid and mixed to obtain a uniform liquid. Then, the remaining monomer is removed by a method such as degassing extrusion. At this time, methyl (meth) acrylate and ethyl (meth) acrylate are preferable as a monomer which is a raw material of the acrylic polymer (A) used in the bulk polymerization method. It is preferable that the monomer is more volatile.

(Method of heating and kneading)
The method of heating and kneading is to heat the solid acrylic polymer (A) to mix it with the polyfunctional acrylate (B), the photopolymerization initiator (C), and optionally other components (D). Is the way. The heating temperature is preferably a temperature at which the acrylic polymer (A) melts, but if heated to a temperature at which the acrylic polymer (A) starts to swell with the polyfunctional acrylate (B), a uniform active energy ray can be obtained. A curable resin composition may be obtained. On the other hand, the heating temperature is preferably 300 ° C or lower, more preferably 250 ° C or lower. When the heating temperature is 300 ° C. or lower, thermal decomposition of the acrylic polymer (A) can be prevented. Further, when the heating temperature is 250 ° C. or lower, it is easy to suppress the phenomenon that the polyfunctional acrylate (B) abnormally polymerizes during kneading. As a device for heating and kneading, a general kneading device can be applied, and examples thereof include a roll mill, a kneader, a Banbury mixer, a twin-screw extruder, and a single-screw extruder.

[Molded body (uncured)]
The molded product according to the present invention (hereinafter also referred to as an uncured molded product) is a molded product obtained by thermoforming the active energy ray-curable resin composition according to the present invention, and can be cured by irradiation with active energy rays. Is. The thermoforming method for the active energy ray-curable resin composition includes injection molding, sheet molding, blow molding, injection blow molding, inflation molding, T die molding, press molding, extrusion molding, foam molding, and film molding by casting method. It is possible to use a known method such as the above, and it is also possible to use a secondary processing molding method such as pressure forming and vacuum forming. 80-250 degreeC is preferable and, as for the thermoforming temperature at the time of thermoforming, 100-200 degreeC is more preferable.

[Molded product (cured product)]
The molded product according to the present invention (hereinafter, also referred to as a molded product that is a cured product) is a cured product of the active energy ray-curable resin composition according to the present invention. The molded product that is a cured product can be obtained by irradiating the uncured molded product with an active energy ray. Examples of the active energy ray include ultraviolet rays, visible rays, electron rays, and the like, but it is preferable to use ultraviolet rays in terms of device size, cost, and combination with the photopolymerization initiator (C). The case of using ultraviolet rays will be described below. Examples of the light source for generating ultraviolet rays include a high pressure mercury lamp, a metal halide lamp, an LED (light emitting diode), and an electrodeless lamp. The wavelength band in the ultraviolet region to be used is preferably selected in consideration of the transmission spectrum of the active energy ray-curable resin composition and the absorption wavelength of the photopolymerization initiator (C).

The irradiation amount of ultraviolet rays may be determined according to the absorption wavelength and content of the photopolymerization initiator (C). For example the integrated light quantity is preferably ^{400~4000mJ / cm 2, 400~2000mJ / cm} 2 is more preferable. When the integrated light amount is 400 mJ / cm ² or more, the active energy ray-curable resin composition can be sufficiently cured, the surface hardness is increased, and the scratch resistance is improved. Further, when the integrated light quantity is 4000 mJ / cm ² or less, it is possible to prevent coloring of the molded product which is a cured product and deterioration of the base material. The irradiation intensity is not particularly limited, but it is preferable to suppress the output to such an extent as not to cause deterioration of the base material.

  The temperature of the molded product at the time of UV irradiation affects the progress of the curing reaction of the active energy ray-curable resin composition. 20-200 degreeC is preferable, as for the temperature of the molded object at the time of ultraviolet irradiation, 40-150 degreeC is more preferable, and 50-130 degreeC is still more preferable. When the temperature of the molded product upon irradiation with ultraviolet rays is 20 ° C. or higher, the reactivity of the generated radicals is high, and the mobility of the polyfunctional acrylate (B) is also high, so the reaction rate is high. When the reaction rate is high, a crosslinked structure is easily formed, and heat resistance, scratch resistance, surface hardness, etc. are improved. Further, since the amount of the remaining double bond groups is small, a molded product which is a cured product having excellent weather resistance can be obtained. On the other hand, when the temperature of the molded product at the time of ultraviolet irradiation is 200 ° C. or lower, the shape of the molded product can be maintained until after the irradiation of the active energy. In addition, it is possible to prevent deterioration of dimensional stability and occurrence of cracks due to increased curing shrinkage and thermal shrinkage. Further, it is preferable that the time for heating the molded body during irradiation of ultraviolet rays is short.

[Use]
The active energy ray-curable resin composition according to the present invention can be suitably used as a material for various molded products. Examples of the use of the molded article include household products, OA equipment, AV equipment, battery electrical equipment applications, lighting equipment, housing applications, sanitary applications, elastic play equipment applications, head lamp covers, rear lamp covers, rear combination lamp covers, visors, Vehicle parts such as bag guards, instrument covers, and meter panels, liquid crystal displays, plasma displays, organic EL displays, field emission displays, light guide plates used for displays such as rear projection televisions, diffusion plates, polarizing plate protective films, 1/4 Examples thereof include wave plates, half-wave plates, viewing angle control films, retardation films such as liquid crystal optical compensation films, display front plates, display substrates, lenses, touch panels, and transparent substrates used for solar cells. In addition, the molded product can be used as a waveguide, a lens, an optical fiber, a coating material for an optical fiber, a lens of an LED, a lens cover, etc. in the fields of optical communication systems, optical switching systems, and optical measurement systems. The molded product can also be used as a modifier for other resins.

  Hereinafter, the present invention will be described with reference to specific examples and comparative examples, but the present invention is not limited thereto.

[Evaluation methods]
(Martens hardness)
In the present invention, the numerical value measured under the following conditions is treated as Martens hardness.
Device: FISCHERSCOPE HM2000 (trade name, manufactured by Helmut Fischer GmbH, micro hardness tester)
Indenter: Vickers indenter (tetrahedral diamond cone)
Evaluation program: [Indentation (100 mN / 5 seconds)] → [Creep (100 mN, 5 seconds) → [Unloading (100 mN / 5 seconds)].

(Mw and Mn measurement)
The Mw and Mn of the polymer were measured using gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, trade name: HLC-8220) under the following conditions.
Column: TSK GUARD Cobalt LUMN SUPER HZ-L (4.6 × 35 mm) and two TSK-GEL SUPER HZM-N (6.0 × 150 mm) are connected in series Eluent: Tetrahydrofuran Measurement temperature: 40 ° C.
Flow rate: 0.6 mL / min. Mw and Mn of the polymer are PMMA (Mp (peak top molecular weight) = 141,500, 55,600, 10,290 and 1,590) produced by Polymer Laboratories. It calculated | required using the calibration curve created using it.

(Handling at room temperature)
It was confirmed whether the pellet-shaped uncured active energy ray-curable resin can maintain its original properties under the conditions of a temperature of 23 ° C. and a humidity of 50% without aggregation of particles. The evaluation was performed based on the following criteria.
Good: Pellets can be maintained.
X: There is aggregation of particles.

[material]
The raw materials used in Examples and Comparative Examples are shown below.
・ Methyl methacrylate (MMA): Acryester M (trade name) manufactured by Mitsubishi Rayon Co., Ltd.
・ Methyl acrylate (MA): Mitsubishi Chemical Co., Ltd. ・ Alkyl methacrylate (SLMA): Mitsubishi Rayon Co., Acryester SLMA (trade name)
2,2'-azobis (2-methylpropionamidine) dihydrochloride (V-50): Wako Pure Chemical Industries, Ltd.2,2'-azobisisobutyronitrile (V-60 (AIBN)): Wako Pure Chemical Industries, Ltd., 1-octanethiol: Wako Pure Chemical Industries, Ltd., sodium sulfate: Wako Pure Chemical Industries, Ltd., 2-sulfoethyl sodium methacrylate: Mitsubishi Rayon, Acryester SEM-Na (trade name) )
* 1,9-Nonanediol dimethacrylate (C9DMA): Shin Nakamura Chemical Co., Ltd., NK ester NOD-N (trade name)
* 1,9-Nonanediol diacrylate (C9DA): V # 260 (trade name) manufactured by Osaka Organic Chemical Industry Co., Ltd.
Trimethylolpropane trimethacrylate (TMPTMA): Shin Nakamura Chemical Co., Ltd., NK ester TMPT (trade name)
Trimethylolpropane triacrylate (TMPTA): manufactured by Toagosei Co., Ltd., Aronix M-309 (trade name)
-Ditrimethylolpropane tetraacrylate (DTMPTA): manufactured by Toagosei Co., Ltd., Aronix M-408 (trade name)
-Dipentaerythritol (penta) hexaacrylate (DPHA): Nippon Kayaku Co., Ltd., KAYARAD DPHA (trade name)
-2- [2-oxo-2-phenylacetoxy-ethoxy] -ethyl = oxyphenylacetate and 2- (2-hydroxyethoxy) -ethyl = oxyethylacetate mixture (Irg.754): manufactured by BASF. , Irgacure 754 (trade name)
2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (Irg.127): manufactured by BASF. Irgacure 127 (trade name)
-Pentaerythritol terakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]: manufactured by BASF, Irganox 1010 (trade name)
4-Methoxyphenol (MEHQ): manufactured by Tokyo Chemical Industry Co., Ltd.

[Production Example 1] Synthesis of dispersant (1) 61.6 parts by mass of 17% by mass aqueous potassium hydroxide solution and 19.1 parts by mass of MMA were placed in a 1200 L capacity reaction vessel equipped with a stirrer, a cooling tube and a thermometer. Parts by weight and 19.3 parts by weight of deionized water were charged. Then, the liquid in the reactor was stirred at room temperature, and after confirming an exothermic peak, the mixture was further stirred for 4 hours. Then, the reaction liquid in the reaction apparatus was cooled to room temperature to obtain an aqueous potassium methacrylate solution.

  Then, 900 parts by mass of deionized water, 60 parts by mass of acrylate ester SEM-Na, and 10 parts by mass of the potassium methacrylate aqueous solution were placed in a reaction vessel having a capacity of 1,050 L equipped with a stirrer, a cooling tube and a thermometer. And 12 parts by mass of MMA were added and stirred, and the temperature in the polymerization apparatus was raised to 50 ° C. while substituting with nitrogen. 0.08 part of V-50 as a polymerization initiator was added thereto, and the temperature was further raised to 60 ° C. After the temperature was raised, MMA was continuously added dropwise at a rate of 0.24 part / minute for 75 minutes using a dropping pump. The reaction solution was kept at 60 ° C. for 6 hours and then cooled to room temperature to obtain a dispersant (1) having a solid content of 10 mass% as a transparent aqueous solution.

[Production Example 2] Synthesis of acrylic polymer (A-1) 150 parts by mass of deionized water, 0.3 parts by mass of sodium sulfate and 0.26 parts by mass of the dispersant (1) prepared in Preparation Example 1 were mixed. To prepare an aqueous dispersion medium for suspension. In a separable flask with a cooling tube, 99 parts by mass of MMA, 1 part by mass of MA, 0.2 parts by mass of n-octanethiol as a chain transfer agent, and 0.1 parts by mass of AIBN were charged, and stirred to prepare a uniform raw material. A composition was obtained. Then, after adding the suspension aqueous dispersion medium to the raw material composition, while stirring the atmosphere in the separable flask with nitrogen by nitrogen bubbling, the stirring rotation speed was increased to obtain a syrup dispersion liquid. The syrup dispersion liquid was heated to 75 ° C. and the external temperature of the separable flask was maintained. When the syrup dispersion liquid reached 75 ° C. after the peak of the heat of polymerization was generated, the syrup dispersion liquid was heated to 85 ° C. and held for 30 minutes to complete the polymerization to obtain a suspension. After cooling the suspension to 40 ° C. or lower, the suspension was filtered through a filter cloth, the filtered product was washed with deionized water, and dried at 40 ° C. for 16 hours to obtain an acrylic polymer (A- 1) was obtained. The mass average molecular weight Mw of the acrylic polymer (A-1) was 98,000, and the number average molecular weight Mn was 52,000.

[Production Example 3] Synthesis of acrylic polymer (A-2) 150 parts by weight of deionized water, 0.3 parts by weight of sodium sulfate, and 0.26 parts by weight of the dispersant (1) produced in Production Example 1 were mixed. To prepare an aqueous dispersion medium for suspension. In a separable flask equipped with a cooling tube, 70 parts by mass of MMA, 30 parts by mass of SLMA, 0.2 parts by mass of n-octanethiol as a chain transfer agent, and 0.1 parts by mass of AIBN were charged and stirred to prepare a uniform raw material. A composition was obtained. Then, after adding the suspension aqueous dispersion medium to the raw material composition, while stirring the atmosphere in the separable flask with nitrogen by nitrogen bubbling, the stirring rotation speed was increased to obtain a syrup dispersion liquid. The syrup dispersion liquid was heated to 75 ° C. and the external temperature of the separable flask was maintained. When the syrup dispersion liquid reached 75 ° C. after the peak of the heat of polymerization was generated, the syrup dispersion liquid was heated to 85 ° C. and held for 30 minutes to complete the polymerization to obtain a suspension. After cooling the suspension to 40 ° C. or lower, the suspension was filtered through a filter cloth, the filtered product was washed with deionized water, and dried at 40 ° C. for 16 hours to obtain an acrylic polymer (A- 2) was obtained. The acrylic polymer (A-2) had Mw of 105,000 and Mn of 54,000.

[Heating test of polyfunctional (meth) acrylate]
A heating test was performed to confirm that the polyfunctional (meth) acrylate did not abnormally polymerize or color during thermoforming. In the heating test, 0.2 parts by mass of MEHQ and 1.0 part by mass of Irganox 1010 were added to 100 parts by mass of polyfunctional (meth) acrylate, and about 0.5 mL of this was added to a test tube and the temperature was increased to 200 ° C. After heating for 30 minutes, the change before and after was observed. The results are shown in Table 1. As shown in Table 1, some of the methacrylates were colored and some gelled, while all of the acrylates did not change in appearance and gelation did not occur. Moreover, volatilization before and after the test could not be confirmed in any of the samples. In the following examples, DTMPTA and DPHA were used as the polyfunctional acrylate (B).

[Example 1]
8.5 g of the acrylic polymer (A-1) of Production Example 2 and 34 g of acetone were mixed and stirred at 50 ° C. for about 1 hour to obtain a uniform and transparent syrup-like solution. Next, 1.5 g of DTMPTA, 20 mg of MEHQ, 50 mg of Irganox 1010, and 50 mg of Irgacure 127 were added, and the mixture was stirred until it became a uniform and transparent syrupy solution. The obtained syrup-like solution was applied on a glass plate and then dried in a dryer at 60 ° C. for 2 hours. The obtained film sample was pulverized to obtain a pellet-shaped uncured active energy ray-curable resin composition. The uncured active energy ray-curable resin composition can be handled as pellets in an environment of room temperature of 23 ° C. and humidity of 50%, and the grains of the pellets are fused to each other or are polyfunctional acrylate (B). The DTMPTA did not bleed.

  Next, the pellet-shaped uncured active energy ray-curable resin composition was thermoformed into a film. First, a 0.5 mm thick spacer made of PTFE (polytetrafluoroethylene) is used between two 188 μm thick films made of polyethylene phthalate (PET) to form pellets of uncured active energy. About 1.5 g of the line curable resin composition was sandwiched. Then, using a heat press machine (manufactured by Toyo Seiki Co., Ltd., product name: Minitest Press), after preheating for about 3 minutes, hot press molding at a pressure of about 1 MPa for about 3 minutes to form a film with a thickness of 0.5 mm. A sample piece was obtained. The hot press molding temperature was the lowest temperature at which a uniform film sample having a predetermined thickness was obtained. Specifically, the method was tried while increasing the temperature in increments of 100 ° C. in steps of 10 ° C. The lowest temperature at which the resin spreads in a uniform thickness and becomes a disk shape was defined as the hot press molding temperature. In this example, the hot press molding temperature was 130 ° C., and the obtained film sample was transparent and had no surface tackiness.

Then, the film sample was irradiated with ultraviolet rays to be cured. A 6-inch UV conveyor system (Model LC-6B Benchtop Conveyor (trade name) manufactured by Heraeus) was used as an ultraviolet irradiation device, and the total light amount was adjusted to 1000 mJ / cm ² using a D bulb. . The film sample was attached to a steel plate having a thickness of 2 mm with Cellotape (registered trademark), put into a dryer, and heated to 60 ° C. The film sample was placed on a conveyor together with the iron plate heated to 60 ° C., and was irradiated with ultraviolet rays to be cured. The obtained film-like sample was transparent, before and after the ultraviolet irradiation, the Martens hardness is increased from 61N / mm ² to 148N / mm ^2. Table 2 shows the evaluation results.

[Examples 2 and 3]
Example 1 was repeated except that the composition of the active energy ray-curable resin composition was changed as shown in Table 2. Table 2 shows the evaluation results. In Examples 2 and 3, a transparent film-like sample was obtained as in Example 1, and the Martens hardness was increased by ultraviolet irradiation.

[Comparative Example 1]
The same procedure as in Example 1 was carried out except that the composition of the active energy ray-curable resin composition was only the acrylic polymer (A-1). Table 2 shows the evaluation results. The Martens hardness was good, but the temperature required for hot press molding was 200 ° C, which was 70 ° C higher than in Examples 1-3.

[Comparative Example 2]
The same procedure as in Example 1 was carried out except that the composition of the active energy ray-curable resin composition was only the acrylic polymer (A-2). Table 2 shows the evaluation results. The hot press molding temperature was 130 ° C., which was equivalent to that of Examples 1 to 3, but the Martens hardness before irradiation with ultraviolet rays was 101 N / mm ² , which was higher than that of Examples 1 to 3.

[Comparative Example 3]
Example 1 was repeated except that the composition of the active energy ray-curable resin composition was changed as shown in Table 2. Table 2 shows the evaluation results. In this comparative example, since the active energy ray-curable resin composition contains 30% by mass of the polyfunctional acrylate (B), the active energy ray-curable resin composition before being irradiated with ultraviolet rays becomes too soft and the handling property at room temperature is low. It became "x". Further, the Martens hardness before irradiation with ultraviolet rays was 5 N / mm ² , which was very low, and there was a possibility that a specific shape could not be maintained. Further, the Martens hardness after ultraviolet irradiation was a low value of 51 N / mm ² .

[Comparative Example 4]
Example 1 was repeated except that the composition of the active energy ray-curable resin composition was changed as shown in Table 2. Table 2 shows the evaluation results. In this comparative example, since the active energy ray-curable resin composition contains only 5% by mass of the polyfunctional acrylate (B), the active energy ray-curable resin composition before irradiation with ultraviolet rays is relatively hard and the hot press molding temperature is high. Was higher by 20 ° C. than in Examples 1-3. Moreover, Martens hardness, before the ultraviolet irradiation 118 N / mm ^2, after ultraviolet irradiation is 128N / mm ^2, it was found that the high hardness by ultraviolet irradiation hardly proceed.

  Since the active energy ray-curable resin composition according to the present invention has high heat resistance, excellent scratch resistance, and surface hardness, for example, household products, OA equipment, AV equipment, battery electrical equipment, lighting equipment, housing applications , Sanitary applications, elastic play equipment applications, head lamp covers, rear lamp covers, rear combination lamp covers, visors, bagguards, instrument covers, meter panels, and other vehicle parts, liquid crystal displays, plasma displays, organic EL displays, field emission displays, rear A light guide plate, a diffusion plate, a polarizing plate protective film, a 1/4 wavelength plate, a 1/2 wavelength plate, a viewing angle control film, a retardation film such as a liquid crystal optical compensation film, a display front plate, which is used for a display such as a projection television. Display board, lens, touch panel It can be suitably used for transparent substrate or the like used for solar cells. In addition, in the fields of optical communication systems, optical switching systems, and optical measurement systems, they can also be used as waveguides, lenses, optical fibers, optical fiber coating materials, LED lenses, lens covers, and the like. It can also be used as a modifier for other resins.

Claims (8)

An acrylic polymer (A), the polyfunctional acrylate (B), and a photopolymerization initiator (C) to including active energy ray curable resin composition,
Before SL acrylic polymer (A) is a methyl methacrylate comprising the 75% by mass or as a monomer unit,
Mass ratio of the previous SL acrylic polymer (A) and the polyfunctional acrylate (B) ((A): (B)) is 75: 25 to 90: A 10,
The photopolymerization initiator (C) is 2- [2-oxo-2-phenyl-acetoxy - ethoxy] - ethyl = oxyphenyl acetate and 2- (2-hydroxyethoxy) - ethyl = O carboxyethyl acetate mixture, and / or, 2-hydroxy-1- {4- [4- (2 - human Dorokishi 2-methyl - propionyl) - benzyl] - phenyl} -2-methyl - the profile pan-1-one An active energy ray curable resin composition containing.   Content of the said photoinitiator (C) is 0.01-10 mass parts with respect to a total of 100 mass parts of the said acrylic polymer (A) and the said polyfunctional acrylate (B). The active energy ray-curable resin composition according to 1. The polyfunctional acrylate (B) weight average molecular weight of 260 or more at which claim 1 or an active energy ray curable resin composition of the mounting serial to 2.   The polyfunctional acrylate (B) is trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol (tri) tetraacrylate, dipentaerythritol (penta) hexaacrylate, tripentaerythritol polyacrylate, tris (2-hydroxyethyl). ) The active energy ray-curable resin composition according to any one of claims 1 to 3, which is at least one member selected from isocyanurate triacrylate and alkoxylated products thereof and caprolactone-modified products thereof.   The acrylic polymer (A) is a methyl methacrylate homopolymer or a copolymer composed of a methyl methacrylate unit and one or more acrylate units. Active energy ray curable resin composition.   The active energy ray-curable resin composition according to any one of claims 1 to 5, wherein the acrylic polymer (A) has a mass average molecular weight of 50,000 to 200,000. A molded product obtained by thermoforming the active energy ray-curable resin composition according to any one of claims 1 to 6, which is curable by irradiation with an active energy beam. A molded product, which is a cured product of the active energy ray-curable resin composition according to any one of claims 1 to 6.