WO2018096967A1 - Photopolymerizable composition containing alicyclic epoxy compound for imprint molding - Google Patents

Photopolymerizable composition containing alicyclic epoxy compound for imprint molding Download PDF

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Publication number
WO2018096967A1
WO2018096967A1 PCT/JP2017/040794 JP2017040794W WO2018096967A1 WO 2018096967 A1 WO2018096967 A1 WO 2018096967A1 JP 2017040794 W JP2017040794 W JP 2017040794W WO 2018096967 A1 WO2018096967 A1 WO 2018096967A1
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Prior art keywords
photopolymerizable composition
component
parts
mass
epoxy compound
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PCT/JP2017/040794
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French (fr)
Japanese (ja)
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偉大 長澤
加藤　拓
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日産化学工業株式会社
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Priority to JP2018552509A priority Critical patent/JPWO2018096967A1/en
Publication of WO2018096967A1 publication Critical patent/WO2018096967A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/36—Moulds for making articles of definite length, i.e. discrete articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present invention relates to a photopolymerizable composition for imprint molding containing an alicyclic epoxy compound. Specifically, the present invention relates to a photopolymerizable composition capable of forming a cured product having excellent optical properties (transparency, high refractive index, high Abbe number).
  • Resin lenses are used in electronic devices such as mobile phones, digital cameras, and in-vehicle cameras, and are required to have excellent optical characteristics according to the purpose of the electronic device. Moreover, high durability, for example, heat resistance and weather resistance, and high productivity that can be molded with a high yield are required in accordance with the usage mode.
  • a thermoplastic transparent resin such as a polycarbonate resin, a cycloolefin polymer, and a methacrylic resin has been used.
  • a lens having a low wavelength dispersion that is, a lens having a high Abbe number is mainly used, and an optical material for forming the lens is required.
  • resin lenses from the injection molding of thermoplastic resins to the press molding using a liquid curable resin at room temperature, in order to improve the yield and production efficiency, and to suppress the optical axis misalignment during lens lamination Transition to wafer level molding has been actively studied.
  • the resin lens In order for the resin lens to exhibit a high Abbe number, it is necessary that absorption in the ultraviolet region is small, while in order to develop a high refractive index, a compound having an aromatic ring such as a benzene ring is employed. It is necessary to increase the electron density. These physical properties are generally in a trade-off relationship, and materials that achieve both a high refractive index and a high Abbe number are limited.
  • curable resins having both high refractive index and high Abbe number examples include cationic polymerizable compounds, photoacid generators, zirconium oxide particles and cations containing a compound having an epoxy group and a compound having an oxetanyl group
  • a photocurable resin composition containing a polymerization accelerator has been reported (Patent Document 1).
  • the cured product obtained from the photocurable resin composition has a transmittance of less than 90% at a wavelength of 400 nm because the transmittance decreases due to scattering by the zirconium oxide particles, and can be suitably used as a lens material. Does not have transparency.
  • an optical photosensitive resin composition containing the cationically polymerizable compound and a photoacid generator has a high refractive index. It has been reported that it can become a hardened
  • a cured product obtained from an optical photosensitive resin composition employing a cationic polymerizable compound having a dicyclopentane structure does not exhibit a refractive index of 1.530 or more.
  • adopted as a cationically polymerizable compound there exists a problem that it is not easy to prepare a solution-form composition.
  • the present invention has a high Abbe number (for example, 56 or more) and a high refractive index (for example, 1.530 or more, preferably 1.54 or more) that can be used as a lens for a high-resolution camera module, and has high transparency.
  • No curable resin material that can provide a cured product that satisfies the above requirements has been desired.
  • the present invention has been made in view of such circumstances, and a photopolymerizable composition suitable for producing a molded product having a high Abbe number and a high refractive index and further having high transparency. It is an issue to provide.
  • the present inventors have obtained a cured product obtained from the photopolymerizable composition by blending a specific alicyclic epoxy compound into the photopolymerizable composition.
  • the present invention is completed by finding that the (molded product) exhibits a high Abbe number (56 or more) and a high refractive index (1.530 or more) at a wavelength of 589 nm and a high transmittance of 90% or more at a wavelength of 400 nm. It came to.
  • the first aspect of the present invention includes the following component (a) and the following component (c) in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (a), or the following (a): Component, 0.01 part by mass with respect to 100 parts by mass of the following (b) component having an upper limit of 200 parts by mass per 100 parts by mass of component (a), and 100 parts by mass of the sum of component (a) and component (b) It is thru
  • the component (b) is an optional component.
  • the component (a) is a liquid at 25 ° C. and 101.3 kPa, for example.
  • the component (a) is, for example, an alicyclic epoxy compound represented by the following formula (1A).
  • the component (b) is preferably a compound containing no aromatic ring.
  • one or more antioxidants are added in an amount of 0.01 to 20 parts by mass, or the component (a) and the component (a) with respect to 100 parts by mass of the component (a).
  • or 20 mass parts may be further contained with respect to 100 mass parts of sum of a component.
  • the photopolymerizable composition of the present invention is, for example, an imprint molding composition and a resin lens composition.
  • the cured product has a refractive index n D at a wavelength of 589 nm of 1.530 to 1.570, and the cured product has an Abbe number ⁇ D of 56 to 65.
  • the second aspect of the present invention is a cured product of the photopolymerizable composition.
  • a third aspect of the present invention is a method for producing a resin lens, including a step of imprint molding the photopolymerizable composition that is the imprint molding composition or the resin lens composition.
  • the mold is also called a mold.
  • a step of taking out and releasing the obtained photopolymerized product, and before, during or before the step of releasing the photopolymerized product, A step of heating later may be further included.
  • the molded body is, for example, a camera module lens.
  • the cured product obtained from the photopolymerizable composition has desirable optical properties (high Abbe number, high refractive index, high transparency as a lens for optical devices, for example, high-resolution camera modules). ). Moreover, the manufacturing method of the molded object using the photopolymerizable composition of this invention can manufacture especially the lens for camera modules efficiently. Further, when the component (a) is a liquid at 25 ° C. and 101.3 kPa, the photopolymerizable composition of the present invention has a viscosity that can be handled sufficiently in a solvent-free form. ) Can be applied by applying a pressing process (imprint technique), and it is excellent in releasability from the mold after molding, and a molded article can be suitably produced.
  • the component (a) of the photopolymerizable composition of the present invention is an alicyclic epoxy compound represented by the formula (1).
  • Examples of the alicyclic epoxy compound include compounds represented by the following formulas (1A) to (1N).
  • the photopolymerizable composition of the present invention is liquid at 25 ° C. and 101.3 kPa, the component (a) alone is not necessarily liquid and may be solid.
  • the photopolymerizable composition of the present invention uses, as the component (b), an epoxy compound, an oxetane compound or a vinyl ether compound different from the alicyclic epoxy compound represented by the formula (1) together with the component (a). Can do.
  • the component (b) is an optional component, and when the photopolymerizable composition of the present invention contains the component (b), the upper limit is 200 parts by mass with respect to 100 parts by mass of the component (a). However, as a specific numerical range of the content, for example, a range of 0.001 parts by mass to 200 parts by mass with respect to 100 parts by mass of the component (a) is given.
  • the refractive index n D of the cured product drops below 1.530.
  • epoxy compound different from the alicyclic epoxy compound represented by the formula (1) various commercially available bifunctional or polyfunctional epoxy compounds can be used without any particular limitation.
  • Examples of the epoxy compound that can be used as the component (b) of the photopolymerizable composition of the present invention include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and (poly) ethylene glycol.
  • the following commercial items can be mentioned as said epoxy compound.
  • the solid epoxy compound include TEPIC (registered trademark) -G, S, L, and HP (all manufactured by Nissan Chemical Industries, Ltd.).
  • the liquid epoxy compound include TEPIC (registered trademark) -PAS B22, PAS B26, PAS B26L, VL, UC (all manufactured by Nissan Chemical Industries, Ltd.), jER (registered trademark) 828.
  • Examples of the oxetane compound that can be used as the component (b) of the photopolymerizable composition of the present invention include di [2- (3-oxetanyl) butyl] ether, 3-ethyl-3-hydroxymethyloxetane, 1,6 -Bis [(3-ethyloxetane-3-yl) methoxy] -2,2,3,3,4,4,5,5-octafluorohexane, 3 (4), 8 (9) -bis [(1 -Ethyl-3-oxetanyl) methoxymethyl-tricyclo [5.2.1.0 2,6 ] decane, 1,2-bis ⁇ [2- (1-ethyl-3-oxetanyl) methoxy] ethylthio ⁇ ethane, , 3-Bis [(3-ethyloxetane-3-yl) methoxymethyl] norbornane, 2-ethyl-2-[(3-ethylox
  • oxetane compound Aron Oxetane (registered trademark) OXT-101, OXT-212, OXT-121, OXT-221 (all manufactured by Toa Gosei Co., Ltd.), and ETERNACOLL (registered trademark) EHO, OXBP, OXTP And OXMA (both manufactured by Ube Industries, Ltd.).
  • OXT-101, OXT-212, OXT-121, OXT-221 all manufactured by Toa Gosei Co., Ltd.
  • ETERNACOLL registered trademark
  • EHO OXBP
  • OXTP And OXMA both manufactured by Ube Industries, Ltd.
  • an oxetane compound containing no aromatic ring is suitable for the present invention from the viewpoint of the Abbe number.
  • Examples of the vinyl ether compound that can be used as the component (b) of the photopolymerizable composition of the present invention include ethyl vinyl ether, isobutyl vinyl ether, hydroxybutyl vinyl ether, butanediol divinyl ether, cyclohexyl vinyl ether, n-butyl vinyl ether, tert-butyl.
  • Examples include vinyl ether, norbornane-2-ol vinyl ether, triethylene glycol divinyl ether, octadecyl vinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, cyclohexane dimethanol monovinyl ether, and cyclohexanediol divinyl ether.
  • vinyl ether compounds from the viewpoint of the Abbe number, a vinyl ether compound containing no aromatic ring is suitable for the present invention.
  • a polymer containing an epoxy group, an oxetanyl group, or a vinyl ether group may be used.
  • a (meth) acrylate polymer containing an epoxy group or an oxetanyl group represented by the following formula (2), formula (3), or formula (4) is preferable.
  • R 13 to R 15 represent a hydrogen atom or a methyl group
  • R 16 represents a methyl group or an ethyl group
  • X represents an alkylene group having 1 to 5 carbon atoms which may include an ether bond or an ester bond.
  • Examples of the raw material monomer for such a (meth) acrylate polymer include glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, 4-hydroxybutyl methacrylate glycidyl ether, 3,4-epoxycyclohexylmethyl acrylate, 3, 4-epoxycyclohexylmethyl methacrylate, (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methyl methacrylate, (3-methyloxetane-3-yl) methyl acrylate, and (3- And methyl oxetane-3-yl) methyl methacrylate.
  • the (meth) acrylate polymer may be a copolymer of the monomer and another (meth) acrylate compound in order to adjust the refractive index and solubility.
  • the other (meth) acrylate compounds include methyl acrylate, methyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, 2-adamantyl acrylate, 2-adamantyl methacrylate, 2- Methyladamantan-2-yl acrylate, 2-methyladamantan-2-yl methacrylate, 2-ethyladamantan-2-yl acrylate, 2-ethyladamantan-2-yl methacrylate, 1,3-adamantanediol diacrylate, 1,3 -Adamantanediol dimethacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, di
  • the average molecular weight of these (meth) acrylate polymers is not particularly limited, but preferably has a weight average molecular weight of 5,000 to 1,000,000, particularly preferably 10,000 to 100,000.
  • the photoacid generator which is the component (c) of the photopolymerizable composition of the present invention is not particularly limited as long as it generates an acid (Lewis acid or Bronsted acid) directly or indirectly by light irradiation. Since the photopolymerizable composition containing the photoacid generator as in the present invention is cured by light irradiation without being heated, it can be used for substrates and members having low heat resistance. Content of (c) component of the photopolymerizable composition of this invention is 0.01 mass part thru
  • Examples of the photoacid generator that can be used as the component (c) of the photopolymerizable composition of the present invention include onium salts such as iodonium salts, sulfonium salts, phosphonium salts, selenium salts, and iron arene complex compounds. Can do.
  • iodonium salt examples include diphenyliodonium, 4,4′-dichlorodiphenyliodonium, 4,4′-dimethoxydiphenyliodonium, 4,4′-di-tert-butyldiphenyliodonium, 4-methylphenyl (4- ( 2-methylpropyl) phenyl) iodonium, 3,3′-dinitrophenyliodonium, 4- (1-ethoxycarbonylethoxy) phenyl (2,4,6-trimethylphenyl) iodonium, 4-methoxyphenyl (phenyl) iodonium, etc.
  • Iodonium chloride, bromide, mesylate, tosylate, trifluoromethanesulfonate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate, hexafluorophosphate, hexafluoroarsene DOO, and such hexafluoroantimonate include diaryliodonium salts.
  • sulfonium salt examples include triphenylsulfonium, diphenyl (4-tert-butylphenyl) sulfonium, tris (4-tert-butylphenyl) sulfonium, diphenyl (4-methoxyphenyl) sulfonium, tris (4-methylphenyl) Sulfonium chloride, bromide, sulfonium such as sulfonium, tris (4-methoxyphenyl) sulfonium, tris (4-ethoxyphenyl) sulfonium, diphenyl (4- (phenylthio) phenyl) sulfonium, tris (4- (phenylthio) phenyl) sulfonium, Triarylsulfones such as trifluoromethanesulfonate, tetrafluoroborate, hexafluorophosphate, hexafluoroarsen
  • Examples of the phosphonium salt include chloride, bromide, tetrafluoro of phosphonium such as tetraphenylphosphonium, ethyltriphenylphosphonium, tetra (p-methoxyphenyl) phosphonium, ethyltri (p-methoxyphenyl) phosphonium, benzyltriphenylphosphonium.
  • Examples include aryl phosphonium salts such as borate, hexafluorophosphate, hexafluoroantimonate.
  • selenium salt examples include triaryl selenium salts such as triphenyl selenium hexafluorophosphate.
  • iron arene complex compound examples include bis ( ⁇ 5-cyclopentadienyl) ( ⁇ 6-isopropylbenzene) iron (II) hexafluorophosphate.
  • these photoacid generators can be used alone or in combination of two or more.
  • photo-acid generator for example, Sun-Aid (registered trademark) SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-100L, SI-L145, SI-L150, SI-L160 SI-L110, SI-L147 (all manufactured by Sanshin Chemical Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6990 (all manufactured by Union Carbide) CPI (registered trademark) -100P, -110P, -101A, -200K, -210S (above, manufactured by San Apro Co., Ltd.), Adekaoptomer SP-150, SP-151, SP-170 SP-171 (all manufactured by ADEKA Corporation), Irgacure (registered trademark) 250, 270, 290 (all manufactured by BASF), CI-2 81, CI-2624, CI-2639,
  • the photopolymerizable composition of the present invention may contain an antioxidant, an ultraviolet absorber, a light stabilizer, a leveling agent, a rheology modifier, and a silane coupling agent as necessary, as long as the effects of the present invention are not impaired. It is possible to contain an adhesion aid such as an antifoaming agent.
  • antioxidants examples include a phenol-based antioxidant, a phosphoric acid-based antioxidant, and a sulfide-based antioxidant, and among these, a phenol-based antioxidant and a phosphoric acid-based antioxidant are preferable. .
  • phenol-based antioxidant examples include IRGANOX (registered trademark) 245, 1010, 1035, 1076, 1135 (all manufactured by BASF Japan Ltd.), Sumilyzer (registered trademark) GA-80, GP, MDP-S, BBM-S, WX-R (all manufactured by Sumitomo Chemical Co., Ltd.), ADK STAB (registered trademark) AO-20, AO-30, AO-40, AO-50 AO-60, AO-80, AO-330 (all manufactured by ADEKA Corporation).
  • Examples of the phosphoric acid antioxidant include IRGAFOS (registered trademark) 168 (manufactured by BASF Japan Ltd.), ADK STAB (registered trademark) PEP-36, PEP-8, HP-18, and HP-10. 2112, 2112RG, 1178, 1500, C, 135A, 3010, and TPP (all manufactured by ADEKA Corporation).
  • sulfide antioxidant examples include IRGANOX (registered trademark) 1726 and 1520L (both manufactured by BASF Japan), Adeka Stub (registered trademark) AO-412S, and AO-503 (all manufactured by ADEKA).
  • the antioxidant When the antioxidant is added to the photopolymerizable composition of the present invention, the antioxidant may be used alone or in combination of two or more. Moreover, as the addition amount, it is 0.01 mass part thru
  • the photopolymerizable composition of the present invention contains the antioxidant in the above-described addition amount, so that the cured product of the photopolymerizable composition is prevented from being yellowed by heating.
  • the method for preparing the photopolymerizable composition of the present invention is not particularly limited.
  • the components (a) and (c), and the component (b) as necessary are mixed in a predetermined ratio, and other additives are further added as desired to mix the solution uniformly.
  • these components for example, after mixing a part of either one or both of component (a) and component (b) to make a uniform solution, add the remaining components, and optionally other Examples thereof include a method in which an additive is further added and mixed to obtain a uniform solution, or a method in which a conventional solvent is used in addition to these components.
  • the ratio of the solid content in the photopolymerizable composition is not particularly limited as long as each component is uniformly dissolved in the solvent. Thru
  • the solid content is obtained by removing the solvent component from all the components of the photopolymerizable composition of the present invention.
  • the photopolymerizable composition of the present invention prepared in a solution is preferably used after being filtered using a filter having a pore size of 0.1 ⁇ m to 5 ⁇ m.
  • the photopolymerizable composition can be exposed (photocured) to obtain a cured product, and the present invention also targets a cured product of the photopolymerizable compound.
  • light rays to be exposed include ultraviolet rays, electron beams, and X-rays.
  • a light source used for ultraviolet irradiation for example, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, and a UV-LED can be used.
  • the post-baking method is not particularly limited, but is usually performed in a range of 50 ° C. to 260 ° C. and 1 minute to 24 hours using a hot plate, an oven or the like.
  • the cured product obtained by photocuring the photopolymerizable composition of the present invention has an Abbe number as high as 56 or higher, and a refractive index as high as 1.530 or higher at a wavelength of 589 nm (D line). Moreover, yellowing by heating is not seen. Therefore, the photopolymerizable composition of the present invention can be suitably used as a composition for a high refractive index resin lens.
  • the photopolymerizable composition of the present invention can be used in various ways in parallel with the formation of a cured product by using conventional molding methods such as compression molding (imprint molding, etc.), casting, injection molding, blow molding, etc.
  • a molded object can be manufactured easily.
  • the molded body thus obtained is also an object of the present invention.
  • a method for producing a molded body for example, a step of filling the space of the photopolymerizable composition of the present invention into a space between a contacting support and a mold, or a space inside a separable mold, the space is filled.
  • the above-mentioned exposure and photopolymerization step can be carried out by applying the conditions for obtaining the above-mentioned cured product.
  • the conditions for the step of heating the photopolymerized product are not particularly limited, but are usually appropriately selected from the range of 50 ° C. to 260 ° C. and 1 minute to 24 hours. Moreover, it does not specifically limit as a heating means, For example, a hotplate and oven are mentioned.
  • the molded body produced by such a method can be suitably used as a lens for a camera module.
  • Agitating and defoaming machine Device Rotating / revolving mixer manufactured by Shinkey Co., Ltd. Nertaro Awatori (registered trademark) ARE-310
  • UV exposure system Batch type UV irradiation system (high pressure mercury lamp 2kW x 1 lamp) manufactured by Eye Graphics Co., Ltd.
  • Transmittance UV-Vis near-infrared spectrophotometer V-670 manufactured by JASCO Corporation Reference: Quartz (4) Refractive index n D , Abbe number ⁇ D Apparatus: Multi-wavelength refractometer Abbemat MW manufactured by Anton Paar Measurement temperature: 23 ° C
  • Intermediate solution for bonding sample and prism monobromonaphthalene
  • the polymer weight average molecular weight and dispersity shown in the following synthesis examples are measurement results by gel permeation chromatography (hereinafter abbreviated as GPC in this specification).
  • GPC gel permeation chromatography
  • a GPC system manufactured by Shimadzu Corporation was used.
  • the configuration and measurement conditions of the GPC system are as follows.
  • GPC GPC system configuration System controller: CBM-20A, column oven: CTO-20A, autosampler: SIL-10AF, detector: SPD-20A and RID-10A, exhaust unit: DGU-20A3
  • ADMA manufactured by Osaka Organic Chemical Industry Co., Ltd. 1-adamantyl methacrylate
  • OXE-10 manufactured by Osaka Organic Chemical Industry Co., Ltd. (3-ethyloxetane-3-yl) methyl acrylate THIDE: manufactured by JX Energy Co., Ltd.
  • Tetrahydroindene diepoxide I1010 BASF Japan K.K. trade name: IRGANOX (registered trademark) 1010]
  • CPI-110P San Apro Co., Ltd.
  • polymer 1 a target oxetanyl group-containing acrylic polymer (hereinafter referred to as polymer 1).
  • polymer 1 a target oxetanyl group-containing acrylic polymer
  • Example 1 [Example 1] (A) THIDE as an alicyclic epoxy compound, (c) a photoacid generator and an antioxidant are blended in the proportions shown in Table 1 below, respectively, and 3 hours at 50 ° C. using the stirring deaerator. Stir and mix. Furthermore, the photopolymerizable composition 1 was prepared by carrying out stirring deaeration for 10 minutes using the same apparatus. In Table 1 below, “part” represents “part by mass”.
  • Example 2 to Example 8 [Example 2 to Example 8] (A) THIDE as the alicyclic epoxy compound, (b) other epoxy compound, (c) photoacid generator, and antioxidant are blended in the proportions shown in Table 1 below, and the stirring deaerator And stirred for 3 hours at 50 ° C. Furthermore, the photopolymerizable composition 2 thru
  • Example 9 (A) THIDE as an alicyclic epoxy compound, (b) polymer 1 obtained in Synthesis Example 1 as an oxetane compound, (c) a photoacid generator, and an antioxidant, respectively, in the proportions shown in Table 1 below Then, the mixture was stirred and mixed at 50 ° C. for 3 hours using the stirring deaerator. Furthermore, the photopolymerizable composition 9 was prepared by stirring and degassing for 10 minutes using the same apparatus.
  • Each photopolymerizable composition prepared in Examples 1 to 9 and Comparative Example 1 is coated with NOVEC (registered trademark) 1720 (manufactured by 3M Japan) together with a 300 ⁇ m thick silicone rubber spacer and dried. Thus, it was sandwiched between two release-treated glass substrates.
  • the sandwiched photopolymerizable composition was subjected to UV exposure at 20 mW / cm 2 for 450 seconds using the UV irradiation apparatus.
  • the cured product obtained after the exposure was peeled off from the release-treated glass substrate, and then heated on an 85 ° C.
  • the cured product obtained from the photopolymerizable composition prepared in Comparative Example 1 had a refractive index n D of less than 1.530 at a wavelength of 589 nm.
  • the cured products obtained from the photopolymerizable compositions prepared in Examples 1 to 9 all have a refractive index n D of 1.530 or more at a wavelength of 589 nm and an Abbe number ⁇ D of 56 or more. became.
  • the cured films obtained from the photopolymerizable compositions prepared in Examples 1 to 9 all showed a transmittance of 90% or more at a wavelength of 400 nm.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Epoxy Resins (AREA)
  • Polyethers (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

[Problem] To provide a photopolymerizable composition which gives a cured object exhibiting a large Abbe number and a high refractive index and is suitable for producing molded objects having high transparency. [Solution] A photopolymerizable composition which comprises the following ingredient (a) and the following ingredient (c), the amount of the ingredient (c) being 0.01-10 parts by mass per 100 parts by mass of the ingredient (a), or comprises the following ingredient (a), the following ingredient (b), and the following ingredient (c), the amount of the ingredient (b) being up to 200 parts by mass per 100 parts by mass of the ingredient (a) and the amount of the ingredient (c) being 0.01-10 parts by mass per 100 parts by mass of the sum of the ingredients (a) and (b). (a) An alicyclic epoxy compound represented by formula (1). (b) An epoxy compound differing from the alicyclic epoxy compound represented by formula (1), an oxetane compound, or a vinyl ether compound. (c) A photo-acid generator. (In formula (1), R1 to R12 may be the same or different and each represent a hydrogen atom, hydrocarbon group, methoxy group, or acetoxy group.)

Description

脂環式エポキシ化合物を含むインプリント成形用光重合性組成物Photopolymerizable composition for imprint molding containing alicyclic epoxy compound
　本発明は脂環式エポキシ化合物を含むインプリント成形用光重合性組成物に関する。詳細には、優れた光学特性（透明性、高屈折率、高アッベ数）を有する硬化物を形成できる、光重合性組成物に関する。 The present invention relates to a photopolymerizable composition for imprint molding containing an alicyclic epoxy compound. Specifically, the present invention relates to a photopolymerizable composition capable of forming a cured product having excellent optical properties (transparency, high refractive index, high Abbe number).
　樹脂レンズは、携帯電話、デジタルカメラ、車載カメラなどの電子機器に用いられており、その電子機器の目的に応じた、優れた光学特性を有するものであることが求められる。また、使用態様に合わせて、高い耐久性、例えば耐熱性及び耐候性、並びに歩留まりよく成形できる高い生産性が求められている。このような樹脂レンズ用の材料としては、例えば、ポリカーボネート樹脂、シクロオレフィンポリマー、メタクリル樹脂等の熱可塑性の透明樹脂が使用されてきた。 Resin lenses are used in electronic devices such as mobile phones, digital cameras, and in-vehicle cameras, and are required to have excellent optical characteristics according to the purpose of the electronic device. Moreover, high durability, for example, heat resistance and weather resistance, and high productivity that can be molded with a high yield are required in accordance with the usage mode. As a material for such a resin lens, for example, a thermoplastic transparent resin such as a polycarbonate resin, a cycloolefin polymer, and a methacrylic resin has been used.
　また、高解像度カメラモジュールには複数枚のレンズが用いられるが、波長分散性が低い、すなわち高アッベ数を有するレンズが主に使用されており、それを形成する光学材料が要求されている。さらに、樹脂レンズの製造にあたり、歩留まりや生産効率向上、さらにはレンズ積層時の光軸ずれの抑制のために、熱可塑性樹脂の射出成型から、室温で液状の硬化性樹脂を使った押し付け成形によるウェハレベル成形への移行が盛んに検討されている。 Further, although a plurality of lenses are used in the high-resolution camera module, a lens having a low wavelength dispersion, that is, a lens having a high Abbe number is mainly used, and an optical material for forming the lens is required. Furthermore, in the production of resin lenses, from the injection molding of thermoplastic resins to the press molding using a liquid curable resin at room temperature, in order to improve the yield and production efficiency, and to suppress the optical axis misalignment during lens lamination Transition to wafer level molding has been actively studied.
　樹脂レンズが高アッベ数を示すためには、紫外領域の吸収が少ないことが必要である一方、高屈折率を発現するためには、ベンゼン環等の芳香族環を有する化合物を採用することにより電子密度を高める必要がある。これらの物性は一般的にトレードオフの関係となっており、高屈折率と高アッベ数を両立する材料は限られている。数少ない高屈折率と高アッベ数を両立した硬化性樹脂の報告例としては、エポキシ基を有する化合物とオキセタニル基を有する化合物とを含有するカチオン重合性化合物、光酸発生剤、酸化ジルコニウム粒子及びカチオン重合促進剤を含む光硬化性樹脂組成物が報告されている（特許文献１）。しかしながら、前記光硬化性樹脂組成物から得られる硬化物は、酸化ジルコニウム粒子による散乱により透過率が低下するため、波長４００ｎｍにおける透過率は９０％に満たない結果となり、レンズ材として好適に使用できる透明性を有していない。 In order for the resin lens to exhibit a high Abbe number, it is necessary that absorption in the ultraviolet region is small, while in order to develop a high refractive index, a compound having an aromatic ring such as a benzene ring is employed. It is necessary to increase the electron density. These physical properties are generally in a trade-off relationship, and materials that achieve both a high refractive index and a high Abbe number are limited. Examples of reported curable resins having both high refractive index and high Abbe number include cationic polymerizable compounds, photoacid generators, zirconium oxide particles and cations containing a compound having an epoxy group and a compound having an oxetanyl group A photocurable resin composition containing a polymerization accelerator has been reported (Patent Document 1). However, the cured product obtained from the photocurable resin composition has a transmittance of less than 90% at a wavelength of 400 nm because the transmittance decreases due to scattering by the zirconium oxide particles, and can be suitably used as a lens material. Does not have transparency.
　一方、架橋環式炭化水素構造、特にジシクロペンタン構造を有するカチオン重合性化合物を採用することで、該カチオン重合性化合物及び光酸発生剤を含有する光学用感光性樹脂組成物は、高屈折率及び高アッベ数を有する硬化物となり得ることが報告されている（特許文献２）。しかしながら、ジシクロペンタン構造を有するカチオン重合性化合物を採用した光学用感光性樹脂組成物から得られる硬化物は、１．５３０以上の屈折率を示さない。また、カチオン重合性化合物としてジシクロペンタジエンジエポキシドを採用する場合、溶液状の組成物を調製することが容易でないという問題がある。 On the other hand, by adopting a cationically polymerizable compound having a crosslinked cyclic hydrocarbon structure, particularly a dicyclopentane structure, an optical photosensitive resin composition containing the cationically polymerizable compound and a photoacid generator has a high refractive index. It has been reported that it can become a hardened | cured material which has a rate and a high Abbe number (patent document 2). However, a cured product obtained from an optical photosensitive resin composition employing a cationic polymerizable compound having a dicyclopentane structure does not exhibit a refractive index of 1.530 or more. Moreover, when dicyclopentadiene diepoxide is employ | adopted as a cationically polymerizable compound, there exists a problem that it is not easy to prepare a solution-form composition.
国際公開ＷＯ２０１６／１０４０３９号International Publication WO2016 / 104039 国際公開ＷＯ２０１６／０３１６０２号International Publication WO2016 / 031602
　このように、高解像度カメラモジュール用レンズとして使用し得る、高アッベ数（例えば５６以上）と高屈折率（例えば１．５３０以上、好ましくは１．５４以上）を有し、かつ、高い透明性を満足する硬化物が得られる硬化性樹脂材料は未だなく、その開発が望まれていた。本発明は、このような事情に鑑みてなされたものであり、硬化物が高アッベ数と高屈折率を示し、さらに高い透明性を有する成形体を作製するのに好適な光重合性組成物を提供することを課題とする。 Thus, it has a high Abbe number (for example, 56 or more) and a high refractive index (for example, 1.530 or more, preferably 1.54 or more) that can be used as a lens for a high-resolution camera module, and has high transparency. No curable resin material that can provide a cured product that satisfies the above requirements has been desired. The present invention has been made in view of such circumstances, and a photopolymerizable composition suitable for producing a molded product having a high Abbe number and a high refractive index and further having high transparency. It is an issue to provide.
　本発明者らは、上記の課題を解決するべく鋭意検討を行った結果、特定の脂環式エポキシ化合物を光重合性組成物に配合することにより、該光重合性組成物から得られる硬化物（成形体）が波長５８９ｎｍにおいて高いアッベ数（５６以上）及び高い屈折率（１．５３０以上）を発現し、波長４００ｎｍにおいて９０％以上の高い透過率を示すことを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have obtained a cured product obtained from the photopolymerizable composition by blending a specific alicyclic epoxy compound into the photopolymerizable composition. The present invention is completed by finding that the (molded product) exhibits a high Abbe number (56 or more) and a high refractive index (1.530 or more) at a wavelength of 589 nm and a high transmittance of 90% or more at a wavelength of 400 nm. It came to.
　すなわち本発明の第一態様は、下記（ａ）成分、及び該（ａ）成分１００質量部に対し０．０１質量部乃至１０質量部の下記（ｃ）成分を含むか、又は
下記（ａ）成分、該（ａ）成分１００質量部に対し２００質量部を上限値とする下記（ｂ）成分、及び該（ａ）成分及び該（ｂ）成分の和１００質量部に対し０．０１質量部乃至１０質量部の下記（ｃ）成分を含む、光重合性組成物である。
（ａ）：下記式（１）で表される脂環式エポキシ化合物
Figure JPOXMLDOC01-appb-C000003
 （式中、Ｒ1乃至Ｒ12は、それぞれ同一であっても異なっていてもよく、水素原子、炭化水素基、メトキシ基又はアセトキシ基を表す。）
（ｂ）：前記式（１）で表される脂環式エポキシ化合物とは異なるエポキシ化合物、オキセタン化合物又はビニルエーテル化合物
（ｃ）：光酸発生剤 That is, the first aspect of the present invention includes the following component (a) and the following component (c) in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (a), or the following (a): Component, 0.01 part by mass with respect to 100 parts by mass of the following (b) component having an upper limit of 200 parts by mass per 100 parts by mass of component (a), and 100 parts by mass of the sum of component (a) and component (b) It is thru | or 10 mass parts of photopolymerizable composition containing the following (c) component.
(A): An alicyclic epoxy compound represented by the following formula (1)
Figure JPOXMLDOC01-appb-C000003
 (In the formula, R 1 to R 12 may be the same or different and each represents a hydrogen atom, a hydrocarbon group, a methoxy group, or an acetoxy group.)
(B): Epoxy compound, oxetane compound or vinyl ether compound different from the alicyclic epoxy compound represented by the formula (1) (c): photoacid generator
　前記（ｂ）成分は任意成分である。 The component (b) is an optional component.
　本発明の光重合性組成物において、前記（ａ）成分は、例えば２５℃、１０１．３ｋＰａで液体である。また前記（ａ）成分は、例えば下記式（１Ａ）で表される脂環式エポキシ化合物である。
Figure JPOXMLDOC01-appb-C000004
 In the photopolymerizable composition of the present invention, the component (a) is a liquid at 25 ° C. and 101.3 kPa, for example. The component (a) is, for example, an alicyclic epoxy compound represented by the following formula (1A).
Figure JPOXMLDOC01-appb-C000004
　本発明の光重合性組成物において、前記（ｂ）成分は芳香族環を含まない化合物であることが好ましい。 In the photopolymerizable composition of the present invention, the component (b) is preferably a compound containing no aromatic ring.
　本発明の光重合性組成物は、一種又は二種以上の酸化防止剤を、前記（ａ）成分１００質量部に対し０．０１質量部乃至２０質量部、又は前記（ａ）成分及び前記（ｂ）成分の和１００質量部に対し０．０１質量部乃至２０質量部さらに含有してもよい。 In the photopolymerizable composition of the present invention, one or more antioxidants are added in an amount of 0.01 to 20 parts by mass, or the component (a) and the component (a) with respect to 100 parts by mass of the component (a). b) 0.01 mass part thru | or 20 mass parts may be further contained with respect to 100 mass parts of sum of a component.
　本発明の光重合性組成物は、例えば、インプリント成形用組成物であり、樹脂レンズ用組成物である。 The photopolymerizable composition of the present invention is, for example, an imprint molding composition and a resin lens composition.
　本発明の光重合性組成物は、その硬化物の波長５８９ｎｍにおける屈折率ｎDが１．５３０以上１．５７０以下であり、かつ該硬化物のアッベ数νDが５６以上６５以下である。 In the photopolymerizable composition of the present invention, the cured product has a refractive index n D at a wavelength of 589 nm of 1.530 to 1.570, and the cured product has an Abbe number ν D of 56 to 65.
　本発明の第二態様は、前記光重合性組成物の硬化物である。 The second aspect of the present invention is a cured product of the photopolymerizable composition.
　本発明の第三態様は、前記インプリント成形用組成物又は前記樹脂レンズ用組成物である光重合性組成物をインプリント成形する工程を含む、樹脂レンズの製造方法である。 A third aspect of the present invention is a method for producing a resin lens, including a step of imprint molding the photopolymerizable composition that is the imprint molding composition or the resin lens composition.
　本発明の第四態様は、前記光重合性組成物を、接し合う支持体と鋳型との間の空間、又は分割可能な鋳型の内部の空間に充填する工程、及び該空間に充填された光重合性組成物を露光して光重合する工程、を含む成形体の製造方法である。前記鋳型はモールドとも称する。 According to a fourth aspect of the present invention, there is provided a step of filling the photopolymerizable composition in a space between the contacting support and the mold, or a space inside the separable mold, and light filled in the space. And a step of photopolymerizing the polymerizable composition by exposing the polymerizable composition. The mold is also called a mold.
　本発明の成形体の製造方法において、前記光重合する工程の後、得られた光重合物を取り出して離型する工程、並びに、該光重合物を、該離型する工程の前、中途又は後において加熱する工程、をさらに含んでもよい。 In the method for producing a molded article of the present invention, after the photopolymerization step, a step of taking out and releasing the obtained photopolymerized product, and before, during or before the step of releasing the photopolymerized product, A step of heating later may be further included.
　本発明の成形体の製造方法において、該成形体は、例えばカメラモジュール用レンズである。 In the method for producing a molded body of the present invention, the molded body is, for example, a camera module lens.
　本発明の光重合性組成物は、該光重合性組成物から得られる硬化物が、光学デバイス、例えば、高解像度カメラモジュール用のレンズとして望ましい光学特性（高アッベ数、高屈折率、高透明性）を有する。また、本発明の光重合性組成物を用いた成形体の製造方法は、特にカメラモジュール用レンズを効率的に製造することができる。さらに、本発明の光重合性組成物は、（ａ）成分が２５℃、１０１．３ｋＰａで液体である場合、無溶剤の形態で十分に取り扱い可能な粘度を有しているため、鋳型（モールド）の押し付け加工（インプリント技術）を適用して成形可能であり、また成形後における該鋳型からの離型性にも優れ、好適に成形体を製造することができる。 In the photopolymerizable composition of the present invention, the cured product obtained from the photopolymerizable composition has desirable optical properties (high Abbe number, high refractive index, high transparency as a lens for optical devices, for example, high-resolution camera modules). ). Moreover, the manufacturing method of the molded object using the photopolymerizable composition of this invention can manufacture especially the lens for camera modules efficiently. Further, when the component (a) is a liquid at 25 ° C. and 101.3 kPa, the photopolymerizable composition of the present invention has a viscosity that can be handled sufficiently in a solvent-free form. ) Can be applied by applying a pressing process (imprint technique), and it is excellent in releasability from the mold after molding, and a molded article can be suitably produced.
［（ａ）成分：脂環式エポキシ化合物］
　本発明の光重合性組成物の（ａ）成分は、前記式（１）で表される脂環式エポキシ化合物である。前記脂環式エポキシ化合物としては、例えば下記式（１Ａ）乃至式（１Ｎ）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000005
 [(A) component: alicyclic epoxy compound]
The component (a) of the photopolymerizable composition of the present invention is an alicyclic epoxy compound represented by the formula (1). Examples of the alicyclic epoxy compound include compounds represented by the following formulas (1A) to (1N).
Figure JPOXMLDOC01-appb-C000005
　本発明の光重合性組成物が２５℃、１０１．３ｋＰａで液体ならば、前記（ａ）成分単独では必ずしも液体である必要はなく、固体でもよい。 If the photopolymerizable composition of the present invention is liquid at 25 ° C. and 101.3 kPa, the component (a) alone is not necessarily liquid and may be solid.
［（ｂ）成分：エポキシ化合物、オキセタン化合物又はビニルエーテル化合物］
　本発明の光重合性組成物は、前記（ａ）成分と共に、前記式（１）で表される脂環式エポキシ化合物とは異なるエポキシ化合物、オキセタン化合物又はビニルエーテル化合物を（ｂ）成分として用いることができる。前記（ｂ）成分は任意成分であり、本発明の光重合性組成物が該（ｂ）成分を含む場合、その含有量は前記（ａ）成分１００質量部に対し２００質量部を上限とするが、具体的な含有量の数値範囲としては、前記（ａ）成分１００質量部に対し例えば０．００１質量部乃至２００質量部の範囲が挙げられる。前記（ｂ）成分の含有量が上限値を超えると、硬化物の架橋密度の低下に伴い、該硬化物の屈折率ｎDが１．５３０未満に低下する。 [(B) component: epoxy compound, oxetane compound or vinyl ether compound]
The photopolymerizable composition of the present invention uses, as the component (b), an epoxy compound, an oxetane compound or a vinyl ether compound different from the alicyclic epoxy compound represented by the formula (1) together with the component (a). Can do. The component (b) is an optional component, and when the photopolymerizable composition of the present invention contains the component (b), the upper limit is 200 parts by mass with respect to 100 parts by mass of the component (a). However, as a specific numerical range of the content, for example, a range of 0.001 parts by mass to 200 parts by mass with respect to 100 parts by mass of the component (a) is given. When the content of the component (b) exceeds the upper limit, with a decrease of the crosslink density of the cured product, the refractive index n D of the cured product drops below 1.530.
　前記式（１）で表される脂環式エポキシ化合物とは異なるエポキシ化合物としては、特に限定されることなく市販されている種々の２官能又は多官能のエポキシ化合物を使用することができる。 As the epoxy compound different from the alicyclic epoxy compound represented by the formula (1), various commercially available bifunctional or polyfunctional epoxy compounds can be used without any particular limitation.
　本発明の光重合性組成物の（ｂ）成分として使用可能なエポキシ化合物としては、例えば、１，４－ブタンジオールジグリシジルエーテル、１，６－へキサンジオールジグリシジルエーテル、（ポリ）エチレングリコールジグリシジルエーテル、（ポリ）プロピレングリコールジグリシジルエーテル、トリメチロールエタントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、１，４－シクロヘキサンジメタノールジグリシジルエーテル、１，２－エポキシ－４－（エポキシエチル）シクロヘキサン、グリセロールトリグリシジルエーテル、ジグリセロールポリジグリシジルエーテル、１，２－シクロヘキサンジカルボン酸ジグリシジルエステル、３，４－エポキシシクロヘキサンカルボン酸３’，４’－エポキシシクロヘキシルメチル、テトラグリシジル－１，３－ビスアミノメチルシクロヘキサン、水素化ビスフェノールＡジグリシジルエーテル、ペンタエリスリトールジグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、トリグリシジルイソシアヌレート、トリス－（３，４－エポキシブチル）イソシアヌレート、トリス－（４，５－エポキシペンチル）イソシアヌレート、トリス－（５，６－エポキシヘキシル）イソシアヌレート、トリス（２－グリシジルオキシエチル）イソシアヌレート、モノアリルジグリシジルイソシアヌレート、Ｎ，Ｎ’－ジグリシジルＮ’’－（２，３－ジプロピオニルオキシプロピル）イソシアヌレート、Ｎ，Ｎ’－ビス（２，３－ジプロピオニルオキシプロピル）Ｎ’’－グリシジルイソシアヌレート、トリス（２，２－ビス（グリシジルオキシメチル）ブチル）３，３’，３’’－（２，４，６－トリオキソ－１，３，５－トリアジン－１，３，５－トリイル）トリプロパノエート、ソルビトールポリグリシジルエーテル、アジピン酸ジグリシジル、１，２，７，８－ジエポキシオクタン、１，６－ジメチロールパーフルオロヘキサンジグリシジルエーテル、４－（スピロ［３，４－エポキシシクロヘキサン－１，５’－［１，３］ジオキサン］－２’－イル）－１，２－エポキシシクロヘキサン、１，２－ビス（３，４－エポキシシクロヘキシルメトキシ）エタン、４，５－エポキシ－２－メチルシクロヘキサンカルボン酸４’，５’－エポキシ－２’－メチルシクロヘキシルメチル、エチレングリコールビス（３，４－エポキシシクロヘキサンカルボキシレート）、ビス（３，４－エポキシシクロヘキシルメチル）アジペート、ビス（２，３－エポキシシクロペンチル）エーテル、（３、３'、４、４'－ジエポキシ）ビシクロヘキシル、トリシクロ［５．２．１．０2,6］デカンジメタノールジグリシジルエーテル等の芳香族環を含まないエポキシ化合物、及び２，６－ジグリシジルフェニルグリシジルエーテル、１，１，３－トリス（４－グリシジルオキシフェニル）プロパン、４，４’－メチレンビス（Ｎ，Ｎ－ジグリシジルアニリン）、トリグリシジル－ｐ－アミノフェノール、テトラグリシジルメタキシレンジアミン、テトラグリシジルジアミノジフェニルメタン、ビスフェノールＡジグリシジルエーテル、ビスフェノールＳジグリシジルエーテル、テトラブロモビスフェノールＡジグリシジルエーテル、レゾルシノールジグリシジルエーテル、フタル酸ジグリシジル、テトラヒドロフタル酸ジグリシジル、ビスフェノールヘキサフルオロアセトンジグリシジルエーテル、ｏ－フタル酸ジグリシジル、ジブロモフェニルグリシジルエーテル等の芳香族環を含むエポキシ化合物が挙げられるが、これらに限定されるものではない。これらのエポキシ化合物の中でも、アッベ数の観点から、芳香族環を含まないエポキシ化合物が、本発明には好適である。 Examples of the epoxy compound that can be used as the component (b) of the photopolymerizable composition of the present invention include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and (poly) ethylene glycol. Diglycidyl ether, (poly) propylene glycol diglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) Cyclohexane, glycerol triglycidyl ether, diglycerol polydiglycidyl ether, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 3,4-epoxycyclohexanecarboxylic acid 3 ′, 4′-epoxy chloride Hexylmethyl, tetraglycidyl-1,3-bisaminomethylcyclohexane, hydrogenated bisphenol A diglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol polyglycidyl ether, neopentyl glycol diglycidyl ether, triglycidyl Isocyanurate, tris- (3,4-epoxybutyl) isocyanurate, tris- (4,5-epoxypentyl) isocyanurate, tris- (5,6-epoxyhexyl) isocyanurate, tris (2-glycidyloxyethyl) Isocyanurate, monoallyl diglycidyl isocyanurate, N, N′-diglycidyl N ″-(2,3-dipropionyloxypropyl) isocyanurate, N , N′-bis (2,3-dipropionyloxypropyl) N ″ -glycidyl isocyanurate, tris (2,2-bis (glycidyloxymethyl) butyl) 3,3 ′, 3 ″-(2,4 , 6-trioxo-1,3,5-triazine-1,3,5-triyl) tripropanoate, sorbitol polyglycidyl ether, diglycidyl adipate, 1,2,7,8-diepoxyoctane, 1,6- Dimethylol perfluorohexane diglycidyl ether, 4- (spiro [3,4-epoxycyclohexane-1,5 ′-[1,3] dioxane] -2′-yl) -1,2-epoxycyclohexane, 1,2 -Bis (3,4-epoxycyclohexylmethoxy) ethane, 4,5-epoxy-2-methylcyclohexanecarboxylic acid 4 ', 5'-epoxy-2'-me Lucyclohexylmethyl, ethylene glycol bis (3,4-epoxycyclohexanecarboxylate), bis (3,4-epoxycyclohexylmethyl) adipate, bis (2,3-epoxycyclopentyl) ether, (3, 3 ', 4, 4 Epoxy compounds not containing an aromatic ring such as' -diepoxy) bicyclohexyl, tricyclo [5.2.1.0 2,6 ] decandimethanol diglycidyl ether, and 2,6-diglycidylphenyl glycidyl ether, 1,3-tris (4-glycidyloxyphenyl) propane, 4,4′-methylenebis (N, N-diglycidylaniline), triglycidyl-p-aminophenol, tetraglycidylmetaxylenediamine, tetraglycidyldiaminodiphenylmethane, bisphenol A jigli Dil ether, bisphenol S diglycidyl ether, tetrabromobisphenol A diglycidyl ether, resorcinol diglycidyl ether, diglycidyl phthalate, diglycidyl tetrahydrophthalate, bisphenol hexafluoroacetone diglycidyl ether, diglycidyl o-phthalate, dibromophenyl glycidyl ether, etc. Although the epoxy compound containing the aromatic ring of this is mentioned, it is not limited to these. Among these epoxy compounds, from the viewpoint of the Abbe number, an epoxy compound containing no aromatic ring is suitable for the present invention.
　なお上記エポキシ化合物として、以下の市販品を挙げることができる。固体エポキシ化合物としては、例えば、ＴＥＰＩＣ（登録商標）－Ｇ、同Ｓ、同Ｌ、同ＨＰ（何れも日産化学工業（株）製）が挙げられる。また、液状エポキシ化合物としては、例えば、ＴＥＰＩＣ（登録商標）－ＰＡＳ　Ｂ２２、同ＰＡＳ　Ｂ２６、同ＰＡＳ　Ｂ２６Ｌ、同ＶＬ、同ＵＣ（何れも日産化学工業（株）製）、ｊＥＲ（登録商標）８２８、同ＹＸ８０００（何れも三菱化学（株）製）、リカレジン（登録商標）ＤＭＥ１００（新日本理化（株）製）、及びセロキサイド（登録商標）２０２１Ｐ、同２０８１、同２０００、同８０００、エポリード（登録商標）ＧＴ－４０１、ＥＨＰＥ３１５０（何れも（株）ダイセル製）、ＥＰ－４０８８Ｌ（（株）ＡＤＥＫＡ製）が挙げられる。これらの市販品の中でも、アッベ数の観点から、芳香族環を含まないエポキシ化合物が、本発明には好適である。 In addition, the following commercial items can be mentioned as said epoxy compound. Examples of the solid epoxy compound include TEPIC (registered trademark) -G, S, L, and HP (all manufactured by Nissan Chemical Industries, Ltd.). Examples of the liquid epoxy compound include TEPIC (registered trademark) -PAS B22, PAS B26, PAS B26L, VL, UC (all manufactured by Nissan Chemical Industries, Ltd.), jER (registered trademark) 828. YX8000 (all manufactured by Mitsubishi Chemical Corporation), Rica Resin (registered trademark) DME100 (manufactured by Shin Nippon Rika Co., Ltd.), and Celoxide (registered trademark) 2021P, 2081, 2000, 8000, Epolide (registered) Trademarks: GT-401, EHPE3150 (all manufactured by Daicel Corporation), and EP-4088L (manufactured by ADEKA Corporation). Among these commercially available products, from the viewpoint of the Abbe number, an epoxy compound containing no aromatic ring is suitable for the present invention.
　本発明の光重合性組成物の（ｂ）成分として使用可能なオキセタン化合物としては、例えば、ジ［２－（３－オキセタニル）ブチル］エーテル、３－エチル－３－ヒドロキシメチルオキセタン、１，６－ビス［（３－エチルオキセタン－３－イル）メトキシ］－２，２，３，３，４，４，５，５－オクタフルオロヘキサン、３（４），８（９）－ビス［（１－エチル－３－オキセタニル）メトキシメチル－トリシクロ［５．２．１．０2,6］デカン、１，２－ビス｛［２－（１－エチル－３－オキセタニル）メトキシ］エチルチオ｝エタン、２，３－ビス［（３－エチルオキセタン－３－イル）メトキシメチル］ノルボルナン、２－エチル－２－［（３－エチルオキセタン－３－イル）メトキシメチル］－１，３－ｏ－ビス［（１－エチル－３－オキセタニル）メチル］－プロパン－１，３－ジオール、２，２－ジメチル－１，３－ｏ－ビス［（３－エチルオキセタン－３－イル）メチル］－プロパン－１，３－ジオール、２－ブチル－２－エチル－１，３－ｏ－ビス［（３－エチルオキセタン－３－イル）メチル］－プロパン－１，３－ジオール、１，４－ｏ－ビス［（３－エチルオキセタン－３－イル）メチル］－ブタン－１，４－ジオール、２，４，６－ｏ－トリス［（３－エチルオキセタン－３－イル）メチル］シアヌル酸等の芳香族環を含まないオキセタン化合物、及び１，４－ビス｛［（３－エチル－３－オキセタニル）メトキシ］メチル｝ベンゼン、１，４－ビス［（３－エチルオキセタン－３－イル）メトキシ］ベンゼン、１，３－ビス［（３－エチルオキセタン－３－イル）メトキシ］ベンゼン、１，２－ビス［（３－エチルオキセタン－３－イル）メトキシ］ベンゼン等の芳香族環を含むオキセタン化合物が挙げられるが、これらに限定されるものではない。これらのオキセタン化合物の中でも、アッベ数の観点から、芳香族環を含まないオキセタン化合物が、本発明には好適である。 Examples of the oxetane compound that can be used as the component (b) of the photopolymerizable composition of the present invention include di [2- (3-oxetanyl) butyl] ether, 3-ethyl-3-hydroxymethyloxetane, 1,6 -Bis [(3-ethyloxetane-3-yl) methoxy] -2,2,3,3,4,4,5,5-octafluorohexane, 3 (4), 8 (9) -bis [(1 -Ethyl-3-oxetanyl) methoxymethyl-tricyclo [5.2.1.0 2,6 ] decane, 1,2-bis {[2- (1-ethyl-3-oxetanyl) methoxy] ethylthio} ethane, , 3-Bis [(3-ethyloxetane-3-yl) methoxymethyl] norbornane, 2-ethyl-2-[(3-ethyloxetane-3-yl) methoxymethyl] -1,3-o-bis [( 1-ethyl -Oxetanyl) methyl] -propane-1,3-diol, 2,2-dimethyl-1,3-o-bis [(3-ethyloxetane-3-yl) methyl] -propane-1,3-diol, -Butyl-2-ethyl-1,3-o-bis [(3-ethyloxetane-3-yl) methyl] -propane-1,3-diol, 1,4-o-bis [(3-ethyloxetane- Oxetane compounds containing no aromatic ring such as 3-yl) methyl] -butane-1,4-diol, 2,4,6-o-tris [(3-ethyloxetane-3-yl) methyl] cyanuric acid, And 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 1,4-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,3-bis [( 3-ethyloxetane Examples include, but are not limited to, oxetane compounds containing an aromatic ring such as 3-yl) methoxy] benzene and 1,2-bis [(3-ethyloxetane-3-yl) methoxy] benzene. Among these oxetane compounds, from the viewpoint of the Abbe number, an oxetane compound containing no aromatic ring is suitable for the present invention.
　なお上記オキセタン化合物として、以下の市販品を挙げることができる。例えば、アロンオキセタン（登録商標）ＯＸＴ－１０１、同ＯＸＴ－２１２、同ＯＸＴ－１２１、同ＯＸＴ－２２１（何れも東亜合成（株）製）、及びＥＴＥＲＮＡＣＯＬＬ（登録商標）ＥＨＯ、同ＯＸＢＰ、同ＯＸＴＰ、同ＯＸＭＡ（何れも宇部興産（株）製）が挙げられる。これらの市販品の中でも、アッベ数の観点から芳香族環を含まないオキセタン化合物が、本発明には好適である。 In addition, the following commercial items can be mentioned as said oxetane compound. For example, Aron Oxetane (registered trademark) OXT-101, OXT-212, OXT-121, OXT-221 (all manufactured by Toa Gosei Co., Ltd.), and ETERNACOLL (registered trademark) EHO, OXBP, OXTP And OXMA (both manufactured by Ube Industries, Ltd.). Among these commercially available products, an oxetane compound containing no aromatic ring is suitable for the present invention from the viewpoint of the Abbe number.
　本発明の光重合性組成物の（ｂ）成分として使用可能なビニルエーテル化合物としては、例えば、エチルビニルエーテル、イソブチルビニルエーテル、ヒドロキシブチルビニルエーテル、ブタンジオールジビニルエーテル、シクロヘキシルビニルエーテル、ｎ－ブチルビニルエーテル、ｔｅｒｔ－ブチルビニルエーテル、ノルボルナン－２－オールビニルエーテル、トリエチレングリコールジビニルエーテル、オクタデシルビニルエーテル、シクロヘキサンジメタノールジビニルエーテル、ジエチレングリコールジビニルエーテル、シクロヘキサンジメタノールモノビニルエーテル、及びシクロヘキサンジオールジビニルエーテルが挙げられる。これらのビニルエーテル化合物の中でも、アッベ数の観点から、芳香族環を含まないビニルエーテル化合物が、本発明には好適である。 Examples of the vinyl ether compound that can be used as the component (b) of the photopolymerizable composition of the present invention include ethyl vinyl ether, isobutyl vinyl ether, hydroxybutyl vinyl ether, butanediol divinyl ether, cyclohexyl vinyl ether, n-butyl vinyl ether, tert-butyl. Examples include vinyl ether, norbornane-2-ol vinyl ether, triethylene glycol divinyl ether, octadecyl vinyl ether, cyclohexane dimethanol divinyl ether, diethylene glycol divinyl ether, cyclohexane dimethanol monovinyl ether, and cyclohexanediol divinyl ether. Among these vinyl ether compounds, from the viewpoint of the Abbe number, a vinyl ether compound containing no aromatic ring is suitable for the present invention.
　本発明の光重合性組成物の（ｂ）成分であるエポキシ化合物、オキセタン化合物又はビニルエーテル化合物として、エポキシ基、オキセタニル基、又はビニルエーテル基を含むポリマーを用いてもよい。特に、相溶性の観点から、下記の式（２）、式（３）又は式（４）で表される、エポキシ基又はオキセタニル基を含む（メタ）アクリレート重合物が好ましい。
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒ13乃至Ｒ15は水素原子又はメチル基を表し、Ｒ16はメチル基又はエチル基を表し、Ｘはエーテル結合又はエステル結合を含んでもよい炭素原子数１乃至５のアルキレン基を表す。） As the epoxy compound, oxetane compound or vinyl ether compound that is the component (b) of the photopolymerizable composition of the present invention, a polymer containing an epoxy group, an oxetanyl group, or a vinyl ether group may be used. In particular, from the viewpoint of compatibility, a (meth) acrylate polymer containing an epoxy group or an oxetanyl group represented by the following formula (2), formula (3), or formula (4) is preferable.
Figure JPOXMLDOC01-appb-C000006
 (Wherein R 13 to R 15 represent a hydrogen atom or a methyl group, R 16 represents a methyl group or an ethyl group, and X represents an alkylene group having 1 to 5 carbon atoms which may include an ether bond or an ester bond. To express.)
　このような（メタ）アクリレート重合物の原料モノマーとしては、例えば、グリシジルアクリレート、グリシジルメタクリレート、４－ヒドロキシブチルアクリレートグリシジルエーテル、４－ヒドロキシブチルメタクリレートグリシジルエーテル、３，４－エポキシシクロヘキシルメチルアクリレート、３，４－エポキシシクロヘキシルメチルメタクリレート、（３－エチルオキセタン－３－イル）メチルアクリレート、（３－エチルオキセタン－３－イル）メチルメタクリレート、（３－メチルオキセタン－３－イル）メチルアクリレート、及び（３－メチルオキセタン－３－イル）メチルメタクリレートが挙げられる。 Examples of the raw material monomer for such a (meth) acrylate polymer include glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, 4-hydroxybutyl methacrylate glycidyl ether, 3,4-epoxycyclohexylmethyl acrylate, 3, 4-epoxycyclohexylmethyl methacrylate, (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methyl methacrylate, (3-methyloxetane-3-yl) methyl acrylate, and (3- And methyl oxetane-3-yl) methyl methacrylate.
　上記（メタ）アクリレート重合物としては、屈折率や溶解性の調整のため、上記モノマーと他の（メタ）アクリレート化合物との共重合体でもよい。該他の（メタ）アクリレート化合物として、例えば、メチルアクリレート、メチルメタクリレート、イソボルニルアクリレート、イソボルニルメタクリレート、１－アダマンチルアクリレート、１－アダマンチルメタクリレート、２－アダマンチルアクリレート、２－アダマンチルメタクリレート、２－メチルアダマンタン－２－イルアクリレート、２－メチルアダマンタン－２－イルメタクリレート、２－エチルアダマンタン－２－イルアクリレート、２－エチルアダマンタン－２－イルメタクリレート、１，３－アダマンタンジオールジアクリレート、１，３－アダマンタンジオールジメタクリレート、ジシクロペンテニルアクリレート、ジシクロペンテニルメタクリレート、ジシクロペンタニルアクリレート、ジシクロペンタニルメタクリレート、ジシクロペンテニルオキシエチルアクリレート、ジシクロペンテニルオキシエチルメタクリレート、トリシクロ［５．２．１．０2,6］デセニルアクリレート、トリシクロ［５．２．１．０2,6］デセニルメタクリレート、トリシクロ［５．２．１．０2,6］デカニルアクリレート、トリシクロ［５．２．１．０2,6］デカニルメタクリレート、トリシクロ［５．２．１．０2,6］デカニルオキシエチルアクリレート、及びトリシクロ［５．２．１．０2,6］デカニルオキシエチルメタクリレートが挙げられる。前記他の（メタ）アクリレート化合物として市販品を用いてもよく、例えば、ＩＢＸＡ、ＡＤＭＡ（以上、大阪有機化学工業（株）製）、ＮＫエステルＡ－ＩＢ、同ＩＢ（以上、新中村化学工業（株）製）、及びファンクリル（登録商標）ＦＡ－５１１ＡＳ、同ＦＡ－５１２ＡＳ、同ＦＡ－５１３ＡＳ、同ＦＡ－５１２Ｍ、同ＦＡ－５１２ＭＴ、同ＦＡ－５１３Ｍ（以上、日立化成（株）製）が挙げられる。 The (meth) acrylate polymer may be a copolymer of the monomer and another (meth) acrylate compound in order to adjust the refractive index and solubility. Examples of the other (meth) acrylate compounds include methyl acrylate, methyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 1-adamantyl acrylate, 1-adamantyl methacrylate, 2-adamantyl acrylate, 2-adamantyl methacrylate, 2- Methyladamantan-2-yl acrylate, 2-methyladamantan-2-yl methacrylate, 2-ethyladamantan-2-yl acrylate, 2-ethyladamantan-2-yl methacrylate, 1,3-adamantanediol diacrylate, 1,3 -Adamantanediol dimethacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl meta Relate, dicyclopentenyl oxyethyl acrylate, dicyclopentenyl oxyethyl methacrylate, tricyclo [5.2.1.0 2, 6] decenyl acrylate, tricyclo [5.2.1.0 2, 6] decenyl Methacrylate, tricyclo [5.2.1.0 2,6 ] decanyl acrylate, tricyclo [5.2.1.0 2,6 ] decanyl methacrylate, tricyclo [5.2.1.0 2,6 ] deca Nyloxyethyl acrylate, and tricyclo [5.2.1.0 2,6 ] decanyloxyethyl methacrylate. Commercially available products may be used as the other (meth) acrylate compounds. For example, IBXA, ADMA (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), NK Ester A-IB, IB (above, Shin-Nakamura Chemical Co., Ltd.) (Manufactured by Hitachi Chemical Co., Ltd.), and FANCLIL (registered trademark) FA-511AS, FA-512AS, FA-513AS, FA-512M, FA-512MT, FA-513M. ).
　これらの（メタ）アクリレート重合物の平均分子量は、特に制限はないが、好ましくは重量平均分子量が５，０００乃至１，０００，０００、特に好ましくは１０，０００乃至１００，０００である。 The average molecular weight of these (meth) acrylate polymers is not particularly limited, but preferably has a weight average molecular weight of 5,000 to 1,000,000, particularly preferably 10,000 to 100,000.
［（ｃ）成分：光酸発生剤］
　本発明の光重合性組成物の（ｃ）成分である光酸発生剤は、光照射により直接又は間接的に酸（ルイス酸あるいはブレンステッド酸）を発生するものであれば特に限定されない。本発明のように光酸発生剤を配合した光重合性組成物は、加熱によらず、光照射で硬化するので、耐熱性の低い基板及び部材に使用することができる。本発明の光重合性組成物の（ｃ）成分の含有量は、前記（ａ）成分１００質量部に対し０．０１質量部乃至１０質量部、又は前記（ａ）成分及び前記（ｂ）成分の和１００質量部に対し０．０１質量部乃至１０質量部である。前記（ｃ）成分の含有量が０．０１質量部よりも少ないと硬化が不十分となり、インプリント成形に十分な離型性・機械強度が得られない。前記（ｃ）成分の含有量が１０質量部を超えると、光酸発生剤由来の着色により硬化物の透明性が損なわれる。 [Component (c): Photoacid generator]
The photoacid generator which is the component (c) of the photopolymerizable composition of the present invention is not particularly limited as long as it generates an acid (Lewis acid or Bronsted acid) directly or indirectly by light irradiation. Since the photopolymerizable composition containing the photoacid generator as in the present invention is cured by light irradiation without being heated, it can be used for substrates and members having low heat resistance. Content of (c) component of the photopolymerizable composition of this invention is 0.01 mass part thru | or 10 mass parts with respect to 100 mass parts of said (a) component, or said (a) component and said (b) component. It is 0.01 mass part thru | or 10 mass parts with respect to 100 mass parts of sum. When the content of the component (c) is less than 0.01 parts by mass, curing becomes insufficient, and sufficient releasability and mechanical strength for imprint molding cannot be obtained. When content of the said (c) component exceeds 10 mass parts, transparency of hardened | cured material will be impaired by coloring derived from a photo-acid generator.
　本発明の光重合性組成物の（ｃ）成分として使用可能な光酸発生剤としては、例えば、ヨードニウム塩、スルホニウム塩、ホスホニウム塩、セレニウム塩等のオニウム塩、及び鉄アレーン錯体化合物を挙げることができる。 Examples of the photoacid generator that can be used as the component (c) of the photopolymerizable composition of the present invention include onium salts such as iodonium salts, sulfonium salts, phosphonium salts, selenium salts, and iron arene complex compounds. Can do.
　上記ヨードニウム塩としては、例えば、ジフェニルヨードニウム、４，４’－ジクロロジフェニルヨードニウム、４，４’－ジメトキシジフェニルヨードニウム、４，４’－ジ－ｔｅｒｔ－ブチルジフェニルヨードニウム、４－メチルフェニル（４－（２－メチルプロピル）フェニル）ヨードニウム、３，３’－ジニトロフェニルヨードニウム、４－（１－エトキシカルボニルエトキシ）フェニル（２，４，６－トリメチルフェニル）ヨードニウム、４－メトキシフェニル（フェニル）ヨードニウム等のヨードニウムの、クロリド、ブロミド、メシレート、トシレート、トリフルオロメタンスルホネート、テトラフルオロボレート、テトラキス（ペンタフルオロフェニル）ボレート、ヘキサフルオロホスフェート、ヘキサフルオロアルセネート、及びヘキサフルオロアンチモネートなどの、ジアリールヨードニウム塩が挙げられる。 Examples of the iodonium salt include diphenyliodonium, 4,4′-dichlorodiphenyliodonium, 4,4′-dimethoxydiphenyliodonium, 4,4′-di-tert-butyldiphenyliodonium, 4-methylphenyl (4- ( 2-methylpropyl) phenyl) iodonium, 3,3′-dinitrophenyliodonium, 4- (1-ethoxycarbonylethoxy) phenyl (2,4,6-trimethylphenyl) iodonium, 4-methoxyphenyl (phenyl) iodonium, etc. Iodonium, chloride, bromide, mesylate, tosylate, trifluoromethanesulfonate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate, hexafluorophosphate, hexafluoroarsene DOO, and such hexafluoroantimonate include diaryliodonium salts.
　上記スルホニウム塩としては、例えば、トリフェニルスルホニウム、ジフェニル（４－ｔｅｒｔ－ブチルフェニル）スルホニウム、トリス（４－ｔｅｒｔ－ブチルフェニル）スルホニウム、ジフェニル（４－メトキシフェニル）スルホニウム、トリス（４－メチルフェニル）スルホニウム、トリス（４－メトキシフェニル）スルホニウム、トリス（４－エトキシフェニル）スルホニウム、ジフェニル（４－（フェニルチオ）フェニル）スルホニウム、トリス（４－（フェニルチオ）フェニル）スルホニウム等のスルホニウムの、クロリド、ブロミド、トリフルオロメタンスルホネート、テトラフルオロボレート、ヘキサフルオロホスフェート、ヘキサフルオロアルセネート、及びヘキサフルオロアンチモネートなどの、トリアリールスルホニウム塩が挙げられる。 Examples of the sulfonium salt include triphenylsulfonium, diphenyl (4-tert-butylphenyl) sulfonium, tris (4-tert-butylphenyl) sulfonium, diphenyl (4-methoxyphenyl) sulfonium, tris (4-methylphenyl) Sulfonium chloride, bromide, sulfonium such as sulfonium, tris (4-methoxyphenyl) sulfonium, tris (4-ethoxyphenyl) sulfonium, diphenyl (4- (phenylthio) phenyl) sulfonium, tris (4- (phenylthio) phenyl) sulfonium, Triarylsulfones such as trifluoromethanesulfonate, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, and hexafluoroantimonate Umm salts.
　上記ホスホニウム塩としては、例えば、テトラフェニルホスホニウム、エチルトリフェニルホスホニウム、テトラ（ｐ－メトキシフェニル）ホスホニウム、エチルトリ（ｐ－メトキシフェニル）ホスホニウム、ベンジルトリフェニルホスホニウム等のホスホニウムの、クロリド、ブロミド、テトラフルオロボレート、ヘキサフルオロホスフェート、ヘキサフルオロアンチモネートなどの、アリールホスホニウム塩が挙げられる。 Examples of the phosphonium salt include chloride, bromide, tetrafluoro of phosphonium such as tetraphenylphosphonium, ethyltriphenylphosphonium, tetra (p-methoxyphenyl) phosphonium, ethyltri (p-methoxyphenyl) phosphonium, benzyltriphenylphosphonium. Examples include aryl phosphonium salts such as borate, hexafluorophosphate, hexafluoroantimonate.
　上記セレニウム塩としては、例えば、トリフェニルセレニウムヘキサフルオロホスフェートなどの、トリアリールセレニウム塩が挙げられる。 Examples of the selenium salt include triaryl selenium salts such as triphenyl selenium hexafluorophosphate.
　上記鉄アレーン錯体化合物としては、例えば、ビス（η５－シクロペンタジエニル）（η６－イソプロピルベンゼン）鉄（ＩＩ）ヘキサフルオロホスフェートが挙げられる。 Examples of the iron arene complex compound include bis (η5-cyclopentadienyl) (η6-isopropylbenzene) iron (II) hexafluorophosphate.
　本発明の光重合性組成物の（ｃ）成分として、これらの光酸発生剤を一種のみで、又は二種以上を組み合わせて用いることができる。 As the component (c) of the photopolymerizable composition of the present invention, these photoacid generators can be used alone or in combination of two or more.
　なお上記光酸発生剤として、以下の市販品を挙げることができる。例えば、サンエイド（登録商標）ＳＩ－６０、同ＳＩ－８０、同ＳＩ－１００、同ＳＩ－６０Ｌ、同ＳＩ－８０Ｌ、同ＳＩ－１００Ｌ、同ＳＩ－Ｌ１４５、同ＳＩ－Ｌ１５０、同ＳＩ－Ｌ１６０、同ＳＩ－Ｌ１１０、同ＳＩ－Ｌ１４７（何れも三新化学工業（株）製）、ＵＶＩ－６９５０、ＵＶＩ－６９７０、ＵＶＩ－６９７４、ＵＶＩ－６９９０、ＵＶＩ－６９９２（何れもユニオンカーバイド社製）、ＣＰＩ（登録商標）－１００Ｐ、同－１１０Ｐ、同－１０１Ａ、同－２００Ｋ、同－２１０Ｓ（以上、サンアプロ（株）製）、アデカオプトマーＳＰ－１５０、同ＳＰ－１５１、同ＳＰ－１７０、同ＳＰ－１７１（何れも（株）ＡＤＥＫＡ製）、イルガキュア（登録商標）２５０、同２７０、同２９０（何れもＢＡＳＦ社製）、ＣＩ－２４８１、ＣＩ－２６２４、ＣＩ－２６３９、ＣＩ－２０６４（何れも日本曹達（株）製）、ＣＤ－１０１０、ＣＤ－１０１１、ＣＤ－１０１２（何れもサートマー社製）、ＤＳ－１００、ＤＳ－１０１、ＤＡＭ－１０１、ＤＡＭ－１０２、ＤＡＭ－１０５、ＤＡＭ－２０１、ＤＳＭ－３０１、ＮＡＩ－１００、ＮＡＩ－１０１、ＮＡＩ－１０５、ＮＡＩ－１０６、ＳＩ－１００、ＳＩ－１０１、ＳＩ－１０５、ＳＩ－１０６、ＰＩ－１０５、ＮＤＩ－１０５、ＢＥＮＺＯＩＮ　ＴＯＳＹＬＡＴＥ、ＭＢＺ－１０１、ＭＢＺ－３０１、ＰＹＲ－１００、ＰＹＲ－２００、ＤＮＢ－１０１、ＮＢ－１０１、ＮＢ－２０１、ＢＢＩ－１０１、ＢＢＩ－１０２、ＢＢＩ－１０３、ＢＢＩ－１０９（以上、みどり化学（株）製）、ＰＣＩ－０６１Ｔ、ＰＣＩ－０６２Ｔ、ＰＣＩ－０２０Ｔ、ＰＣＩ－０２２Ｔ（何れも日本化薬（株）製）、及びＩＢＰＦ、ＩＢＣＦ（何れも三和ケミカル（株）製）を挙げることができる。 In addition, the following commercial items can be mentioned as said photo-acid generator. For example, Sun-Aid (registered trademark) SI-60, SI-80, SI-100, SI-60L, SI-80L, SI-100L, SI-100L, SI-L145, SI-L150, SI-L160 SI-L110, SI-L147 (all manufactured by Sanshin Chemical Co., Ltd.), UVI-6950, UVI-6970, UVI-6974, UVI-6990, UVI-6990 (all manufactured by Union Carbide) CPI (registered trademark) -100P, -110P, -101A, -200K, -210S (above, manufactured by San Apro Co., Ltd.), Adekaoptomer SP-150, SP-151, SP-170 SP-171 (all manufactured by ADEKA Corporation), Irgacure (registered trademark) 250, 270, 290 (all manufactured by BASF), CI-2 81, CI-2624, CI-2639, CI-2064 (all manufactured by Nippon Soda Co., Ltd.), CD-1010, CD-1011, CD-1012 (all manufactured by Sartomer), DS-100, DS-101 , DAM-101, DAM-102, DAM-105, DAM-201, DSM-301, NAI-100, NAI-101, NAI-105, NAI-106, SI-100, SI-101, SI-105, SI -106, PI-105, NDI-105, BENZOIN TOSYLATE, MBZ-101, MBZ-301, PYR-100, PYR-200, DNB-101, NB-101, NB-201, BBI-101, BBI-102, BBI-103, BBI-109 (above, manufactured by Midori Chemical Co., Ltd.), PCI-061T, P I-062T, PCI-020T, PCI-022T (manufactured by both Nippon Kayaku Co.), and IBPF, mention may be made of IBCF (both Sanwa Chemical Co., Ltd.).
＜その他添加剤＞
　さらに本発明の光重合性組成物は、本発明の効果を損なわない限りにおいて、必要に応じて、酸化防止剤、紫外線吸収剤、光安定化剤、レベリング剤、レオロジー調整剤、シランカップリング剤等の接着補助剤、消泡剤などを含有することができる。 <Other additives>
Furthermore, the photopolymerizable composition of the present invention may contain an antioxidant, an ultraviolet absorber, a light stabilizer, a leveling agent, a rheology modifier, and a silane coupling agent as necessary, as long as the effects of the present invention are not impaired. It is possible to contain an adhesion aid such as an antifoaming agent.
　上記酸化防止剤としては、例えば、フェノール系酸化防止剤、リン酸系酸化防止剤、及びスルフィド系酸化防止剤が挙げられるが、これらの中でもフェノール系酸化防止剤及びリン酸系酸化防止剤が好ましい。 Examples of the antioxidant include a phenol-based antioxidant, a phosphoric acid-based antioxidant, and a sulfide-based antioxidant, and among these, a phenol-based antioxidant and a phosphoric acid-based antioxidant are preferable. .
　上記フェノール系酸化防止剤としては、例えば、ＩＲＧＡＮＯＸ（登録商標）２４５、同１０１０、同１０３５、同１０７６、同１１３５（何れもＢＡＳＦジャパン（株）製）、スミライザー（登録商標）ＧＡ－８０、同ＧＰ、同ＭＤＰ－Ｓ、同ＢＢＭ－Ｓ、同ＷＸ－Ｒ（何れも住友化学（株）製）、アデカスタブ（登録商標）ＡＯ－２０、同ＡＯ－３０、同ＡＯ－４０、同ＡＯ－５０、同ＡＯ－６０、同ＡＯ－８０、同ＡＯ－３３０（何れも（株）ＡＤＥＫＡ製）が挙げられる。 Examples of the phenol-based antioxidant include IRGANOX (registered trademark) 245, 1010, 1035, 1076, 1135 (all manufactured by BASF Japan Ltd.), Sumilyzer (registered trademark) GA-80, GP, MDP-S, BBM-S, WX-R (all manufactured by Sumitomo Chemical Co., Ltd.), ADK STAB (registered trademark) AO-20, AO-30, AO-40, AO-50 AO-60, AO-80, AO-330 (all manufactured by ADEKA Corporation).
　上記リン酸系酸化防止剤としては、例えば、ＩＲＧＡＦＯＳ（登録商標）１６８（ＢＡＳＦジャパン（株）製）、アデカスタブ（登録商標）ＰＥＰ－３６、同ＰＥＰ－８、同ＨＰ－１８、同ＨＰ－１０、同２１１２、同２１１２ＲＧ、同１１７８、同１５００、同Ｃ、同１３５Ａ、同３０１０、同ＴＰＰ（何れも（株）ＡＤＥＫＡ製）が挙げられる。 Examples of the phosphoric acid antioxidant include IRGAFOS (registered trademark) 168 (manufactured by BASF Japan Ltd.), ADK STAB (registered trademark) PEP-36, PEP-8, HP-18, and HP-10. 2112, 2112RG, 1178, 1500, C, 135A, 3010, and TPP (all manufactured by ADEKA Corporation).
　上記スルフィド系酸化防止剤としては、例えば、ＩＲＧＡＮＯＸ（登録商標）１７２６、同１５２０Ｌ（何れもＢＡＳＦジャパン（株）製）、アデカスタブ（登録商標）ＡＯ－４１２Ｓ、同ＡＯ－５０３（何れも（株）ＡＤＥＫＡ製）が挙げられる。 Examples of the sulfide antioxidant include IRGANOX (registered trademark) 1726 and 1520L (both manufactured by BASF Japan), Adeka Stub (registered trademark) AO-412S, and AO-503 (all manufactured by ADEKA).
　本発明の光重合性組成物に酸化防止剤が添加される場合、該酸化防止剤は一種のみで、又は二種以上を混合して用いてもよい。また、その添加量としては、重合性成分、すなわち上記（ａ）成分１００質量部に対し０．０１質量部乃至２０質量部、又は上記（ａ）成分及び（ｂ）成分の総量１００質量部に対して０．０１質量部乃至２０質量部、さらに好ましくは０．１質量部乃至１０質量部である。本発明の光重合性組成物は、酸化防止剤を前記添加量で含有することにより、該光重合性組成物の硬化物は、加熱による黄変が抑制される。 When the antioxidant is added to the photopolymerizable composition of the present invention, the antioxidant may be used alone or in combination of two or more. Moreover, as the addition amount, it is 0.01 mass part thru | or 20 mass parts with respect to 100 mass parts of polymerizable components, ie, said (a) component, or the total amount of said (a) component and (b) component is 100 mass parts. On the other hand, it is 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass. The photopolymerizable composition of the present invention contains the antioxidant in the above-described addition amount, so that the cured product of the photopolymerizable composition is prevented from being yellowed by heating.
＜光重合性組成物の調製方法＞
　本発明の光重合性組成物の調製方法は、特に限定されない。調製法としては、例えば、（ａ）成分及び（ｃ）成分、並びに必要に応じて（ｂ）成分を所定の割合で混合し、所望によりその他添加剤をさらに添加して混合し均一な溶液とする方法、これら各成分のうち、例えば（ａ）成分及び（ｂ）成分のうち何れか一方又は両方の一部を混合して均一な溶液とした後、残りの各成分を加え、所望によりその他添加剤をさらに添加して混合し均一な溶液とする方法、又はこれらの成分に加えさらに慣用の溶媒を使用する方法が挙げられる。 <Method for Preparing Photopolymerizable Composition>
The method for preparing the photopolymerizable composition of the present invention is not particularly limited. As a preparation method, for example, the components (a) and (c), and the component (b) as necessary are mixed in a predetermined ratio, and other additives are further added as desired to mix the solution uniformly. Among these components, for example, after mixing a part of either one or both of component (a) and component (b) to make a uniform solution, add the remaining components, and optionally other Examples thereof include a method in which an additive is further added and mixed to obtain a uniform solution, or a method in which a conventional solvent is used in addition to these components.
　本発明の光重合性組成物が溶媒を含有する場合、該光重合性組成物における固形分の割合は、各成分が溶媒に均一に溶解している限りは特に限定されないが、例えば１質量％乃至５０質量％であり、又は１質量％乃至３０質量％であり、又は１質量％乃至２５質量％である。ここで固形分とは、本発明の光重合性組成物の全成分から溶媒成分を除いたものである。 When the photopolymerizable composition of the present invention contains a solvent, the ratio of the solid content in the photopolymerizable composition is not particularly limited as long as each component is uniformly dissolved in the solvent. Thru | or 50 mass%, or 1 thru | or 30 mass%, or 1 thru | or 25 mass%. Here, the solid content is obtained by removing the solvent component from all the components of the photopolymerizable composition of the present invention.
　また、溶液に調製した本発明の光重合性組成物は、孔径が０．１μｍ乃至５μｍのフィルタなどを用いてろ過した後、使用することが好ましい。 The photopolymerizable composition of the present invention prepared in a solution is preferably used after being filtered using a filter having a pore size of 0.1 μm to 5 μm.
＜＜硬化物＞＞
　上記光重合性組成物を、露光（光硬化）して、硬化物を得ることができ、本発明は上記光重合性化合物の硬化物も対象とする。露光する光線としては、例えば、紫外線、電子線及びＸ線が挙げられる。紫外線照射に用いる光源としては、例えば、太陽光線、ケミカルランプ、低圧水銀灯、高圧水銀灯、メタルハライドランプ、キセノンランプ、及びＵＶ－ＬＥＤが使用できる。また、露光後、硬化物の物性を安定化させるためにポストベークを施してもよい。ポストベークの方法としては、特に限定されないが、通常、ホットプレート、オーブン等を使用して、５０℃乃至２６０℃、１分乃至２４時間の範囲で行われる。 << cured product >>
The photopolymerizable composition can be exposed (photocured) to obtain a cured product, and the present invention also targets a cured product of the photopolymerizable compound. Examples of light rays to be exposed include ultraviolet rays, electron beams, and X-rays. As a light source used for ultraviolet irradiation, for example, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, and a UV-LED can be used. Moreover, you may post-bake in order to stabilize the physical property of hardened | cured material after exposure. The post-baking method is not particularly limited, but is usually performed in a range of 50 ° C. to 260 ° C. and 1 minute to 24 hours using a hot plate, an oven or the like.
　本発明の光重合性組成物を光硬化することにより得られる硬化物は、アッベ数が５６以上と高いものであり、波長５８９ｎｍ（Ｄ線）における屈折率が１．５３０以上と高いものであり、また、加熱による黄変も見られない。そのため、本発明の光重合性組成物は、高屈折率樹脂レンズ用組成物として好適に使用することができる。 The cured product obtained by photocuring the photopolymerizable composition of the present invention has an Abbe number as high as 56 or higher, and a refractive index as high as 1.530 or higher at a wavelength of 589 nm (D line). Moreover, yellowing by heating is not seen. Therefore, the photopolymerizable composition of the present invention can be suitably used as a composition for a high refractive index resin lens.
＜＜成形体＞＞
　本発明の光重合性組成物は、例えば、圧縮成形（インプリント成形等）、注型、射出成形、ブロー成形などの慣用の成形法を使用することによって、硬化物の形成と並行して各種成形体を容易に製造することができる。こうして得られる成形体も本発明の対象である。成形体を製造する方法としては、例えば接し合う支持体と鋳型との間の空間、又は分割可能な鋳型の内部の空間に本発明の光重合性組成物を充填する工程、該空間に充填された組成物を露光して光重合する工程、得られた光重合物を取り出して離型する工程、並びに、該光重合物を、該離型の前、中途又は後において加熱する工程を含む方法が挙げられる。 << Molded Article >>
The photopolymerizable composition of the present invention can be used in various ways in parallel with the formation of a cured product by using conventional molding methods such as compression molding (imprint molding, etc.), casting, injection molding, blow molding, etc. A molded object can be manufactured easily. The molded body thus obtained is also an object of the present invention. As a method for producing a molded body, for example, a step of filling the space of the photopolymerizable composition of the present invention into a space between a contacting support and a mold, or a space inside a separable mold, the space is filled. A step of exposing the resulting composition to photopolymerization, a step of taking out and releasing the obtained photopolymer, and a step of heating the photopolymer before, during or after the release Is mentioned.
　上記露光して光重合する工程は、前述の硬化物を得るための条件を適用して実施することができる。さらに、上記光重合物を加熱する工程の条件としては、特に限定されないが、通常、５０℃乃至２６０℃、１分乃至２４時間の範囲から適宜選択される。また、加熱手段としては、特に限定されないが、例えば、ホットプレート及びオーブンが挙げられる。このような方法によって製造された成形体は、カメラモジュール用レンズとして好適に使用することができる。 The above-mentioned exposure and photopolymerization step can be carried out by applying the conditions for obtaining the above-mentioned cured product. Furthermore, the conditions for the step of heating the photopolymerized product are not particularly limited, but are usually appropriately selected from the range of 50 ° C. to 260 ° C. and 1 minute to 24 hours. Moreover, it does not specifically limit as a heating means, For example, a hotplate and oven are mentioned. The molded body produced by such a method can be suitably used as a lens for a camera module.
　以下、実施例を挙げて、本発明をより具体的に説明するが、本発明は下記の実施例に限定されるものではない。なお、下記実施例において、試料の調製及び物性の分析に用いた装置及び条件は、以下の通りである。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. In the following examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.
（１）撹拌脱泡機
　装置：（株）シンキー製　自転・公転ミキサー　あわとり練太郎（登録商標）ＡＲＥ－３１０
（２）ＵＶ露光
　装置：アイグラフィックス（株）製　バッチ式ＵＶ照射装置（高圧水銀灯２ｋＷ×１灯）
（３）透過率
　装置：日本分光（株）製　紫外可視近赤外分光光度計Ｖ－６７０
　リファレンス：石英
（４）屈折率ｎD、アッベ数νD
　装置：アントンパール社製　多波長屈折計Ａｂｂｅｍａｔ　ＭＷ
　測定温度：２３℃
　試料とプリズムを接着するための中間液：モノブロモナフタレン (1) Agitating and defoaming machine Device: Rotating / revolving mixer manufactured by Shinkey Co., Ltd. Nertaro Awatori (registered trademark) ARE-310
(2) UV exposure system: Batch type UV irradiation system (high pressure mercury lamp 2kW x 1 lamp) manufactured by Eye Graphics Co., Ltd.
(3) Transmittance: UV-Vis near-infrared spectrophotometer V-670 manufactured by JASCO Corporation
Reference: Quartz (4) Refractive index n D , Abbe number ν D
Apparatus: Multi-wavelength refractometer Abbemat MW manufactured by Anton Paar
Measurement temperature: 23 ° C
Intermediate solution for bonding sample and prism: monobromonaphthalene
　さらに、下記合成例に示すポリマーの重量平均分子量及び分散度は、ゲルパーミエーションクロマトグラフィー（以下、本明細書ではＧＰＣと略称する。）による測定結果である。測定には、（株）島津製作所製ＧＰＣシステムを用いた。当該ＧＰＣシステムの構成と、測定条件は下記のとおりである。
（５）ＧＰＣ
ＧＰＣシステム構成
システムコントローラ：ＣＢＭ－２０Ａ、カラムオーブン：ＣＴＯ－２０Ａ、オートサンプラ：ＳＩＬ－１０ＡＦ、検出器：ＳＰＤ－２０Ａ及びＲＩＤ－１０Ａ、排気ユニット：ＤＧＵ－２０Ａ３
ＧＰＣカラム：Ｓｈｏｄｅｘ（登録商標）ＫＦ－８０４Ｌ及びＫＦ－８０３Ｌ
カラム温度：４０℃
溶媒：テトラヒドロフラン
流量：１ｍＬ／分
標準試料：異なる重量平均分子量（１９７０００、５５１００、１２８００、３９５０、１２６０）のポリスチレン５種 Furthermore, the polymer weight average molecular weight and dispersity shown in the following synthesis examples are measurement results by gel permeation chromatography (hereinafter abbreviated as GPC in this specification). For the measurement, a GPC system manufactured by Shimadzu Corporation was used. The configuration and measurement conditions of the GPC system are as follows.
(5) GPC
GPC system configuration System controller: CBM-20A, column oven: CTO-20A, autosampler: SIL-10AF, detector: SPD-20A and RID-10A, exhaust unit: DGU-20A3
GPC columns: Shodex® KF-804L and KF-803L
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Flow rate: 1 mL / min Standard sample: 5 types of polystyrene with different weight average molecular weights (197000, 55100, 12800, 3950, 1260)
　下記合成例、実施例及び比較例において使用した化合物の供給元は以下の通りである。
ＡＤＭＡ：大阪有機化学工業（株）製　１－アダマンチルメタクリレート
ＯＸＥ－１０：大阪有機化学工業（株）製　（３－エチルオキセタン－３－イル）メチルアクリレート
ＴＨＩＤＥ：ＪＸエネルギー（株）製　テトラヒドロインデンジエポキシド
Ｉ１０１０：ＢＡＳＦジャパン（株）製　商品名：ＩＲＧＡＮＯＸ（登録商標）１０１０］
ＣＰＩ－１１０Ｐ：サンアプロ（株）製　商品名：ＣＰＩ（登録商標）－１１０Ｐ
ＥＨＰＥ３１５０：（株）ダイセル製　商品名：ＥＨＰＥ３１５０
ＣＥＬ２０２１Ｐ：（株）ダイセル製　商品名：セロキサイド（登録商標）２０２１Ｐ
ＥＰ－４０８８Ｌ：（株）ＡＤＥＫＡ製　商品名：ＥＰ－４０８８Ｌ
ＹＸ８０００：三菱化学（株）製　商品名：ｊＥＲ（登録商標）ＹＸ８０００ The suppliers of the compounds used in the following synthesis examples, examples and comparative examples are as follows.
ADMA: manufactured by Osaka Organic Chemical Industry Co., Ltd. 1-adamantyl methacrylate OXE-10: manufactured by Osaka Organic Chemical Industry Co., Ltd. (3-ethyloxetane-3-yl) methyl acrylate THIDE: manufactured by JX Energy Co., Ltd. Tetrahydroindene diepoxide I1010: BASF Japan K.K. trade name: IRGANOX (registered trademark) 1010]
CPI-110P: San Apro Co., Ltd. Product name: CPI (registered trademark) -110P
EHPE3150: Made by Daicel Corporation Product name: EHPE3150
CEL2021P: Daicel Co., Ltd. Product name: Celoxide (registered trademark) 2021P
EP-4088L: ADEKA Corporation Product name: EP-4088L
YX8000: Mitsubishi Chemical Corporation product name: jER (registered trademark) YX8000
［合成例１］
　凝縮器を備えた２００ｍＬの反応フラスコに、プロピレングリコールモノメチルエーテルアセテート３５．７ｇを仕込み、窒素バルーンを用いて該反応フラスコ中の空気を窒素で置換した。その後、反応温度を７０℃まで昇温し、滴下ロートを用いて、ＡＤＭＡ（２０．０ｇ、９０．８ｍｍｏｌ）、ＯＸＥ－１０（１０．３ｇ、６０．５ｍｍｏｌ）、アゾビスイソブチロニトリル（０．９９４ｇ、６．０５ｍｍｏｌ）の混合物を、約１２０分間かけて前記反応フラスコに滴下した。滴下終了後、反応温度を７０℃で維持し、１６時間撹拌した。撹拌終了後、得られた反応物を室温（およそ２５℃）に冷却し、メタノール（１１３０ｇ）へ再沈殿した。濾過により固体を濾別し、真空乾燥機を用いて１Ｔｏｒｒ以下、５０℃で８時間乾燥することで、目的とするオキセタニル基含有アクリルポリマー（以下、ポリマー１と称する。）を得た。得られたポリマー１をＧＰＣで測定したところ、ポリスチレン換算で重量平均分子量Ｍｗは４５，０００、分散度：Ｍｗ／Ｍｎは１．７であった。 [Synthesis Example 1]
A 200 mL reaction flask equipped with a condenser was charged with 35.7 g of propylene glycol monomethyl ether acetate, and the air in the reaction flask was replaced with nitrogen using a nitrogen balloon. Thereafter, the reaction temperature was raised to 70 ° C., and ADMA (20.0 g, 90.8 mmol), OXE-10 (10.3 g, 60.5 mmol), azobisisobutyronitrile (0 .994 g, 6.05 mmol) was added dropwise to the reaction flask over about 120 minutes. After completion of the dropwise addition, the reaction temperature was maintained at 70 ° C. and stirred for 16 hours. After completion of stirring, the resulting reaction was cooled to room temperature (approximately 25 ° C.) and reprecipitated into methanol (1130 g). The solid was separated by filtration, and dried at 1 Torr or less and 50 ° C. for 8 hours using a vacuum dryer to obtain a target oxetanyl group-containing acrylic polymer (hereinafter referred to as polymer 1). When the obtained polymer 1 was measured by GPC, the weight average molecular weight Mw was 45,000 and dispersion degree: Mw / Mn was 1.7 in polystyrene conversion.
［実施例１］
　（ａ）脂環式エポキシ化合物としてＴＨＩＤＥ、（ｃ）光酸発生剤、及び酸化防止剤を、それぞれ下記表１に記載の割合で配合し、前記撹拌脱泡機を用いて５０℃で３時間撹拌混合した。さらに同装置を用いて１０分間撹拌脱泡することで光重合性組成物１を調製した。なお、下記表１中、「部」は「質量部」を表す。 [Example 1]
(A) THIDE as an alicyclic epoxy compound, (c) a photoacid generator and an antioxidant are blended in the proportions shown in Table 1 below, respectively, and 3 hours at 50 ° C. using the stirring deaerator. Stir and mix. Furthermore, the photopolymerizable composition 1 was prepared by carrying out stirring deaeration for 10 minutes using the same apparatus. In Table 1 below, “part” represents “part by mass”.
［実施例２乃至実施例８］
　（ａ）脂環式エポキシ化合物としてＴＨＩＤＥ、（ｂ）その他のエポキシ化合物、（ｃ）光酸発生剤、及び酸化防止剤を、それぞれ下記表１に記載の割合で配合し、前記撹拌脱泡機を用いて５０℃で３時間撹拌混合した。さらに同装置を用いて１０分間撹拌脱泡することで光重合性組成物２乃至光重合性組成物８を調製した。 [Example 2 to Example 8]
(A) THIDE as the alicyclic epoxy compound, (b) other epoxy compound, (c) photoacid generator, and antioxidant are blended in the proportions shown in Table 1 below, and the stirring deaerator And stirred for 3 hours at 50 ° C. Furthermore, the photopolymerizable composition 2 thru | or the photopolymerizable composition 8 were prepared by stirring and degassing for 10 minutes using the same apparatus.
［実施例９］
　（ａ）脂環式エポキシ化合物としてＴＨＩＤＥ、（ｂ）オキセタン化合物として合成例１で得たポリマー１、（ｃ）光酸発生剤、及び酸化防止剤を、それぞれ下記表１に記載の割合で配合し、前記撹拌脱泡機を用いて５０℃で３時間撹拌混合した。さらに同装置を用いて１０分間撹拌脱泡することで光重合性組成物９を調製した。 [Example 9]
(A) THIDE as an alicyclic epoxy compound, (b) polymer 1 obtained in Synthesis Example 1 as an oxetane compound, (c) a photoacid generator, and an antioxidant, respectively, in the proportions shown in Table 1 below Then, the mixture was stirred and mixed at 50 ° C. for 3 hours using the stirring deaerator. Furthermore, the photopolymerizable composition 9 was prepared by stirring and degassing for 10 minutes using the same apparatus.
［比較例１］
　（ｂ）その他のエポキシ化合物、（ｃ）光酸発生剤、及び酸化防止剤を、それぞれ下記表１に記載の割合で配合し、上記撹拌脱泡機を用いて５０℃で３時間撹拌混合した。さらに同撹拌脱泡機を用いて１０分間撹拌脱泡することで光重合性組成物１０を調製した。 [Comparative Example 1]
(B) Other epoxy compound, (c) photoacid generator, and antioxidant were blended in the proportions shown in Table 1 below, and stirred and mixed at 50 ° C. for 3 hours using the above stirring deaerator. . Further, the photopolymerizable composition 10 was prepared by stirring and defoaming for 10 minutes using the same stirring and defoaming machine.
［硬化膜の作製及び透過率評価］
　実施例１乃至実施例９及び比較例１で調製した各光重合性組成物を、３００μｍ厚のシリコーンゴム製スペーサーとともに、ＮＯＶＥＣ（登録商標）１７２０（スリーエムジャパン（株）製）を塗布・乾燥することで離型処理したガラス基板と、石英基板で挟み込んだ。この挟み込んだ光重合性組成物を、上記ＵＶ照射装置を用いて２０ｍＷ／ｃｍ2で４５０秒間ＵＶ露光した。露光後得られた硬化物を、前記離型処理したガラス基板から剥離した後、８５℃のホットプレートで６０分間加熱することで、前記石英基板上に、直径３０ｍｍ、厚さ３００μｍの硬化膜を作製した。得られた硬化膜の波長４００ｎｍの透過率を、上記紫外可視近赤外分光光度計を用いて測定した。結果を下記表１に示す。 [Preparation of cured film and evaluation of transmittance]
Each photopolymerizable composition prepared in Examples 1 to 9 and Comparative Example 1 is coated with NOVEC (registered trademark) 1720 (manufactured by 3M Japan) together with a 300 μm thick silicone rubber spacer and dried. This was sandwiched between a glass substrate that had been released from the mold and a quartz substrate. The sandwiched photopolymerizable composition was subjected to UV exposure at 20 mW / cm 2 for 450 seconds using the UV irradiation apparatus. The cured product obtained after the exposure is peeled off from the release-treated glass substrate, and then heated on an 85 ° C. hot plate for 60 minutes to form a cured film having a diameter of 30 mm and a thickness of 300 μm on the quartz substrate. Produced. The transmittance | permeability of wavelength 400nm of the obtained cured film was measured using the said ultraviolet visible near infrared spectrophotometer. The results are shown in Table 1 below.
［硬化物の作製及び屈折率・アッベ数評価］
　実施例１乃至実施例９及び比較例１で調製した各光重合性組成物を、３００μｍ厚のシリコーンゴム製スペーサーとともに、ＮＯＶＥＣ（登録商標）１７２０（スリーエムジャパン（株）製）を塗布・乾燥することで離型処理したガラス基板２枚で挟み込んだ。この挟み込んだ光重合性組成物を、上記ＵＶ照射装置を用いて２０ｍＷ／ｃｍ2で４５０秒間ＵＶ露光した。露光後得られた硬化物を、離型処理したガラス基板から剥離した後、８５℃のホットプレートで６０分間加熱することで、直径５ｍｍ、厚さ３００μｍの硬化物を作製した。得られた硬化物の波長５８９ｎｍにおける屈折率ｎD、及びアッベ数νDを、上記多波長屈折計を用いて測定した。結果を下記表１に合わせて示す。 [Production of cured product and evaluation of refractive index and Abbe number]
Each photopolymerizable composition prepared in Examples 1 to 9 and Comparative Example 1 is coated with NOVEC (registered trademark) 1720 (manufactured by 3M Japan) together with a 300 μm thick silicone rubber spacer and dried. Thus, it was sandwiched between two release-treated glass substrates. The sandwiched photopolymerizable composition was subjected to UV exposure at 20 mW / cm 2 for 450 seconds using the UV irradiation apparatus. The cured product obtained after the exposure was peeled off from the release-treated glass substrate, and then heated on an 85 ° C. hot plate for 60 minutes to produce a cured product having a diameter of 5 mm and a thickness of 300 μm. The refractive index n D and Abbe number ν D at a wavelength of 589 nm of the obtained cured product were measured using the multi-wavelength refractometer. The results are shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　比較例１で調製した光重合性組成物から得られた硬化物は、波長５８９ｎｍにおける屈折率ｎDが１．５３０に満たなかった。一方、実施例１乃至実施例９で調製した光重合性組成物から得られた硬化物は、いずれも、波長５８９ｎｍにおける屈折率ｎDが１．５３０以上、且つアッベ数νDが５６以上となった。さらに、実施例１乃至実施例９で調製した光重合性組成物から得られた硬化膜は、いずれも、波長４００ｎｍにおいて９０％以上の透過率を示した。 The cured product obtained from the photopolymerizable composition prepared in Comparative Example 1 had a refractive index n D of less than 1.530 at a wavelength of 589 nm. On the other hand, the cured products obtained from the photopolymerizable compositions prepared in Examples 1 to 9 all have a refractive index n D of 1.530 or more at a wavelength of 589 nm and an Abbe number ν D of 56 or more. became. Furthermore, the cured films obtained from the photopolymerizable compositions prepared in Examples 1 to 9 all showed a transmittance of 90% or more at a wavelength of 400 nm.

Claims (13)

  1. 下記（ａ）成分、及び該（ａ）成分１００質量部に対し０．０１質量部乃至１０質量部の下記（ｃ）成分を含むか、又は
    下記（ａ）成分、該（ａ）成分１００質量部に対し２００質量部を上限値とする下記（ｂ）成分、及び該（ａ）成分及び該（ｂ）成分の和１００質量部に対し０．０１質量部乃至１０質量部の下記（ｃ）成分を含む、光重合性組成物。
    （ａ）：下記式（１）で表される脂環式エポキシ化合物
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ1乃至Ｒ12は、それぞれ同一であっても異なっていてもよく、水素原子、炭化水素基、メトキシ基又はアセトキシ基を表す。）
    （ｂ）：前記式（１）で表される脂環式エポキシ化合物とは異なるエポキシ化合物、オキセタン化合物又はビニルエーテル化合物
    （ｃ）：光酸発生剤     The following (a) component and 0.01 to 10 parts by mass of the following (c) component are included with respect to 100 parts by mass of the (a) component, or the following (a) component and the (a) component 100 parts by mass. The following (b) component having an upper limit of 200 parts by mass with respect to parts, and 0.01 to 10 parts by mass of the following (c) with respect to 100 parts by mass of the sum of the component (a) and the component (b) A photopolymerizable composition comprising components.
    (A): An alicyclic epoxy compound represented by the following formula (1)
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, R 1 to R 12 may be the same or different and each represents a hydrogen atom, a hydrocarbon group, a methoxy group, or an acetoxy group.)
    (B): Epoxy compound, oxetane compound or vinyl ether compound different from the alicyclic epoxy compound represented by the formula (1) (c): photoacid generator
  2. 前記（ａ）成分は２５℃、１０１．３ｋＰａで液体である、請求項１に記載の光重合性組成物。 The photopolymerizable composition according to claim 1, wherein the component (a) is a liquid at 25 ° C. and 101.3 kPa.
  3. 前記（ａ）成分は下記式（１Ａ）で表される脂環式エポキシ化合物である、請求項１又は請求項２に記載の光重合性組成物。
    Figure JPOXMLDOC01-appb-C000002
         The photopolymerizable composition according to claim 1, wherein the component (a) is an alicyclic epoxy compound represented by the following formula (1A).
    Figure JPOXMLDOC01-appb-C000002
  4. 前記（ｂ）成分は芳香族環を含まない化合物である、請求項１に記載の光重合性組成物。 The photopolymerizable composition according to claim 1, wherein the component (b) is a compound not containing an aromatic ring.
  5. 一種又は二種以上の酸化防止剤を、前記（ａ）成分１００質量部に対し０．０１質量部乃至２０質量部、又は前記（ａ）成分及び前記（ｂ）成分の和１００質量部に対し０．０１質量部乃至２０質量部さらに含有する、請求項１乃至請求項４の何れか一項に記載の光重合性組成物。 One or more antioxidants may be added in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of the component (a), or 100 parts by mass of the sum of the component (a) and the component (b). The photopolymerizable composition according to any one of claims 1 to 4, further comprising 0.01 to 20 parts by mass.
  6. インプリント成形用組成物である、請求項１乃至請求項５の何れか一項に記載の光重合性組成物。 The photopolymerizable composition according to any one of claims 1 to 5, which is an imprint molding composition.
  7. 樹脂レンズ用組成物である、請求項１乃至請求項６の何れか一項に記載の光重合性組成物。 The photopolymerizable composition according to any one of claims 1 to 6, which is a resin lens composition.
  8. 前記光重合性組成物は、その硬化物の波長５８９ｎｍにおける屈折率ｎDが１．５３０以上１．５７０以下であり、かつ該硬化物のアッベ数νDが５６以上６５以下である、請求項１乃至請求項７のうち何れか一項に記載の光重合性組成物。 The photopolymerizable composition has a refractive index n D of 1.530 to 1.570 at a wavelength of 589 nm of the cured product, and an Abbe number ν D of the cured product of 56 to 65. The photopolymerizable composition according to any one of claims 1 to 7.
  9. 請求項８に記載の光重合性組成物の硬化物。 A cured product of the photopolymerizable composition according to claim 8.
  10. 請求項６又は請求項７に記載の光重合性組成物をインプリント成形する工程を含む、樹脂レンズの製造方法。 The manufacturing method of a resin lens including the process of imprint-molding the photopolymerizable composition of Claim 6 or Claim 7.
  11. 光重合性組成物の成形体の製造方法であって、
    請求項１乃至請求項８の何れか一項に記載の光重合性組成物を、接し合う支持体と鋳型との間の空間、又は分割可能な鋳型の内部の空間に充填する工程、及び該空間に充填された光重合性組成物を露光して光重合する工程、を含む成形体の製造方法。     A method for producing a molded article of a photopolymerizable composition comprising:
    Filling the photopolymerizable composition according to any one of claims 1 to 8 into a space between a contacting support and a mold, or a space inside a separable mold; and A method for producing a molded body, comprising a step of exposing and photopolymerizing a photopolymerizable composition filled in a space.
  12. 前記光重合する工程の後、得られた光重合物を取り出して離型する工程、並びに、該光重合物を、該離型する工程の前、中途又は後において加熱する工程、を含む請求項１１に記載の成形体の製造方法。 After the photopolymerization step, the step of taking out and releasing the obtained photopolymerization product, and the step of heating the photopolymerization product before, during or after the release step are included. The manufacturing method of the molded object of 11.
  13. 前記成形体がカメラモジュール用レンズである、請求項１１又は請求項１２に記載の成形体の製造方法。 The manufacturing method of the molded object of Claim 11 or Claim 12 whose said molded object is a lens for camera modules.
PCT/JP2017/040794 2016-11-24 2017-11-13 Photopolymerizable composition containing alicyclic epoxy compound for imprint molding WO2018096967A1 (en)

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