WO2013031550A1 - Photocurable resin composition, wafer level lens, and method of producing the lens - Google Patents

Photocurable resin composition, wafer level lens, and method of producing the lens Download PDF

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Publication number
WO2013031550A1
WO2013031550A1 PCT/JP2012/070866 JP2012070866W WO2013031550A1 WO 2013031550 A1 WO2013031550 A1 WO 2013031550A1 JP 2012070866 W JP2012070866 W JP 2012070866W WO 2013031550 A1 WO2013031550 A1 WO 2013031550A1
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WIPO (PCT)
Prior art keywords
resin composition
group
photocurable resin
compound
composition according
Prior art date
Application number
PCT/JP2012/070866
Other languages
French (fr)
Inventor
Kana Fujii
Kazuto Shimada
Tatsuhiko Obayashi
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Fujifilm Corporation
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Publication date
Priority claimed from JP2011185035A external-priority patent/JP2013043983A/en
Priority claimed from JP2011185034A external-priority patent/JP2013043982A/en
Application filed by Fujifilm Corporation filed Critical Fujifilm Corporation
Publication of WO2013031550A1 publication Critical patent/WO2013031550A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/0006—Arrays
    • G02B3/0012—Arrays characterised by the manufacturing method
    • G02B3/0031—Replication or moulding, e.g. hot embossing, UV-casting, injection moulding
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • G02B3/0006—Arrays
    • G02B3/0037—Arrays characterized by the distribution or form of lenses
    • G02B3/005—Arrays characterized by the distribution or form of lenses arranged along a single direction only, e.g. lenticular sheets

Definitions

  • the present invention relates to a photocurable resin composition and a lens and a wafer level lens which are produced by using the photocurable resin composition.
  • the present invention also relates to methods of producing a lens and a wafer level lens.
  • image pickup units have been mounted on mobile terminals of electronic devices such as mobile phones and personal digital assistants (PDAs) .
  • image pickup units comprise solid- state image sensing devices, such as charge coupled device (CCD) image sensors and complementary metal-oxide semiconductor (CMOS) image sensors, and lenses on the solid-state image sensing devices.
  • CCD charge coupled device
  • CMOS complementary metal-oxide semiconductor
  • the method of producing an image pickup unit include a process involving production of only lenses on a substrate such as a glass wafer, cutting of the substrate into lenses having a suitable size for being combined separate sensors, and integration of each lens with an image sensor into an image pick-up unit; a process involving formation of multiple resin lenses using a mold, integration of the lenses with a sensor substrate, and then cutting of the substrate; and a process involving cutting of a lens group into multiple lenses suitable for being combined with separate sensors, and integration of each lens with an image sensor prepared as an individual piece in advance into an image pick-up unit .
  • photocurable resin compositions are used as alternatives for glass lenses.
  • the lenses of a photocurable resin composition are formed by injecting the composition into, for example, a mold and curing it.
  • a photocurable resin composition comprising a prepolymer having polymerizable groups have also been investigated for a reduction in shrinkage of the composition during curing.
  • Such photocurable resin compositions are described in Japanese Patent Laid-open Nos . 2003-286316 and 2006-213851. Japanese Patent Laid-Open No.
  • 2003-286316 discloses a process of forming fine features with high accuracy by photopolymerization of a composition comprising an alicyclic hydrocarbon skeleton and a radically polymerizable compound to reduce volumetric shrinkage during curing.
  • the curable resin composition described in Japanese Patent Laid-Open No. 2003-286316 less shrinks during curing, has good mold releasability and high scratch resistance, and is stable for a long time even at 60°C.
  • the curable resin composition described in Japanese Patent Laid-Open No. 2006-213851 contains adamantyl acrylate.
  • compositions described in Japanese Patent Laid-Open Nos. 2003-286316 and 2006-213851 are not well suited for a process for producing lenses and thus not suitable for production of lenses, in particular, wafer level lenses.
  • One cause therefor is high viscosity of the compositions described in Japanese Patent Laid-Open Nos. 2003-286316 and 2006-213851.
  • lenses prepared using the resin composition in Japanese Patent Laid-Open No 2006-213851 have relatively low transparency.
  • the field of lenses requires a curable resin composition that exhibits a low volumetric change during curing and can form lenses with low haze.
  • the present inventors have studied in view of the above-described problems and have found that the problems can be solved by the following mean ⁇ 1>, preferably means ⁇ 2> to ⁇ 17>, shown below.
  • a photocurable resin composition comprising: a resin (A) having an alicyclic hydrocarbon group and having a weight average molecular weight of 40000 or less; a compound (B) having an alicyclic hydrocarbon group and a polymerizable group; and a compound (C) generating a radical or an acid by irradiation of active light or radiation, or a photocurable resin composition comprising: a resin (A) having an alicyclic hydrocarbon group; a compound (B) having an alicyclic hydrocarbon group and a polymerizable group; a compound (C) generating a radical or an acid by irradiation of active light or radiation; and a surfactant (D) .
  • the photocurable resin composition according to ⁇ 1> comprising: the resin (A) having an alicyclic hydrocarbon group and having a weight average molecular weight of 40000 or less; the compound (B) having an alicyclic hydrocarbon group and a polymerizable group; and the compound (C) generating a radical or an acid by irradiation of active light or radiation.
  • the photocurable resin composition according to ⁇ 1> comprising: the resin (A) having an alicyclic hydrocarbon group; the compound (B) having an alicyclic hydrocarbon group and a polymerizable group; the compound (C) generating a radical or an acid by irradiation of active light or radiation; andthe surfactant (D) .
  • ⁇ 6> The photocurable resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the polymerizable group of the compound (B) is a (meth) acryloyl group and/or an epoxy group .
  • ⁇ 8> The photocurable resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the resin (A) comprises a repeating unit having an alicyclic hydrocarbon group and a repeating unit having a polymerizable group.
  • the photocurable resin composition according to any one of ⁇ 1> to ⁇ 9>, wherein the resin (A) has at least one polymerizable group selected from acryloyl, methacryloyl, vinyl, ally, isocyanate, and epoxy groups.
  • R 1 represents a hydrogen atom or a substituent
  • L 1 represents a divalent linking group or a single bond
  • a represents a monocyclic or polycyclic ring.
  • R 3 to R 6 each independently represent a hydrogen atom or a substituent; and L 3 represents a divalent linking group or a single bond.
  • a method of producing a lens comprising: curing a photocurable resin composition according to any one of ⁇ 1> to ⁇ 13>.
  • a method of producing a wafer level lens comprising: curing a photocurable resin composition according to any one of ⁇ 1> to ⁇ 13>.
  • the present invention can provide a photocurable resin composition that has satisfactory optical characteristics, can be easily adjusted to a process, and can provide a molded product having less haze and a low volumetric shrinkage rate.
  • the invention can also provide a curable resin composition that has satisfactory optical characteristics, can be easily adjusted to a process, requires less force for releasing from a mold, and can provide a molded product having satisfactory adhesion to glass.
  • FIG. 1 is a plan view illustrating an example configuration of a wafer level lens array
  • FIG. 2 is a cross-sectional view of the wafer level lens array shown in FIG. 1 taken along the line A-A;
  • FIG. 3 illustrates supplying of a molding material for forming lenses on a substrate
  • FIGs. 4A to 4C illustrate steps of forming lenses on a substrate
  • FIG. 5 illustrates another example configuration of a wafer level lens array
  • the reference number 10 denotes a substrate
  • the reference number 12 denotes a lens (wafer level lens)
  • the reference number 14 denotes a patterned light-shielding film.
  • the photocurable resin composition according to a first embodiment of the present invention comprises a resin (A) having an alicyclic hydrocarbon group and having a weight average molecular weight of 40000 or less, a compound (B) having an alicyclic hydrocarbon group and a polymerizable group, and a compound (C) generating a radical or an acid by irradiation of active light or radiation.
  • the resin (A) used in the present invention comprises an alicyclic hydrocarbon group and has a weight average molecular weight of 40000 or less.
  • the alicyclic hydrocarbon group has a main chain composed of carbon atoms and has an alicyclic structure in the main chain or a side chain.
  • the resin (A) further has a polymerizable group.
  • the resin (A) of the present invention preferably comprises repeating units each comprising a main chain composed of carbon atoms and an alicyclic structure in the main chain or a side chain and repeating units each comprising a polymerizable group (preferably, repeating units each comprising a polymerizable group in a side chain) ; more preferably comprises repeating units each comprising a main chain composed of carbon atoms and an alicyclic structure in the main chain or a side chain and repeating units each comprising a main chain composed of carbon atoms and a polymerizable group in a side chain.
  • the resin (A) preferably comprises at least one of the repeating unit represented by Formula (1) and the repeating unit represented by Formula (2) :
  • R 1 represents a hydrogen atom or a substituent ;
  • L 1 represents a divalent linking group or a single bond; and
  • a represents a monocyclic or polycyclic ring,
  • ⁇ represents a monocyclic or polycyclic ring.
  • R 1 preferably represents a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group.
  • L 1 preferably represents a divalent linking group selected from -CO-, -0-, -CH 2 -, and combinations thereof or a single bond, more preferably a divalent linking group selected from -CO-, -0-, -CH 2 -, and combinations thereof.
  • a is preferably a cyclic skeletal structure composed of 6 to 20 carbon atoms, more preferably a cyclic skeletal structure selected from the following Group (1) :
  • the cyclic structures may have substituents or may not.
  • the substituents are preferably alkyl groups, more preferably alkyl groups having 1 to 3 carbon atoms, further more preferably methyl groups.
  • ⁇ is a cyclic skeletal structure composed of 6 to 20 carbon atoms, preferably a cyclic skeletal structure selected from the following Group (2):
  • the cyclic structures may have substituents or may not.
  • substituents examples include alkyl, allyl, oxo, hydroxy, and cyano groups and halogen atoms, and these substituents may be further substituted by these substituents.
  • the substituent is preferably composed of one or more of carbon, hydrogen, oxygen, and nitrogen atoms.
  • the total number of carbon, oxygen, and nitrogen atoms constituting the substituent is preferably 1 to 10, more preferably 1 to 5.
  • the repeating unit represented by Formula (1) is preferred to the repeating unit represented by Formula (2).
  • Examples of the polymerizable group of the resin (A) in the present invention include acryloyl, methacryloyl (throughout the specification, acryloyl and methacryloyl groups may be collectively referred to as " (meth) acryloyl group"), vinyl, allyl, isocyanate, and epoxy groups.
  • the polymerizable group is more preferably a (meth) acryloyl, epoxy, or vinyl group; more preferably a (meth) acryloyl or vinyl group; and further more preferably a vinyl group.
  • the resin (A) of the present invention preferably comprises repeating units represented by Formula (3) :
  • R 3 to R 6 each independently represent a hydrogen atom or a substituent; and L 3 represents a divalent linking group or a single bond.
  • R 3 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further more preferably a hydrogen atom or a methyl group.
  • R 4 and R 5 are each preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and further more preferably a hydrogen atom.
  • R 6 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further more preferably a hydrogen atom or a methyl group.
  • the resin (A) can be generally synthesized by a known method using a photocurable resin composition comprising a polymerizable compound, for example, through radical polymerization, ionic polymerization, or ring-opening polymerization.
  • the repeating units represented by Formulae (1) to (3) may be used alone or in combination.
  • polymerizable compound that can form the repeating unit represented by Formula (1) through polymerization are shown as Group A1 below; specific examples of the polymerizable compound that can form the repeating unit represented by Formula (2) through polymerization are shown as Group A2 below; and specific examples of the polymerizable compound that can form the repeating unit represented by Formula (3) through polymerization are shown as Group A3 below, but the compounds that can be used in the present invention are not limited to these examples.
  • the resin (A) used in the present invention may be produced by copolymerization of a monomer that can form a repeating unit represented by Formula (1), (2), or (3) with another monomer, for example, a monomer described in Polymer Handbook, 2nd ed. , J. Brandrup, Wiley Interscience (1975), Chapter 2, pp. 1-483.
  • the monomer include compounds having one addition-polymerizable unsaturated bond, such as styrene derivatives, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylcarbazole, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides , dialkyl itaconates, and dialkyl or monoalkyl esters of fumaric acid.
  • styrene derivatives examples include styrene,
  • acrylic esters examples include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert- butyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, benzyl methacrylate, methoxybenzyl acrylate, furfuryl acrylate, and tetrahydrofurfuryl acrylate.
  • methacrylic esters examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, tert-butyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, furfuryl methacrylate, and tetrahydrofurfuryl methacrylate.
  • acrylamides examples include acrylamide, N- alkyl acrylamide (the alkyl group is of 1 to 3 carbon atoms, such as a methyl, ethyl, or propyl group), N, N-dialkyl acrylamide (the alkyl group is of 1 to 6 carbon atoms) , N- hydroxyethyl-N-methyl acrylamide, and N-2-acetamideethyl-N- acetyl acrylamide. [0040]
  • methacrylamides examples include methacrylamide, N-alkyl methacrylamide (the alkyl group is of 1 to 3 carbon atoms, such as a methyl, ethyl, or propyl group), N,N- dialkyl methacrylamide (the alkyl group is of 1 to 6 carbon atoms), N-hydroxyethyl-N-methyl methacrylamide, and N-2- acetamideethyl-N-acetyl methacrylamide .
  • N-alkyl methacrylamide the alkyl group is of 1 to 3 carbon atoms, such as a methyl, ethyl, or propyl group
  • N,N- dialkyl methacrylamide the alkyl group is of 1 to 6 carbon atoms
  • N-hydroxyethyl-N-methyl methacrylamide N-2- acetamideethyl-N-acetyl methacrylamide .
  • dialkyl itaconates examples include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.
  • dialkyl or monoalkyl esters of fumaric acid examples include dibutyl fumarate.
  • monomer examples include crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, and maleylonitrile .
  • the resin (A) is preferably composed of 5 to 100% by mass of a repeating unit represented by Formula (1) and/or a repeating unit represented by Formula (2), 0 to 95% by mass of a repeating unit represented by Formula (3) , and 5% by mass or less of a repeating unit derived from any other polymerizable monomer.
  • the content of the repeating unit represented by Formula (1) and/or the repeating unit represented by Formula (2) is preferably 5 to 95% by mass, more preferably 30 to 90% by mass, and further more preferably 40 to 80% by mass.
  • the content of the repeating unit represented by Formula (3) is preferably 5 to 95% by mass, more preferably 10 to 70% by mass, and further more preferably 20 to 60% by mass.
  • the resin (A) preferably has a weight average molecular weight (Mw) of 40000 or less from the viewpoint of viscosity and more preferably 3000 to 25000 from the viewpoint of volumetric shrinkage.
  • the resin (A) preferably has a molecular weight distribution (Pd) of 1.0 to 6.0, more preferably 1.0 to 3.5.
  • the content of the resin (A) in the photocurable resin composition of the present invention is preferably in a range of 5 to 60% by mass, more preferably 7 to 50% by mass, and further more preferably 10 to 40% by mass.
  • the polymerizable compound (B) used in the present invention comprises an alicyclic hydrocarbon group and a polymerizable group.
  • the polymerizable compound (B) is outside the definition of the "resin (A) comprising an alicyclic hydrocarbon group and having a weight average molecular weight of 40000 or less” and is usually a compound having a molecular weight of 1000 or less and is preferably a monomer or an oligomer.
  • the polymerizable group is preferably acryloyl, methacryloyl , propenyl, vinyl, allyl, isocyanate, or epoxy group and more preferably at least one of a (meth) acryloyl group and an epoxy group from the viewpoint of curing properties.
  • One molecule may contain one polymerizable group or two or more polymerizable groups.
  • the polymerizable compound (B) preferably has an alicyclic structure of 6 to 16 carbon atoms, more preferably 6 to 10 carbon atoms.
  • the polymerizable group and the alicyclic structure are linked to each other directly or via a linking group, preferably directly or via a divalent linking group selected from -CO-, -O-, -CH 2 -, and combinations thereof.
  • the polymerizable compound (B) preferably has a molecular weight of 100 to 700, more preferably 130 to 600, and further more preferably 150 to 400.
  • polymerizable compound (B) Specific examples of the polymerizable compound (B) are shown below, but are not limited to these structures.
  • the photocurable resin composition preferably comprises both a polymerizable compound having a (meth) acrylate group and a polymerizable compound having an epoxy group.
  • the content of two or more of the polymerizable compound (B) in the photocurable resin composition of the present invention is preferably in a range of 20 to 90% by mass, more preferably 25 to 80% by mass, and further more preferably 30 to 70% by mass.
  • the ratio of the resin (A) to the polymerizable compound (B) is preferably 1:1.9 to 1:4 from the viewpoint of viscosity, more preferably 1:1.9 to 1:3.5 from the viewpoint of volumetric shrinkage rate.
  • the compound that generates a radical by irradiation of active light or radiation in the present invention, the compound that generates a radical by irradiation of active light or radiation
  • (photo) polymerization initiator can be selected from, for example, compounds known as radical polymerization initiators within a range that does not depart from the gist of the present invention
  • the polymerization initiator is preferably a photopolymerization initiator that is photosensitive to, for example, light from the ultraviolet to visible region or may be an activator that generates an active radical through any action with a photoexcited sensitizer, or an initiator that initiates cationic polymerization depending on the type of a monomer.
  • the photopolymerization initiator preferably comprises at least one component having a molar extinction coefficient of about 50 or more in the range of about 300 to 800 nm (more preferably 330 to 500 nm) .
  • photopolymerization initiator examples include halogenated hydrocarbon derivatives (e.g., those having a triazine skeleton or an oxadiazole skeleton) , acylphosphine compounds (e.g., acylphosphine oxide), hexaarylbiimidazole , oxime compounds (e.g., oxime derivatives), organic peroxides, thio compounds, ketone compounds, aromatic onium salts, keto oxime ethers, aminoacetophenone compounds, and hydroxyacetophenone .
  • halogenated hydrocarbon derivatives e.g., those having a triazine skeleton or an oxadiazole skeleton
  • acylphosphine compounds e.g., acylphosphine oxide
  • hexaarylbiimidazole examples include halogenated hydrocarbon derivatives (e.g., those having a triazine skeleton or an o
  • halogenated hydrocarbon compound having a triazine skeleton examples include compounds described in akabayashi, et al . , Bull. Chem. Soc. Japan, 42, 2924 (1969) ; compounds described in British Patent No. 1388492; compounds described in Japanese Patent Laid-Open No. Sho 53-133428; compounds described in German Patent No. 3337024; compounds described in F.C. Schaefer, et al., J. Org. Chem., 29, 1527 (1964); compounds described in Japanese Patent Laid-Open No. Sho 62-58241; compounds described in Japanese Patent Laid-Open No. Hei 5-281728; compounds described in Japanese Patent Laid-Open No. Hei 5- 34920; and compounds described in U.S. Patent No. 4212976.
  • Examples of the compounds described in U.S. Patent No. 4212976 include compounds having an oxadiazole skeleton (e.g., 2-trichloromethyl-5-phenyl-l , 3 , 4-oxadiazole, 2- trichloromethyl-5- (4-chlorophenyl) -1, 3, 4-oxadiazole, 2- trichloromethyl-5- (1-naphthyl) -1, 3, -oxadiazole, 2- trichloromethyl-5- (2-naphthyl) -1,3, 4-oxadiazole, 2- tribromomethyl-5-phenyl-l, 3, 4-oxadiazole, 2-tribromomethyl- 5- (2-naphthyl) -1, 3, -oxadiazole, 2-trichloromethyl-5- styryl-1, 3, 4-oxadiazole, 2-trichloromethyl-5- (4- chlorstyryl) -1,3, 4-oxadiazole, 2-t
  • photopolymerization initiator examples include acridine derivatives (e.g., 9-phenylacrydine and l,7-bis(9, 9' -acridinyl) heptane) , N-phenylglycine, polyhalogen compounds (e.g., carbon tetrabromide , phenyl tribromomethyl sulfone, and phenyl trichloromethyl ketone) , coumarins (e.g., 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- ( 2-benzofuroyl ) -7- ( 1-pyrrolidinyl ) coumarin, 3-benzoyl-7- diethylaminocoumarin, 3- (2-methoxybenzoyl) -7- diethylaminocoumarin, 3- ( -dimethylaminobenzoyl ) -7- diethylaminocoumarin, 3, 3'
  • acylphosphine oxides e.g., bis(2,4,6- trimethylbenzoyl) -phenylphosphine oxide, bis (2,6- dimethoxybenzoyl ) -2,4, 4-trimethyl-pentylphenylphosphine oxide, and Lucirin TPO
  • metallocenes e.g., bis(n5-2,4- cyclopentadien-l-yl) -bis (2, 6-difluoro-3- (lH-pyrrol-l-yl) - phenyl
  • n5-cyclopentadienyl- 6-cumenyl- iron 1+) -hexafluorophosphate ( 1- )
  • ketone compound examples include benzophenone,
  • Hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds are also suitable for photopolymerization initiators. More specifically, for example, aminoacetophenone initiators described in Japanese Patent Laid-Open No. 10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can be used.
  • Examples of the commercially available hydroxyacetophenone initiator include IRGACURE-184 , DAROCUR-1173, IRGACURE-500 , IRGACURE-2959, and IRGACURE-127 (trade names, all are manufactured by BASF) .
  • Examples of the commercially available aminoacetophenone initiator include IRGACURE-907 , IRGACURE-369, and IRGACURE-379 (trade names, all are manufactured by BASF) .
  • As the aminoacetophenone initiator compounds having absorption wavelengths matched to long wavelengths, such as 365 nm or 405 nm, of light sources described in Japanese Patent Laid- Open No. 2009-191179 can also be used.
  • Examples of the commercially available acylphosphine initiator include IRGACURE-819 and DAROCUR-TPO (trade names, all are manufactured by BASF) .
  • More preferred examples of the photopolymerization initiator include oxime compounds.
  • Specific examples of the oxime compound include compounds described in Japanese Patent Laid-Open Nos. 2001-233842, 2000-80068, and 2006- 342166.
  • oxime ester compounds examples include compounds described in J.C.S. Perkin II, (1979), pp. 1653-
  • IRGACURE-OXE01 manufactured by BASF
  • IRGACURE-OXE02 manufactured by BASF
  • oxime ester compound compounds described in National Publication of International Patent Application No. 2009-519904, where oxime is linked to the N-position of carbazole; compounds described in U.S. Patent No. 7626957, where a hetero-substituent is introduced into the benzophenone moiety; compounds available from ADEKA as initiators, described in Japanese Patent Laid-Open No. 2010-15025 and U.S. Patent Publication No. 2009-292039, where a nitro group is introduced into the dye moiety; ketoxime compounds described in International Patent No. WO2009/131189; compounds described in U.S. Patent No.
  • the cyclic oxime compounds described in Japanese Patent Laid-Open Nos. 2007-231000 and 2007- 322744 can be suitably used.
  • the cyclic oxime compounds fused to a carbazole dye, described in Japanese Patent Laid-Open Nos. 2010-32985 and 2010-185072 have high light absorptivity, which is preferable from the viewpoint of an increase in sensitivity.
  • Patent Laid-Open No. 2009-242469 having an unsaturated bond at a specific site of the oxime compound, can achieve high sensitivity through regeneration of an active radical from a polymerization inactive radical and therefore can be suitably used.
  • oxime compounds having specific substituents described in Japanese Patent Laid-Open No. 2007-269779 and oxime compounds having thioaryl groups described in Japanese Patent Laid-Open No. 2009-191061.
  • the oxime photopolymerization initiator is preferably a compound represented by the following Formula (1), wherein the N-0 bond may be of oxime is an (E)-form, a (Z)-form, or a mixture of the (E)-form and the (Z) -form:
  • R and B each independently represent a monovalent substituent;
  • A represents a divalent organic group; and
  • Ar represents an aryl group.
  • the monovalent substituent represented by R is preferably a monovalent nonmetallic atom group.
  • Examples of the monovalent nonmetallic atom group include alkyl, aryl, acyl, alkoxycarbonyl , aryloxycarbonyl , heterocyclic, alkylthiocarbonyl , and arylthiocarbonyl groups. These groups may have one or more substituents .
  • the substituent may be further substituted by another substituent .
  • substituents examples include halogen atoms, aryloxy, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acyl, alkyl, and aryl groups.
  • the alkyl group that optionally has a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl , 2-ethylhexyl , phenacyl, 1- naphthoylmethyl , 2-naphthoylmethyl , 4- methylsulfanylphenacyl , 4-phenylsulfanylphenacyl, 4- dimethylaminophenacyl , 4-cyanophenacyl , 4-methylphenacyl , 2-methylphenacyl , 3-fluorophenacyl, 3- trifluoromethyl
  • the aryl group that optionally has a substituent is preferably an aryl group having 6 to 30 carbon atoms, and specific examples thereof include phenyl, biphenyl, 1- naphthyl, 2-naphthyl, 9-anthryl, 9-phenanthryl , 1-pyrenyl, 5-naphthacenyl , 1-indenyl, 2-azulenyl, 9-fluorenyl, terphenyl, quaterphenyl, o-, m-, and p-tolyl, xylyl, o-, m-, and p-cumenyl, mesityl, pentalenyl, binaphthalenyl , ternaphthalenyl , quaternaphthalenyl , heptalenyl, biphenylenyl , indacenyl, fluoranthenyl, acenaphthylenyl , aceanthryl
  • the acyl group that optionally has a substituent is preferably an acyl group having 2 to 20 carbon atoms, and specific examples thereof include acetyl, propanoyl, butanoyl, trifluoroacetyl, pentanoyl, benzoyl, 1-naphthoyl, 2-naphthoyl, 4-methylsulfanylbenzoyl, 4- phenylsulfanylbenzoyl , 4-dimethylaminobenzoyl , 4- diethylaminobenzoyl, 2-chlorobenzoyl , 2-methylbenzoyl , 2- methoxybenzoyl , 2-butoxybenzoyl , 3-chlorobenzoyl , 3- trifluoromethylbenzoyl , 3-cyanobenzoyl , 3-nitrobenzoyl , 4- fluorobenzoyl , 4-cyanobenzoyl , and 4-methoxybenzoyl groups.
  • the alkoxycarbonyl group that optionally has a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and specific examples thereof include methoxycarbonyl , ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, hexyloxycarbonyl , octyloxycarbonyl , decyloxycarbonyl, octadecyloxycarbonyl , and trifluoromethyloxycarbonyl groups .
  • the heterocyclic group that optionally has a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen, oxygen, sulfur, or phosphorus atom, and specific examples thereof include thienyl, benzo [b] thienyl, naphtho [2, 3-b] thienyl, thianthrenyl , furyl, pyranyl, isobenzofuranyl , chromenyl, xanthenyl, phenoxanthiinyl , 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, 3H-indolyl, indolyl, lH-indazolyl , purinyl, 4H-quinolizinyl , isoquinolyl, quinolyl,
  • the monovalent substituent represented by B is an aryl, heterocyclic, arylcarbonyl, or heterocyclic carbonyl group. These groups may have one or more substituents . Examples of the substituent include the substituents described above. These substituents may be further substituted by another substituent .
  • Y, X, and n respectively have the same definitions as Y, X, and n in Formula (2) described later, and preferred examples thereof are also the same.
  • Examples of the divalent organic group represnted by ⁇ include alkylene, cyclohexylene , and alkynylene groups having 1 to 12 carbon atoms. These groups may have one or more substituents. Examples of the substituent include the substituents described above. These substituents may be further substituted by another substituent.
  • A is preferably an unsubstituted alkylene group or an alkylene group substituted by alkyl (e.g., methyl, ethyl, tert-butyl, or dodecyl) , alkenyl (e.g., vinyl or ally), or aryl (e.g., phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthryl, phenanthryl, or styryl) group.
  • alkyl e.g., methyl, ethyl, tert-butyl, or dodecyl
  • alkenyl e.g., vinyl or ally
  • aryl e.g., phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthryl, phenanthryl, or styryl
  • the aryl group represented by Ar preferably has 6 to 30 carbon atoms and may have a substituent.
  • substituent are the same as those of the substituted aryl groups shown above as specific examples of the aryl group that optionally has a substituent.
  • the substituent is preferably a substituted or unsubstituted phenyl group, from the viewpoints of enhancing the sensitivity and suppressing coloration by heating or aging.
  • the oxime compound is preferably represented by Formula (2 ) :
  • R and X each independently represent a monovalent substituent
  • a and Y each independently represent a divalent organic group
  • Ar represents an aryl group
  • n is an integer of 0 to 5.
  • R, A, and Ar respectively have the same definitions as R, A, and Ar in Formula (1), and preferred examples thereof are also the same.
  • Examples of the monovalent substituent represented by X include alkyl, aryl, alkoxy, aryloxy, acyloxy, acyl, alkoxycarbonyl, amino, and heterocyclic groups and halogen atoms. These groups may have one or more substituents . Examples of the substituent include the substituents described above. These substituents may be further substituted by another substituent.
  • X is preferably an alkyl group, from the viewpoints of solvent solubility and enhancement of absorption efficiency in the long wavelength region.
  • n represents an integer of 0 to 5 and is preferably an integer of 0 to 2.
  • Examples of the divalent organic group represented by Y include structures shown below. In the groups shown below, indicates the bonding site with the carbon atom adjacent to Y in Formula (2) .
  • the oxime compound is preferably a compound represented by the following Formula (3) .
  • R and X each independently represent a monovalent substituent;
  • A represents a divalent organic group;
  • Ar represents an aryl group; and
  • n is an integer of 0 to 5.
  • R, X, A, Ar, and n respectively have the same definitions as R, X, A, Ar, and n in Formula (2), and preferred examples thereof are also the same.
  • the oxime compound has a maximum absorption wavelength in the wavelength region of 350 to 500 nm, preferably has an absorption wavelength in the wavelength region of 360 to 480 nm, and further more preferably shows high absorbance at 365 nm and 455 nm.
  • the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1000 to 300000, more preferably 2000 to 300000, and further more preferably 5000 to 200000.
  • the molar extinction coefficient of a compound can be measured by a known method. Specifically, for example, the molar extinction coefficient is preferably measured at a concentration of 0.01 g/L in an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Carry-5 spctrophotometer, manufactured by Varian Inc.).
  • a combination of two or more of the photopolymerization initiators is optionally used.
  • the content of the photopolymerization initiator (total content in the case of combined use of two or more photopolymerization initiators) in the photocurable resin composition is preferably in the range of 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and further more preferably 0.5 to 8% by mass, based on the total amount (total mass) of the composition, from the viewpoint of volumetric shrinkage rate.
  • a content in this range can provide high sensitivity and pattern formability.
  • the photocurable resin composition may comprise a sensitizer for the purpose of enhancing the radical- generating efficiency of the photopolymerization initiator and shifting the photosensitive wavelength to the longer wavelength side.
  • the sensitizer used in the present invention sensitizes the photopolymerization initiator in the Compound (C) preferably by an electron transfer mechanism or an energy transfer mechanism.
  • Examples of the sensitizer comprised in the photocurable resin composition include compounds described in paragraphs [0101] to [0154] of Japanese Patent Laid-Open No. 2008-32803.
  • the content of the sensitizer in the photocurable resin composition is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, in terms of the solid content, from the viewpoints of light absorption efficiency at the depth and intiation decomposition efficiency.
  • the sensitizers may be used alone or in combination.
  • the compound that generates an acid by irradiation of active light or radiation may be any known acid generator, and preferred examples thereof include the compounds represented by the following Formulae (ZI), (ZII), and (ZIII) .
  • R201 / ⁇ 3 ⁇ 402 and R203 each independently represent an organic group.
  • the organic groups as R201 / R202, and R203 have 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
  • Two of R 2 oi to R203 may bond to each other to form a ring structure where the ring contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl bond.
  • the group formed by bonding of two of R 2 oi to R203 is, for example, an alkylene group (e.g., butylene or pentylene) .
  • Z ⁇ represents a non-nucleophilic anion (having significantly low ability of causing a nucleophilic reaction).
  • Z " include sulfonate anions (e.g., aliphatic sulfonate anions, aromatic sulfonate anions, and camphorsulfonate anions), carboxylate anions (e.g., aliphatic carboxylate anions, aromatic carboxylate anions, and aralkylcarboxylate anions) , sulfonylimide anions, bis (alkylsulfonyl ) imide anions, and tris (alkylsulfonyl ) raethide anions.
  • sulfonate anions e.g., aliphatic sulfonate anions, aromatic sulfonate anions, and camphorsulfonate anions
  • carboxylate anions e.g., aliphatic carboxylate anions, aromatic
  • the aliphatic moieties of the aliphatic sulfonate anions and the aliphatic carboxylate anions may be alkyl groups or cycloalkyl groups, and preferred examples thereof include linear or branched alkyl groups having 1 to 30 carbon atoms and cycloalkyl groups having 3 to 30 carbon atoms .
  • Preferred examples of the aromatic moieties of the aromatic sulfonate anions and the aromatic carboxylate anions include aryl groups having 6 to 14 carbon atoms, e.g., phenyl, tolyl, and naphthyl groups.
  • the alkyl, cycloalkyl, and aryl groups may have substituents .
  • substituents include halogens such as fluorine, nitro, carboxyl, hydroxyl, amino, cyano, alkoxy (preferably having 1 to 15 carbon atoms) , cycloalkyl (preferably having 3 to 15 carbon atoms) , aryl (preferably having 6 to 14 carbon atoms), alkoxycarbonyl (preferably having 2 to 7 carbon atoms) , acyl (preferably having 2 to 12 carbon atoms) , alkoxycarbonyloxy (preferably having 2 to 7 carbon atoms) , alkylthio (preferably having 1 to 15 carbon atoms), alkylsulfonyl (preferably having 1 to 15 carbon atoms) , alkyliminosulfonyl (preferably having 2 to 15 carbon atoms) , aryloxysulfonyl (preferably having 6 to 20 carbon atoms) , alkylaryloxysulfon
  • each group may further have alkyl (preferably having 1 to 15 carbon atoms) groups as substituents.
  • the aralkyl group of the aralkylcarboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, and examples thereof include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthylbutyl groups.
  • Examples of the sulfonylimide anion include saccharin anions .
  • the alkyl groups of the bis (alkylsulfonyl ) imide anion and the tris (alkylsulfonyl ) methide anion are preferably alkyl groups having 1 to 5 carbon atoms.
  • substituent of these alkyl groups include halogen atoms, halogenated alkyl, alkoxy, alkylthio, alkyloxysulfonyl , aryloxysulfonyl, and cycloalkylaryloxysulfonyl groups, and preferred substituents are a fluorine atom and fluorinated alkyl groups.
  • Z- examples include phosphorus fluoride, boron fluoride, and antimony fluoride.
  • Z- is preferably an aliphatic sulfonate anion having a substituent of a fluorine atom at least on the a-position of sulfonic acid, an aromatic sulfonate anion having a substituent of a fluorine atom or a fluorine containing group at least on the ⁇ -position, a bis (alkylsulfonyl) imide anion of which the alkyl group has a substituent of a fluorine atom, or a tris (alkylsulfonyl) methide anion of which the alkyl group has a substituent of a fluorine atom.
  • the non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably having 4 to 8 carbon atoms) or a benzenesulfonate anion having a fluorine atom, and more preferably a nonafluorobutanesulfonate anion, a perfluorooctanesulfonate anion, a pentafluorobenzenesulfonate anion, or a 3,5- bis (trifluoromethyl) benzenesulfonate anion.
  • the generated acid preferably has an acid strength pKa of -1 or less for the purpose of improving the sensitivity.
  • Examples of the organic groups represented by R201 / 202 / and R203 include aryl groups (preferably having 6 to 15 carbon atoms) , linear or branched alkyl groups (preferably having 1 to 10 carbon atoms) , and cycloalkyl groups (preferably having 3 to 15 carbon atoms) .
  • At least one of R2o: R202, and R203 is preferably an aryl group, and more preferably all of them are aryl groups.
  • the aryl group may be not only a group such as phenyl or naphthyl, but also a heteroaryl group such as indole or pyrrole. These aryl groups may further have substituents .
  • substituents include, but not limited to, halogens such as fluorine, nitro, carboxyl, hydroxyl, amino, cyano, alkoxy (preferably having 1 to 15 carbon atoms), cycloalkyl (preferably having 3 to 15 carbon atoms) , aryl (preferably having 6 to 14 carbon atoms) , alkoxycarbonyl (preferably having 2 to 7 carbon atoms) , acyl (preferably having 2 to 12 carbon atoms) , and alkoxycarbonyloxy (preferably having 2 to 7 carbon atoms) .
  • halogens such as fluorine, nitro, carboxyl, hydroxyl, amino, cyano, alkoxy (preferably having 1 to 15 carbon atoms), cycloalkyl (preferably having 3 to 15 carbon atoms) , aryl (preferably having 6 to 14 carbon atoms) , alkoxycarbonyl (preferably having 2 to 7 carbon atoms) , acyl (preferably having 2 to 12 carbon atoms)
  • R201 R202r and R203 m y bond to each other via a single bond or a linking group.
  • the linking group include, but not limited to, alkylene groups (preferably having 1 to 3 carbon atoms) , -0-, -S-, -CO-, and -SO2-.
  • Preferred examples of the structure where at least one of R201, R202, and R203 is not an aryl group include cationic structures of compounds described in paragraphs [0047] and [0048] of Japanese Patent Laid-Open No. 2004-233661, compounds described in paragraphs [0040] to [0046] of Japanese Patent Laid-Open No. 2003-35948, compounds represented by Formulae (1-1) to (1-70) in U.S. Patent Publication No. 2003/0224288, and compounds represented by Formulae (IA-1) to (IA-54) and (IB-1) to (IB-24) in U.S. Patent Publication No. 2003/0077540.
  • R201, R202 / and R 2 o3 has a structure represented by Ar-CO-X- and the other group or groups are linear or branched alkyl or cycloalkyl:
  • the linear or branched alkyl and/or cycloalkyl of the other groups may bond to each other to form a ring structure.
  • Ar represents an aryl group optionally having a substituent, and specific examples thereof include the same aryl groups as R2oi ? R202 / or R 2 o3- Ar is preferably a phenyl group optionally having a substituent.
  • X represents an alkylene group optionally having a substituent, specifically, an alkylene group having 1 to 6 carbon atoms, preferably a linear or branched alkylene group having 1 to 3 carbon atoms.
  • the linear or branched alkyl or cycloalkyl group being the other group (s) preferably has 1 to 6 carbon atoms. These groups may further have substituents . When the number of the other groups is two, these groups preferably bond to each other to form a ring structure (preferably 5 to 7- membered ring) .
  • R201 / R202, and R203 are aryl groups optionally having substituents and the other group or groups are linear or branched alkyl or cycloalkyl:
  • the aryl group are the same aryl groups as R2oii R202/ or R203 and the aryl group is preferably a phenyl or naphthyl group.
  • the aryl group preferably has any of hydroxyl, alkoxy, and alkyl groups as a substituent.
  • the substituent is more preferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms.
  • the linear or branched alkyl or cycloalkyl group as R201 / 3 ⁇ 402, or R203 preferably has 1 to 6 carbon atoms. These groups may further have substituents . When two groups are other than the aryl group, these two groups may bond to each other to form a ring structure.
  • R 2 04 to R 2 07 each independently represent an aryl, alkyl, or cycloalkyl group.
  • the aryl, alkyl, and cycloalkyl groups of R 2 o 4 to R 2 o 7 are the same as those of R 2 oi to R 20 3 in Formula (ZI) .
  • the aryl, alkyl, and cycloalkyl groups of R 204 to R 207 may have substituents .
  • substituents are the same as those of the aryl, alkyl, and cycloalkyl groups of R 20 i to R 20 3 in Formula (ZI) .
  • Z ⁇ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anions as Z ⁇ in Formula (ZI) .
  • Examples of the acid generator further include the compounds represented by the following Formulae (ZIV) , (ZV), and (ZVI) :
  • Ar 3 and Ar 4 each independently represent an aryl group;
  • R 2 os, R209, and R210 each independently represent an alkyl, cycloalkyl, or aryl group;
  • A represents an alkylene, alkenylene, or arylene group .
  • the acid generators may be used alone or in combination .
  • the content of the acid generator in the composition is preferably 0.1 to 20% by mass, more preferably 0.1 to 15% by mass, and further more preferably 0.1 to 10% by mass based on the total solid content of the composition.
  • composition of the present invention may comprise one or more polymerization inhibitors.
  • the polymerization inhibitor include phenolic hydroxyl group- containing compounds, quinones, N-oxide compounds, piperidin-l-oxyl free radical compounds, pyrrolidin-l-oxyl free radical compounds, N-nitrosophenylhydroxylamines , anilines, pyridines, aliphatic tertiary amines, and cationic dyes.
  • polymerization inhibitor examples include hydroquinone, p-methoxyphenol , di-t-butyl-p-cresol , pyrogallol, resorcinol, catechol, t-butylcatechol , hydroquinone monoalkyl ethers (e.g., hydroquinone monomethyl ether and hydroquinone monobutyl ether) , benzoquinone, 4, -thiobis ( 3-methyl-6-t-butylphenol ) , 2,2'- methylenebis (4-methyl-6-t-butylphenol) , 2,2,6,6- tetramethylpiperidine and its derivatives, di-t- butylnitroxide, 2, 2, 6, 6-tetramethylpiperidin-N-oxide and its derivatives, piperidine 1-oxyl free radical, 2,2,6,6- tetramethylpiperidine 1-oxyl free radical, 4-oxo-2, 2, 6, 6- tetramethylpiperidine 1-oxyl free radical, 4-hydroxy
  • the content of the polymerization inhibitor in the composition is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and further more preferably 1 to 10% by mass, based on the total amount (total mass) of the composition from the viewpoint of volumetric shrinkage rate .
  • the curable resin composition of the present invention may further contain additives such as a surfactant and a dissolution modulator.
  • the curable resin composition of the present invention preferably contains 15% by mass or less of components other the components (A) to (D) .
  • the photocurable resin composition of the present invention may contain various surfactants from the viewpoint of further improving the coating properties.
  • the surfactant include fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.
  • the photocurable resin composition of the present invention containing a fluorine surfactant can provide a coating solution having improved liquid characteristics (in particularly, fluidity) to further improve the uniformity in application thickness and reduce the necessary volume of the solvent.
  • the interfacial tension between the coating solution and a coated surface is reduced to enhance wettability of the coated surface, resulting in an improvement in coating properties for the coated surface. Consequently, even in formation of a thin film of several micrometers thickness by a small amount of the solution, the solution can effectively form the film with low irregularity in thickness, i.e., with a uniform thickness .
  • the content of fluorine in the fluorine surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and further more preferably 7 to 25% by mass.
  • the fluorine surfactant containing fluorine in this range is effective for improving uniformity in film thickness and reducing the necessary volume of the solvent and also has satisfactory solubility in the photocurable resin composition .
  • fluorine surfactant examples include MEGAFAC
  • F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, and F781 (all manufactured by DIC Corp.), Fluorad FC430, FC431, and FC171 (all manufactured by Sumitomo 3M Ltd.), and Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (all manufactured by Asahi Glass Co., Ltd. ) .
  • nonionic surfactant examples include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate) , polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester (e.g., Pluronic L10, L31, L61, L62, 10R5, 17R2, and 25R2 and Tetronic 304, 701, 704, 901, 904, and 150R1 manufactured by BASF; and Solsperse 20000 manufactured by
  • cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita & Co., Ltd.), organosiloxane polymers (trade name: KP341, manufactured by Shin-Etsu Chemical Co., Ltd.), and (meth) acrylic acid (co) polymers (trade name: Polyflow No. 75, No. 90, and No. 95, manufactured by Kyoeisha Chemical Co., Ltd., and trade name: 001, manufactured by Yusho Co., Ltd.).
  • phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita & Co., Ltd.
  • organosiloxane polymers trade name: KP341, manufactured by Shin-Etsu Chemical Co., Ltd.
  • acrylic acid (co) polymers trade name: Polyflow No. 75, No. 90, and No. 95, manufactured by Kyoeisha Chemical Co., Ltd., and trade name: 001, manufactured by Yusho Co., Ltd.
  • anionic surfactant examples include W004, W005, and W017 (manufactured by Yusho Co., Ltd.).
  • silicone surfactant examples include “ToraySilicone DC3PA” , “ToraySilicone SH7PA”, “ToraySilicone DC11PA”, “ToraySilicone SH21PA”, “ToraySilicone SH28PA”,
  • ToraySilicone SH29PA ToraySilicone SH30PA
  • ToraySilicone SH8400 manufactured by Dow Corning Toray Co., Ltd.
  • TEZ-4440 TEZF-4300
  • TEZF-4445 TEZF-4460
  • TEZF-4452 Momentive Performance Materials Inc.
  • KP341 KF6001
  • KF6002 manufactured by Shin-Etsu Chemical Co., Ltd.
  • BYK307 "BYK323"
  • BYK330 manufactured by BYK-Chemie GmbH.
  • the surfactants may be used alone or in combination.
  • the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total mass of the photocurable resin composition.
  • the composition of the present invention may contain a solvent.
  • the content of the solvent is preferably 10% by mass or less, and more preferably 5% by mass or less from the viewpoint of reducing air bubbles in a molded product.
  • the photocurable resin composition of the present invention do not substantially contain a solvent.
  • “Not substantially contain” means that, for example, the content of a solvent is 1% by mass or less of the photocurable resin composition.
  • the curable resin composition of the present invention can have a viscosity of 0.1 to 25 Pa-s, further 0.3 to 15 Pa-s, and further 0.3 to 7 Pa-s.
  • high optical characteristics and a low volumetric shrinkage rate can be maintained even at such a low viscosity.
  • the volumetric shrinkage rate during curing is preferably 10% or less, more preferably 5% or less, and further more preferably 3% or less.
  • curable resin compositions it is technically difficult to achieve compatibility between a high refractive index and a high Abbe number. Specifically, it is difficult to achieve both a refractive index of 1.5 or more and an Abbe number of 50 or more.
  • compositions for forming lenses contain inorganic particles in order to increase the refractive index and the Abbe number
  • the present invention can achieve a high refractive index and a high Abbe number even if the composition does not substantially contain such inorganic particles (e.g., the content of the inorganic particles is 1% by mass or less of the composition) .
  • the haze after curing is preferably 5% or less, more preferably 3% or less.
  • the glass transition temperature after curing is preferably 200°C or more, and more preferably 260°C or more.
  • the photocurable resin composition according to a second embodiment of the present invention comprises a resin (A) having an alicyclic hydrocarbon group, a compound
  • the resin (A) used in the present invention comprises an alicyclic hydrocarbon group.
  • the alicyclic hydrocarbon group has a main chain composed of carbon atoms and has an alicyclic structure in the main chain or a side chain.
  • the resin (A) further has a polymerizable group.
  • the resin (A) of the present invention preferably comprises repeating units each comprising a main chain composed of carbon atoms and an alicyclic structure in the main chain or a side chain and repeating units each comprising a polymerizable group (preferably, repeating units each comprising a polymerizable group in a side chain) ; more preferably, comprises repeating units each comprising a main chain composed of carbon atoms and an alicyclic structure in the main chain or a side chain and repeating units each comprising a main chain composed of carbon atoms and a polymerizable group in a side chain.
  • the resin (A) preferably comprises at least one of the repeating unit represented by Formula (1) and the repeating unit represented by Formula (2) :
  • R 1 represents a hydrogen atom or a substituent
  • L 1 represents a divalent linking group or a single bond
  • ⁇ represents a monocyclic or polycyclic ring.
  • R 1 preferably represents a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further more preferably a hydrogen atom or a methyl group.
  • L 1 preferably represents a divalent linking group selected from -CO-, -0-, -CH 2 -, and combinations thereof or a single bond, more preferably a divalent linking group selected from -CO-, -0-, -C3 ⁇ 4-, and combinations thereof.
  • a is preferably a cyclic skeletal structure composed of 6 to 20 carbon atoms, more preferably a cyclic skeletal structure selected from the following Group (1) :
  • the cyclic structures may have substituents or may not.
  • the substituents are preferably alkyl groups, more preferably alkyl groups having 1 to 3 carbon atoms, further more preferably methyl groups.
  • ⁇ is a cyclic skeletal structure composed of 6 to 20 carbon atoms, preferably a cyclic skeletal structure selected from the following Group (2):
  • the cyclic structures may have substituents or may not.
  • substituents include alkyl, allyl, oxo, hydroxy, and cyano groups and halogen atoms, and these substituents may be further substituted by these substituents.
  • the substituent is preferably composed of one or more of carbon, hydrogen, oxygen, and nitrogen atoms.
  • the total number of carbon, oxygen, and nitrogen atoms constituting the substituent is preferably 1 to 10, more preferably 1 to 5.
  • the repeating unit represented by Formula (1) is preferred to the repeating unit represented by Formula (2) .
  • Examples of the polymerizable group of the resin (A) in the present invention include acryloyl, methacryloyl (throughout the specification, acryloyl and methacryloyl groups may be collectively referred to as " (meth) acryloyl group"), vinyl, allyl, isocyanate, and epoxy groups.
  • the polymerizable group is more preferably a (meth) acryloyl , epoxy, or vinyl group; more preferably a (meth) acryloyl or vinyl group; and further more preferably a vinyl group.
  • the resin (A) of the present invention preferably comprises repeating units represented by Formula (3) :
  • R 3 to R 6 each independently represent a hydrogen atom or a substituent; and L 3 represents a divalent linking group or a single bond.
  • R 3 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further more preferably a hydrogen atom or a methyl group.
  • R 4 and R 5 are each preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and further more preferably a hydrogen atom.
  • R 6 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further more preferably a hydrogen atom or a methyl group.
  • the resin (A) can be generally synthesized by a known process using a photocurable resin composition comprising a polymerizable compound, for example, through radical polymerization, ionic polymerization, or ring-opening polymerization.
  • the repeating units represented by Formulae (1) to (3) may be used alone or in combination.
  • Specific examples of the polymerizable compound that can form the repeating unit represented by Formula (1) through polymerization, specific examples of the polymerizable compound that can form the repeating unit represented by Formula (2) through polymerization, and specific examples of the polymerizable compound that can form the repeating unit represented by Formula (3) through polymerization are the same as those in the first embodiment .
  • the resin (A) used in the present invention may be produced by copolymerization of a monomer that can form a repeating unit represented by Formula (1), (2), or (3) with another monomer, for example, a monomer described in Polymer Handbook, 2nd ed., J. Brandrup, Wiley Interscience (1975), Chapter 2, pp. 1-483.
  • monomer examples include crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, and maleylonitrile .
  • the resin (A) is preferably composed of 5 to 100% by mass of a repeating unit represented by Formula (1) and/or a repeating unit represented by Formula (2), 0 to 95% by mass of a repeating unit represented by Formula (3), and 5% by mass or less of a repeating unit derived from any other polymerizable monomer.
  • the content of the repeating unit represented by Formula (1) and/or the repeating unit represented by Formula (2) is preferably 5 to 95% by mass, more preferably 30 to 90% by mass, and further more preferably 40 to 80% by mass.
  • the content of the repeating unit represented by Formula (3) is preferably 5 to 95% by mass, more preferably 10 to 70% by mass, and further more preferably 20 to 60% by mass.
  • the resin (A) preferably has a molecular weight of 40000 or less from the viewpoint of viscosity and more preferably 3000 to 25000 from the viewpoint of volumetric shrinkage .
  • the resin (A) preferably has a molecular weight distribution (Pd) of 1.0 to 6.0, more preferably 1.0 to 3.5.
  • the content of the resin (A) in the photocurable resin composition of the present invention is preferably in a range of 5 to 60% by mass, more preferably 7 to 50% by mass, and further more preferably 10 to 40% by mass.
  • the polymerizable compound (B) used in the present invention comprises an alicyclic hydrocarbon group and a polymerizable group.
  • the polymerizable compound (B) is outside the definition of the "resin (A) having an alicyclic hydrocarbon group and having a weight average molecular weight of 40000 or less” and is usually a compound having a molecular weight of 1000 or less and is preferably a monomer or an oligomer.
  • the polymerizable group is preferably acryloyl, methacryloyl, propenyl, vinyl, allyl, isocyanate, or epoxy group and more preferably at least one of a (meth) acryloyl group and an epoxy group from the viewpoint of curing properties.
  • One molecule may contain one polymerizable group or two or more polymerizable groups.
  • the polymerizable compound (B) preferably has an alicyclic structure of 6 to 16 carbon atoms, more preferably 6 to 10 carbon atoms.
  • the polymerizable group and the alicyclic structure are linked to each other directly or via a linking group, preferably directly or via a divalent linking group selected from -CO-, -0-, -CH 2 -, and combinations thereof.
  • the polymerizable compound (B) preferably has a molecular weight of 100 to 700, more preferably 130 to 600, and further more preferably 150 to 400.
  • polymerizable compound (B) Specific examples of the polymerizable compound (B) are shown below, but are not limited to these structures.
  • the photocurable resin composition preferably comprises both a polymerizable compound having a (meth) acrylate group and a polymerizable compound having an epoxy group.
  • the content of two or more of the polymerizable compound (B) in the photocurable resin composition of the present invention is preferably in a range of 20 to 90% by mass, more preferably 25 to 80% by mass, and further more preferably 30 to 70% by mass.
  • the ratio of the resin (A) to the polymerizable compound (B) is preferably 1:1.9 to 1:4 from the viewpoint of viscosity, more preferably 1:2.3 to 1:3.5 from the viewpoint of volumetric shrinkage rate.
  • the compound that generates a radical by irradiation of active light or radiation (hereinafter also referred to as " (photo) polymerization initiator”) can be selected from, for example, compounds known as radical polymerization initiators within a range that does not depart from the gist of the present invention .
  • the compound (C) that generates a radical or an acid by irradiation of active light or radiation in the second embodiment is the same compound (C) in the first embodiment, and the preferable range of the content thereof is also the same as that in the first embodiment.
  • the photocurable resin composition according to the second embodiment of the present invention comprises a surfactant.
  • useful surfactants include fluorine surfactants containing fluorine atoms, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants containing silicon atoms. Surfactants containing silicon atoms and/or fluorine atoms are preferred.
  • the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total mass of the photocurable resin composition.
  • the surfactants may be used alone or in combination.
  • the content of the surfactant containing fluorine atoms is preferably 4% by mass or less of the solid content in the photocurable resin composition from the viewpoint of adhesion to glass.
  • the lower limit is not particularly defined, but may be, for example, 0.1% by mass or more.
  • the content of the surfactant containing silicon atoms can be, for example, 0.5 to 10% by mass of the solid content of the photocurable resin composition.
  • a higher content of the surfactant is preferred from the viewpoint of reducing the force for releasing, but from the veiwpoint of disorder or deformation in shape, the content is preferably 0.5 to 5% by mass.
  • fluorine surfactant examples include MEGAFAC
  • F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, and F781 (all manufactured by DIC Corp.), Fluorad FC430, FC431, and FC171 (all manufactured by Sumitomo 3M Ltd.), and Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (all manufactured by Asahi Glass Co., Ltd. ) .
  • the content of fluorine in the fluorine surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and further more preferably 7 to 25% by mass.
  • the fluorine surfactant containing fluorine in this range is effective for improving uniformity in film thickness and reducing the necessary volume of the solvent and also has satisfactory solubility in the photocurable resin composition .
  • nonionic surfactant examples include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate) , polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester (e.g., Pluronic L10, L31, L61, L62, 10R5, 17R2, and 25R2 and Tetronic 304, 701, 704, 901, 904, and 150R1 manufactured by BASF; and Solsperse 20000 manufactured by The Lubrizol Corp.).
  • cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita & Co., Ltd.), organosiloxane polymers (trade name: KP341, manufactured by Shin-Etsu Chemical Co., Ltd.), and (meth) acrylic acid (co) polymers (trade name: Polyflow No. 75, No. 90, and No. 95, manufactured by Kyoeisha Chemical Co., Ltd., and trade name: W001, manufactured by Yusho Co., Ltd.).
  • phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita & Co., Ltd.
  • organosiloxane polymers trade name: KP341, manufactured by Shin-Etsu Chemical Co., Ltd.
  • acrylic acid (co) polymers trade name: Polyflow No. 75, No. 90, and No. 95, manufactured by Kyoeisha Chemical Co., Ltd., and trade name: W001, manufactured by Yusho Co., Ltd.
  • anionic surfactant examples include W004, W005, and W017 (manufactured by Yusho Co., Ltd.) .
  • silicone surfactant examples include “ToraySilicone
  • ToraySilicone SH29PA ToraySilicone SH30PA
  • ToraySilicone SH8400 manufactured by Dow Corning Toray Co., Ltd.
  • TEZ-4440 TEZF-4300
  • TEZF-4445 TEZF-4460
  • TEZF-4452 Momentive Performance Materials Inc.
  • KP341 KF6001
  • KF6002 manufactured by Shin-Etsu Chemical Co., Ltd.
  • BYK307 "BYK323"
  • BYK330 manufactured by BYK-Chemie GmbH.
  • the photocurable resin composition according to the second embodiment of the present invention may further contain additives such as a polymerization inhibitor and a dissolution modulator, as in the first embodiment.
  • the curable resin composition according to the second embodiment of the present invention preferably contains 15% by mass or less of components other the components (A) to (D) .
  • the composition of the present invention may contain a solvent.
  • the content of the solvent is preferably 10% by mass or less, and more preferably 5% by mass or less from the viewpoint of reducing air bubbles in a molded product.
  • the photocurable resin composition of the present invention do not substantially contain a solvent.
  • “Not substantially contain” means that, for example, the content of a solvent is 1% by mass or less of the photocurable resin composition.
  • the curable resin composition of the present invention can have a viscosity of 0.1 to 25 Pa-s, further 0.3 to 15 Pa-s, and further 0.3 to 7 Pa-s.
  • high optical characteristics and a low volumetric shrinkage rate can be maintained even at such a low viscosity.
  • the volumetric shrinkage rate during curing is preferably 10% or less, more preferably 5% or less, and further more preferably 3% or less.
  • curable resin compositions it is technically difficult to achieve compatibility between a high refractive index and a high Abbe number. Specifically, it is difficult to achieve both a refractive index of 1.5 or more and an Abbe number of 50 or more.
  • compositions for forming lenses contain inorganic particles in order to increase the refractive index and the Abbe number, but the present invention can achieve a high refractive index and a high Abbe number even if the composition does not substantially contain such inorganic particles (e.g., the content of the inorganic particles is 1% by mass or less of the composition) .
  • the haze after curing is preferably 5% or less, more preferably 3% or less.
  • the glass transition temperature after curing is preferably 200°C or more, and more preferably 260°C or more.
  • the cured product of the curable resin composition of the present invention can be preferably used as optical components of, for example, various display devices (e.g., liquid crystal displays and plasma displays), various projectors (e.g., OHPs and liquid crystal projectors), optical fiber communication systems
  • various display devices e.g., liquid crystal displays and plasma displays
  • various projectors e.g., OHPs and liquid crystal projectors
  • optical fiber communication systems e.g., optical fiber communication systems
  • the cured product of the present invention can be preferably used as optical components, in particular, lenses.
  • FIG. 1 is a plan view illustrating an example configuration of a wafer level lens array.
  • FIG. 2 is a cross-sectional view of the wafer level lens array shown in FIG. 1 taken along the line A-A.
  • the wafer level lens array comprises a substrate 10 and a plurality of lenses 12 arranged on the substrate 10.
  • the lenses 12 are one- dimensionally or two-dimensionally arranged on the substrate 10.
  • a light-shielding film 14 may be provided between adjacent lenses 12 for preventing transmission of light from regions other than the lenses.
  • a configuration shown in FIG. 1, i.e., a plurality of lenses 12 two-dime sionally arranged on a substrate 10 will be described as an example.
  • the lenses 12 and the substrate 10 are made of a cured product of the photocurable resin composition of the present invention, where the lenses 12 are integrally formed on the substrate 10 or are separately formed and immobilized to the substrate 10.
  • the photocurable resin composition according to the second embodiment of the present invention is preferably used in integral molding of the lenses 12 and the substrate 10.
  • the wafer level lens array of the present invention may have any size, for example, 6 to 12 inches.
  • the curable resin composition of the present invention can advantageously form a satisfactory wafer level lens array even if the size is 8 inches or more.
  • the composition can be more preferably applied to a wafer level lens array having a size of 8 to 12 inches.
  • conventional wafer level lens arrays tend to warp with an increase in size, but the photocurable resin composition of the present invention can form a satisfactory wafer level lens array even if the size is 8 inches or more.
  • the wafer level lens array of the present invention is not limited thereto and can be provided in various forms such as a multi-layer structure or lens modules separated by dicing.
  • Method of producing molded product is not limited thereto and can be provided in various forms such as a multi-layer structure or lens modules separated by dicing.
  • Molded products such as optical components can be produced using the photocurable resin composition of the present invention by a known method.
  • the photocurable resin composition of the present invention is injected into a mold and is irradiated with active energy and/or heated to be hardened into a molded product.
  • combination of irradiation with active energy and heating is preferred, which can suppress the shrinkage during curing in dies (preferably molding dies) to precisely transfer the mold shape and inhibit leakage to the gap (clearance) between the dies.
  • FIG. 3 illustrates supplying of a molding material, i.e., the photocurable resin composition (shown as M in FIG. 3) of the present invention, on a substrate.
  • the molding material M is dropped onto a substrate 10 with a dispenser 50 at positions to form lenses.
  • the molding material M is supplied in an amount corresponding to one lens 12 per position.
  • a mold 60 for forming lenses is disposed.
  • the mold 60 has concaves 62 for transferring shapes of lenses 12, the number of concaves corresponding to the required number of lenses 12.
  • the mold 60 is pressed to the molding material M on the substrate 10 to mold the molding material M into shapes along the concaves. Then, when the molding material M is a thermosetting resin or ultraviolet curable resin, the molding material M is cured by being irradiated with heat or ultraviolet rays from the outside of the mold while the mold 60 is being pressed to the molding material M.
  • the molding material M is a thermosetting resin or ultraviolet curable resin
  • FIG. 5 illustrates another example configuration of a wafer level lens array.
  • the wafer level lens array shown in FIG. 5 is a monolithic configuration where a substrate 10 and lenses 12 are formed through a one-shot process.
  • a plurality of concave lenses 12 are formed on one surface (the upper surface in the drawing) of the substrate 10, and a plurality of convex lenses 20 are formed on the other surface (the lower surface) .
  • a patterned light-shielding film 14 may be formed on the substrate 10 in the region excluding the lens surfaces 12a, i.e., the surfaces of the substrate 10 and the edges 12b.
  • B-3 3, 4-Epoxycyclohexenylmethyl 3 ' , 4 ' -epoxycyclohexene carboxylate (manufactured by Daicel Corp., Celloxide 2021)
  • B-4 tert-Butyl methacrylate
  • a solution was dropped onto a hydrophobized glass substrate to form a solution layer with a thickness of 1 mm.
  • the layer was exposed to light of 4000 mJ/cm 2 to heat at 180°C for 2 hr using a high-pressure mercury lamp HB-50101BY (Ushio Inc.) under a N 2 atmosphere. Subsequently, the glass substrate was removed to give a hardened film having a thickness of 1 mm.
  • the refractive index of the resulting film for light of 589 nm wavelength was measured with an Abbe refractometer (DR-M4, manufactured by Atago Co., Ltd.).
  • the refractive indices of the hardened film produced in "(1) Measurement of refractive index” were measured for light of 486 nm, 589 nm, and 656 nm wavelengths with an Abbe refractometer (DR-M4, manufactured by Atago Co., Ltd.).
  • the Abbe number was calculated from the following expression using the refractive index n F at a wavelength of 486 nm, the refractive index n D at a wavelength of 589 nm, and the refractive index n C at a wavelength of 656 nm. A higher Abbe number is preferred.
  • the shear viscosity of the prepared solution was measured with a rheometer (manufactured by Anton Paar, Physica MCR301) to calculate the viscosity.
  • a prepared solution was poured in an aluminum cup of 0.8 cm diameter and was exposed to light of 4000 mJ/cm 2 using a high-pressure mercury lamp HB-50101BY (Ushio Inc.) to obtain about 0.35 g of a molded product.
  • the volume VI of the resulting molded product was measured with a dry- type automatic densitometer (manufactured by Shimadzu Corp., AccuPyc 1330-03) .
  • the molded product was annealed at 180°C for 2 hr under a N 2 atmosphere.
  • the volume V2 of this molded product was measured with the dry- type automatic densitometer.
  • volumetric shrinkage was determined from the following expression :
  • volumetric shrinkage rate (%) [ (V1-V2 ) /VI ] xlOO
  • a smaller percentage means a lower volumetric shrinkage rate .
  • a solution was dropped onto a hydrophobized glass substrate to form a solution layer with a thickness of 1 mm.
  • the layer was exposed to light of 4000 mJ/cm 2 to heat at 180°C for 2 hr using a mercury lamp under a N 2 atmosphere. Subsequently, the glass substrate was removed to give a hardened film having a thickness of 1 mm.
  • the hardened film was evaluated by visual observation.
  • the evaluation criteria are as follows, where a smaller number means less haze: 1: The film is transparent and clear and does not have air bubbles;
  • composition of the present invention can achieve compatibility among a high refractive index, a high Abbe number, low viscosity, a low volumetric shrinkage rate, and low haze.
  • B-3' 3, 4-Epoxycyclohexenylmethyl 3 ' , 4 ' -epoxycyclohexene carboxylate (manufactured by Daicel Corp., Celloxide 2021)
  • B-4' tert-Butyl methacrylate
  • E-l' p-Methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd., M0122)
  • Refractive indices were measured as in Example 1A.
  • Viscosity was measured as in Example 1A.
  • a polydimethylsiloxane mold of 2 x 2 cm was set to an air-compression UV imprint apparatus (manufactured by MEPJ) equipped with a function, of measuring force for releasing, and about 1 ⁇ L of a prepared solution was applied onto the mold.
  • a glass wafer was placed on the solution such that the distance between the mold and the glass wafer was 200 jim. Subsequently, the glass wafer was exposed to light for 100 sec, and the mold was then removed. On this occasion, the force (N/cm 2 ) for releasing was calculated from the maximum force (N) applied to the mold and the testing area (cm 2 ) .
  • a prepared solution was applied onto a glass substrate of 7 x 7 cm with a spin coater at 1000 rpm. This substrate was exposed to light of 4000 mJ/cm 2 using a high-pressure mercury lamp HB-50101BY (Ushio Inc.). The resulting film was used in a Japanese Industrial Standard (JIS) cross-cut tape peeling test.
  • JIS Japanese Industrial Standard
  • composition of the present invention can achieve compatibility among a high refractive index, a high Abbe number, low viscosity, a low force for releasing, and high adhesion to glass.

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Abstract

Disclosed is a photocurable resin composition which achieves compatibility among a high refractive index, a high Abbe number, and high transparency. The photocurable resin composition comprises a resin (A) having an alicyclic hydrocarbon group and having a weight average molecular weight of 40000 or less; a compound (B) having an alicyclic hydrocarbon group and a polymerizable group; an a compound (C) generating a radical or an acid by irradiation of active light or radiation, or a photocurable reisn composition comprising: a resin (A) having an alicyclic hydrocarbon group; a compound (B) having an alicyclic hydrocarbon group and a polymerizable group; a compound (C) generating a radical or an acid by irradiation of active light or radiation; and a surfactant (D).

Description

DESCRIPTION
PHOTOCURABLE RESIN COMPOSITION, WAFER LEVEL LENS, AND METHOD OF PRODUCING THE LENS
BACKGROUND OF THE INVENTION
1. TECHNICAL FIELD
[0001]
The present invention relates to a photocurable resin composition and a lens and a wafer level lens which are produced by using the photocurable resin composition. The present invention also relates to methods of producing a lens and a wafer level lens.
2. BACKGROUND ART
[0002]
In recent years, small and thin image pickup units have been mounted on mobile terminals of electronic devices such as mobile phones and personal digital assistants (PDAs) . In general, such image pickup units comprise solid- state image sensing devices, such as charge coupled device (CCD) image sensors and complementary metal-oxide semiconductor (CMOS) image sensors, and lenses on the solid-state image sensing devices.
[0003]
The spread of smaller and thinner mobile terminals requires a further reduction in size of image pickup units to be mounted on such mobile terminals and also requires an increase in productive efficiency. As a measure for these requirements, a method of mass-producing an image pickup unit is known; this involves integration of a lens substrate provided with multiple lenses thereon with a sensor substrate provided with respective solid-state image sensing devices thereon and separation of the composite into individual assemblies each comprising a lens and a solid-state image sensing device. Other examples of the method of producing an image pickup unit include a process involving production of only lenses on a substrate such as a glass wafer, cutting of the substrate into lenses having a suitable size for being combined separate sensors, and integration of each lens with an image sensor into an image pick-up unit; a process involving formation of multiple resin lenses using a mold, integration of the lenses with a sensor substrate, and then cutting of the substrate; and a process involving cutting of a lens group into multiple lenses suitable for being combined with separate sensors, and integration of each lens with an image sensor prepared as an individual piece in advance into an image pick-up unit .
[0004]
In order to produce optical components such as lenses, photocurable resin compositions are used as alternatives for glass lenses. The lenses of a photocurable resin composition are formed by injecting the composition into, for example, a mold and curing it. In particular, a photocurable resin composition comprising a prepolymer having polymerizable groups have also been investigated for a reduction in shrinkage of the composition during curing. Such photocurable resin compositions are described in Japanese Patent Laid-open Nos . 2003-286316 and 2006-213851. Japanese Patent Laid-Open No. 2003-286316 discloses a process of forming fine features with high accuracy by photopolymerization of a composition comprising an alicyclic hydrocarbon skeleton and a radically polymerizable compound to reduce volumetric shrinkage during curing. The curable resin composition described in Japanese Patent Laid-Open No. 2003-286316 less shrinks during curing, has good mold releasability and high scratch resistance, and is stable for a long time even at 60°C. The curable resin composition described in Japanese Patent Laid-Open No. 2006-213851 contains adamantyl acrylate. SUMMARY OF THE INVENTION
[0005]
Unfortunately, the compositions described in Japanese Patent Laid-Open Nos. 2003-286316 and 2006-213851 are not well suited for a process for producing lenses and thus not suitable for production of lenses, in particular, wafer level lenses. One cause therefor is high viscosity of the compositions described in Japanese Patent Laid-Open Nos. 2003-286316 and 2006-213851. In addition, lenses prepared using the resin composition in Japanese Patent Laid-Open No 2006-213851 have relatively low transparency.
[0006]
Furthermore, the field of lenses requires a curable resin composition that exhibits a low volumetric change during curing and can form lenses with low haze. In addition, it is technically difficult to achieve compatibility among a high refractive index, a high Abbe number, and high transparency. It is an object of the present invention to provide a photocurable resin composition that solves these problems.
[0007]
The present inventors have studied in view of the above-described problems and have found that the problems can be solved by the following mean <1>, preferably means <2> to <17>, shown below.
<1> A photocurable resin composition comprising: a resin (A) having an alicyclic hydrocarbon group and having a weight average molecular weight of 40000 or less; a compound (B) having an alicyclic hydrocarbon group and a polymerizable group; and a compound (C) generating a radical or an acid by irradiation of active light or radiation, or a photocurable resin composition comprising: a resin (A) having an alicyclic hydrocarbon group; a compound (B) having an alicyclic hydrocarbon group and a polymerizable group; a compound (C) generating a radical or an acid by irradiation of active light or radiation; and a surfactant (D) .
<2> The photocurable resin composition according to <1>, comprising: the resin (A) having an alicyclic hydrocarbon group and having a weight average molecular weight of 40000 or less; the compound (B) having an alicyclic hydrocarbon group and a polymerizable group; and the compound (C) generating a radical or an acid by irradiation of active light or radiation.
<3> The photocurable resin composition according to <1> or <2>, the composition further comprising a polymerization inhibitor (D) .
<4> The photocurable resin composition according to <1>, comprising: the resin (A) having an alicyclic hydrocarbon group; the compound (B) having an alicyclic hydrocarbon group and a polymerizable group; the compound (C) generating a radical or an acid by irradiation of active light or radiation; andthe surfactant (D) .
<5> The photocurable resin composition according to <1> or <4>, wherein the surfactant (D) contains a silicon atom and/or a fluorine atom.
<6> The photocurable resin composition according to any one of <1> to <5>, wherein the polymerizable group of the compound (B) is a (meth) acryloyl group and/or an epoxy group .
<7> The photocurable resin composition according to any one of <1> to <6>, wherein the ratio of the resin (A) to the compound (B) is 1:1.9 to 1:4.
<8> The photocurable resin composition according to any one of <1> to <7>, wherein the resin (A) comprises a repeating unit having an alicyclic hydrocarbon group and a repeating unit having a polymerizable group.
<9> The photocurable resin composition according to any one of <1> to <8>, wherein the alicyclic hydrocarbon group of the resin (A) has a hydrocarbon group having 6 or more carbon atoms.
<10> The photocurable resin composition according to any one of <1> to <9>, wherein the resin (A) has at least one polymerizable group selected from acryloyl, methacryloyl, vinyl, ally, isocyanate, and epoxy groups.
<11> The photocurable resin composition according to any one of <1> to <10>, wherein the resin (A) comprises a repeating unit represented by Formula (1):
Figure imgf000006_0001
wherein R1 represents a hydrogen atom or a substituent; L1 represents a divalent linking group or a single bond; and a represents a monocyclic or polycyclic ring.
<12> The photocurable resin composition according to <11>, wherein the resin (A) further comprises a repeating unit represented by Formula (3) :
Figure imgf000006_0002
wherein R3 to R6 each independently represent a hydrogen atom or a substituent; and L3 represents a divalent linking group or a single bond.
<13> The photocurable resin composition according to any one of <1> to <12>, being used for a wafer level lens.
<14> A lens formed of a photocurable resin composition according to any one of <1> to <13>.
<15> A wafer level lens formed of a photocurable resin composition according to any one of <1> to <13>.
<16> A method of producing a lens comprising: curing a photocurable resin composition according to any one of <1> to <13>.
<17> A method of producing a wafer level lens comprising: curing a photocurable resin composition according to any one of <1> to <13>.
[0008]
The present invention can provide a photocurable resin composition that has satisfactory optical characteristics, can be easily adjusted to a process, and can provide a molded product having less haze and a low volumetric shrinkage rate.
[0009]
The invention can also provide a curable resin composition that has satisfactory optical characteristics, can be easily adjusted to a process, requires less force for releasing from a mold, and can provide a molded product having satisfactory adhesion to glass.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010]
FIG. 1 is a plan view illustrating an example configuration of a wafer level lens array;
FIG. 2 is a cross-sectional view of the wafer level lens array shown in FIG. 1 taken along the line A-A;
FIG. 3 illustrates supplying of a molding material for forming lenses on a substrate;
FIGs. 4A to 4C illustrate steps of forming lenses on a substrate; and
FIG. 5 illustrates another example configuration of a wafer level lens array,
where the reference number 10 denotes a substrate, the reference number 12 denotes a lens (wafer level lens), and the reference number 14 denotes a patterned light-shielding film.
MODE FOR CARRYING OUT THE INVENTION
[0011]
The present invention will now be described in detail. Note that the expression "to" for defining a range is used as a meaning that the numbers shown before and after "to" are included in the lower limit and the upper limit, respectively, throughout the specification.
First Embodiment
[0012]
The photocurable resin composition according to a first embodiment of the present invention comprises a resin (A) having an alicyclic hydrocarbon group and having a weight average molecular weight of 40000 or less, a compound (B) having an alicyclic hydrocarbon group and a polymerizable group, and a compound (C) generating a radical or an acid by irradiation of active light or radiation.
[0013]
The photocurable resin composition according to the first embodiment of the present invention will now be described in detail.
Resin (A)
[0014]
The resin (A) used in the present invention comprises an alicyclic hydrocarbon group and has a weight average molecular weight of 40000 or less.
[0015]
The alicyclic hydrocarbon group has a main chain composed of carbon atoms and has an alicyclic structure in the main chain or a side chain.
[0016]
Preferably, the resin (A) further has a polymerizable group. The resin (A) of the present invention preferably comprises repeating units each comprising a main chain composed of carbon atoms and an alicyclic structure in the main chain or a side chain and repeating units each comprising a polymerizable group (preferably, repeating units each comprising a polymerizable group in a side chain) ; more preferably comprises repeating units each comprising a main chain composed of carbon atoms and an alicyclic structure in the main chain or a side chain and repeating units each comprising a main chain composed of carbon atoms and a polymerizable group in a side chain.
[0017]
The resin (A) preferably comprises at least one of the repeating unit represented by Formula (1) and the repeating unit represented by Formula (2) :
Figure imgf000009_0001
wherein, R1 represents a hydrogen atom or a substituent ; L1 represents a divalent linking group or a single bond; and a represents a monocyclic or polycyclic ring,
Figure imgf000009_0002
wherein, β represents a monocyclic or polycyclic ring.
[0018]
In Formula (1), R1 preferably represents a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group.
[0019]
In Formula (1), L1 preferably represents a divalent linking group selected from -CO-, -0-, -CH2-, and combinations thereof or a single bond, more preferably a divalent linking group selected from -CO-, -0-, -CH2-, and combinations thereof. L1 preferably" has -C (=0) -0- on the side bonding to the main chain.
[0020]
In Formula (1), a is preferably a cyclic skeletal structure composed of 6 to 20 carbon atoms, more preferably a cyclic skeletal structure selected from the following Group (1) :
Figure imgf000010_0001
[0021]
The cyclic structures may have substituents or may not. The substituents are preferably alkyl groups, more preferably alkyl groups having 1 to 3 carbon atoms, further more preferably methyl groups.
[0022]
In Formula (2) , β is a cyclic skeletal structure composed of 6 to 20 carbon atoms, preferably a cyclic skeletal structure selected from the following Group (2):
Figure imgf000010_0002
[0023]
The cyclic structures may have substituents or may not.
Examples of the substituent include alkyl, allyl, oxo, hydroxy, and cyano groups and halogen atoms, and these substituents may be further substituted by these substituents. The substituent is preferably composed of one or more of carbon, hydrogen, oxygen, and nitrogen atoms.
The total number of carbon, oxygen, and nitrogen atoms constituting the substituent is preferably 1 to 10, more preferably 1 to 5.
[0024]
The repeating unit represented by Formula (1) is preferred to the repeating unit represented by Formula (2).
[0025]
Examples of the polymerizable group of the resin (A) in the present invention include acryloyl, methacryloyl (throughout the specification, acryloyl and methacryloyl groups may be collectively referred to as " (meth) acryloyl group"), vinyl, allyl, isocyanate, and epoxy groups. The polymerizable group is more preferably a (meth) acryloyl, epoxy, or vinyl group; more preferably a (meth) acryloyl or vinyl group; and further more preferably a vinyl group.
[0026]
In particular, the resin (A) of the present invention preferably comprises repeating units represented by Formula (3) :
Figure imgf000011_0001
wherein, R3 to R6 each independently represent a hydrogen atom or a substituent; and L3 represents a divalent linking group or a single bond.
[0027]
R3 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further more preferably a hydrogen atom or a methyl group.
[0028]
R4 and R5 are each preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and further more preferably a hydrogen atom.
[0029]
R6 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further more preferably a hydrogen atom or a methyl group.
[0030]
L3 preferably represents a divalent linking group selected from -CO-, -0-, -CH2-, and combinations thereof and more preferably has a structure represented by -C(=0)-0-.
[0031] The resin (A) can be generally synthesized by a known method using a photocurable resin composition comprising a polymerizable compound, for example, through radical polymerization, ionic polymerization, or ring-opening polymerization.
[0032]
The repeating units represented by Formulae (1) to (3) may be used alone or in combination.
[0033]
Specific examples of the polymerizable compound that can form the repeating unit represented by Formula (1) through polymerization are shown as Group A1 below; specific examples of the polymerizable compound that can form the repeating unit represented by Formula (2) through polymerization are shown as Group A2 below; and specific examples of the polymerizable compound that can form the repeating unit represented by Formula (3) through polymerization are shown as Group A3 below, but the compounds that can be used in the present invention are not limited to these examples.
Figure imgf000013_0001
Figure imgf000014_0001
Copolymerizable monomers
[0034]
The resin (A) used in the present invention may be produced by copolymerization of a monomer that can form a repeating unit represented by Formula (1), (2), or (3) with another monomer, for example, a monomer described in Polymer Handbook, 2nd ed. , J. Brandrup, Wiley Interscience (1975), Chapter 2, pp. 1-483.
[0035]
Specific examples of the monomer include compounds having one addition-polymerizable unsaturated bond, such as styrene derivatives, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylcarbazole, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides , dialkyl itaconates, and dialkyl or monoalkyl esters of fumaric acid.
[0036]
Examples of the styrene derivatives include styrene,
2 , 4 , 6-tribromostyrene, 2-phenylstyrene, and 4-chlorostyrene .
[0037]
Examples of the acrylic esters include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert- butyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, benzyl methacrylate, methoxybenzyl acrylate, furfuryl acrylate, and tetrahydrofurfuryl acrylate.
[0038]
Examples of the methacrylic esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, tert-butyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, furfuryl methacrylate, and tetrahydrofurfuryl methacrylate.
[0039]
Examples of the acrylamides include acrylamide, N- alkyl acrylamide (the alkyl group is of 1 to 3 carbon atoms, such as a methyl, ethyl, or propyl group), N, N-dialkyl acrylamide (the alkyl group is of 1 to 6 carbon atoms) , N- hydroxyethyl-N-methyl acrylamide, and N-2-acetamideethyl-N- acetyl acrylamide. [0040]
Examples of the methacrylamides include methacrylamide, N-alkyl methacrylamide (the alkyl group is of 1 to 3 carbon atoms, such as a methyl, ethyl, or propyl group), N,N- dialkyl methacrylamide (the alkyl group is of 1 to 6 carbon atoms), N-hydroxyethyl-N-methyl methacrylamide, and N-2- acetamideethyl-N-acetyl methacrylamide .
[0041]
Examples of the dialkyl itaconates include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate. Examples of the dialkyl or monoalkyl esters of fumaric acid include dibutyl fumarate.
[0042]
Other examples of the monomer include crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, and maleylonitrile .
[0043]
The resin (A) is preferably composed of 5 to 100% by mass of a repeating unit represented by Formula (1) and/or a repeating unit represented by Formula (2), 0 to 95% by mass of a repeating unit represented by Formula (3) , and 5% by mass or less of a repeating unit derived from any other polymerizable monomer. The content of the repeating unit represented by Formula (1) and/or the repeating unit represented by Formula (2) is preferably 5 to 95% by mass, more preferably 30 to 90% by mass, and further more preferably 40 to 80% by mass. The content of the repeating unit represented by Formula (3) is preferably 5 to 95% by mass, more preferably 10 to 70% by mass, and further more preferably 20 to 60% by mass.
[0044]
The resin (A) preferably has a weight average molecular weight (Mw) of 40000 or less from the viewpoint of viscosity and more preferably 3000 to 25000 from the viewpoint of volumetric shrinkage.
[0045]
The resin (A) preferably has a molecular weight distribution (Pd) of 1.0 to 6.0, more preferably 1.0 to 3.5. [0046]
The content of the resin (A) in the photocurable resin composition of the present invention is preferably in a range of 5 to 60% by mass, more preferably 7 to 50% by mass, and further more preferably 10 to 40% by mass.
Polymerizable compound (B)
[0047]
The polymerizable compound (B) used in the present invention comprises an alicyclic hydrocarbon group and a polymerizable group. In this regard, the polymerizable compound (B) is outside the definition of the "resin (A) comprising an alicyclic hydrocarbon group and having a weight average molecular weight of 40000 or less" and is usually a compound having a molecular weight of 1000 or less and is preferably a monomer or an oligomer.
[0048]
The polymerizable group is preferably acryloyl, methacryloyl , propenyl, vinyl, allyl, isocyanate, or epoxy group and more preferably at least one of a (meth) acryloyl group and an epoxy group from the viewpoint of curing properties. One molecule may contain one polymerizable group or two or more polymerizable groups.
[0049]
The polymerizable compound (B) preferably has an alicyclic structure of 6 to 16 carbon atoms, more preferably 6 to 10 carbon atoms.
[0050]
The polymerizable group and the alicyclic structure are linked to each other directly or via a linking group, preferably directly or via a divalent linking group selected from -CO-, -O-, -CH2-, and combinations thereof.
[0051]
The polymerizable compound (B) preferably has a molecular weight of 100 to 700, more preferably 130 to 600, and further more preferably 150 to 400.
[0052]
Specific examples of the polymerizable compound (B) are shown below, but are not limited to these structures.
Figure imgf000018_0001
These polymerizable compounds (B) may be contained alone or in combination (as a mixture) in the photocurable resin composition. In the present invention, the photocurable resin composition preferably comprises both a polymerizable compound having a (meth) acrylate group and a polymerizable compound having an epoxy group.
[0054]
The content of two or more of the polymerizable compound (B) in the photocurable resin composition of the present invention is preferably in a range of 20 to 90% by mass, more preferably 25 to 80% by mass, and further more preferably 30 to 70% by mass.
[0055]
The ratio of the resin (A) to the polymerizable compound (B) is preferably 1:1.9 to 1:4 from the viewpoint of viscosity, more preferably 1:1.9 to 1:3.5 from the viewpoint of volumetric shrinkage rate.
Compound (C) generating a radical or an acid by irradiation of active light or radiation
[0056]
In the present invention, the compound that generates a radical by irradiation of active light or radiation
(hereinafter also referred to as " (photo) polymerization initiator") can be selected from, for example, compounds known as radical polymerization initiators within a range that does not depart from the gist of the present invention
[0057]
The polymerization initiator is preferably a photopolymerization initiator that is photosensitive to, for example, light from the ultraviolet to visible region or may be an activator that generates an active radical through any action with a photoexcited sensitizer, or an initiator that initiates cationic polymerization depending on the type of a monomer.
[0058]
The photopolymerization initiator preferably comprises at least one component having a molar extinction coefficient of about 50 or more in the range of about 300 to 800 nm (more preferably 330 to 500 nm) . [0059]
Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., those having a triazine skeleton or an oxadiazole skeleton) , acylphosphine compounds (e.g., acylphosphine oxide), hexaarylbiimidazole , oxime compounds (e.g., oxime derivatives), organic peroxides, thio compounds, ketone compounds, aromatic onium salts, keto oxime ethers, aminoacetophenone compounds, and hydroxyacetophenone .
[0060]
Examples of the halogenated hydrocarbon compound having a triazine skeleton include compounds described in akabayashi, et al . , Bull. Chem. Soc. Japan, 42, 2924 (1969) ; compounds described in British Patent No. 1388492; compounds described in Japanese Patent Laid-Open No. Sho 53-133428; compounds described in German Patent No. 3337024; compounds described in F.C. Schaefer, et al., J. Org. Chem., 29, 1527 (1964); compounds described in Japanese Patent Laid-Open No. Sho 62-58241; compounds described in Japanese Patent Laid-Open No. Hei 5-281728; compounds described in Japanese Patent Laid-Open No. Hei 5- 34920; and compounds described in U.S. Patent No. 4212976.
[0061]
Examples of the compounds described in U.S. Patent No. 4212976 include compounds having an oxadiazole skeleton (e.g., 2-trichloromethyl-5-phenyl-l , 3 , 4-oxadiazole, 2- trichloromethyl-5- (4-chlorophenyl) -1, 3, 4-oxadiazole, 2- trichloromethyl-5- (1-naphthyl) -1, 3, -oxadiazole, 2- trichloromethyl-5- (2-naphthyl) -1,3, 4-oxadiazole, 2- tribromomethyl-5-phenyl-l, 3, 4-oxadiazole, 2-tribromomethyl- 5- (2-naphthyl) -1, 3, -oxadiazole, 2-trichloromethyl-5- styryl-1, 3, 4-oxadiazole, 2-trichloromethyl-5- (4- chlorstyryl) -1,3, 4-oxadiazole, 2-trichloromethyl-5- ( 4- methoxystyryl ) -1, 3, -oxadiazole, 2-trichloromethyl-5- (1- naphthyl) -1, 3, 4-oxadiazole, 2-trichloromethyl-5- (4-n- butoxystyryl) -1, 3, 4-oxadiazole, and 2-tibromomethyl-5- styryl-1, 3, 4-oxadiazole) .
[0062] Other examples of the photopolymerization initiator include acridine derivatives (e.g., 9-phenylacrydine and l,7-bis(9, 9' -acridinyl) heptane) , N-phenylglycine, polyhalogen compounds (e.g., carbon tetrabromide , phenyl tribromomethyl sulfone, and phenyl trichloromethyl ketone) , coumarins (e.g., 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- ( 2-benzofuroyl ) -7- ( 1-pyrrolidinyl ) coumarin, 3-benzoyl-7- diethylaminocoumarin, 3- (2-methoxybenzoyl) -7- diethylaminocoumarin, 3- ( -dimethylaminobenzoyl ) -7- diethylaminocoumarin, 3, 3' -carbonylbis (5, 7-di-n- propoxycoumarin) , 3,3' -carbonylbis (7-diethylaminocoumarin) , 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7- diethylaminocoumarin, 3- ( 4-diethylaminocinnamoyl ) -7- diethylaminocoumarin, 7-methoxy-3- (3- pyridylcarbonyl ) coumarin, 3-benzoyl-5 , 7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, and coumarin compounds described in Japanese Patent Laid-Open Nos. Hei 5-19475, Hei 7-271028, 2002-363206, 2002-363207, 2002-363208, and 2002-363209), acylphosphine oxides (e.g., bis(2,4,6- trimethylbenzoyl) -phenylphosphine oxide, bis (2,6- dimethoxybenzoyl ) -2,4, 4-trimethyl-pentylphenylphosphine oxide, and Lucirin TPO) , metallocenes (e.g., bis(n5-2,4- cyclopentadien-l-yl) -bis (2, 6-difluoro-3- (lH-pyrrol-l-yl) - phenyl) titanium and n5-cyclopentadienyl- 6-cumenyl- iron ( 1+) -hexafluorophosphate ( 1- ) ) , and compounds described in Japanese Patent Laid-Open No. Sho 53-133428, Japanese Patent Publication Nos. 57-1819 and 57-6096, and U.S. Patent No. 3615455.
[0063]
Examples of the ketone compound include benzophenone,
2-methylbenzophenone, 3-methylbenzophenone, 4 methylbenzophenone, 4-methoxybenzophenone, 2 chlorobenzophenone , 4-chlorobenzophenone, 4 bromobenzophenone , 2-carboxybenzophenone , 2 ethoxycarbonylbenzophenone, benzophenonetetracarboxyli acid and its tetramethyl ester, 4,4' bis (dialkylamino) benzophenones (e.g., 4,4' bis (dimethylamino) benzophenone) , 4,4' bis (dicyclohexylamino) benzophenone, 4,4'- bis (diethylamino) benzophenone, 4,4'- bis (dehydroxyethylamino) benzophenone, 4-methoxy- ' - dimethylaminobenzophenone, 4 , 4 ' -dimethoxybenzophenone, 4- dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzil, anthraquinone, 2-t-butylanthraquinone, 2- methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro-thioxanthone, 2,4- diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-l- (4-morpholinophenyl) -1-butanone, 2-methyl-l- [ 4-
(methylthio) phenyl] -2-morpholino-l-propanone, 2-hydroxy-2- methyl [ 4- ( 1-methylvinyl) phenyl ] propanol oligomer, benzoin, benzoin ethers (e.g., benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, and benzyl dimethyl ketal) , acridone, chloroacridone, N-methylacridone, N-butylacridone, and N- butyl-chloroacridone .
[0064]
Hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds are also suitable for photopolymerization initiators. More specifically, for example, aminoacetophenone initiators described in Japanese Patent Laid-Open No. 10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can be used.
[0065]
Examples of the commercially available hydroxyacetophenone initiator include IRGACURE-184 , DAROCUR-1173, IRGACURE-500 , IRGACURE-2959, and IRGACURE-127 (trade names, all are manufactured by BASF) . Examples of the commercially available aminoacetophenone initiator include IRGACURE-907 , IRGACURE-369, and IRGACURE-379 (trade names, all are manufactured by BASF) . As the aminoacetophenone initiator, compounds having absorption wavelengths matched to long wavelengths, such as 365 nm or 405 nm, of light sources described in Japanese Patent Laid- Open No. 2009-191179 can also be used. Examples of the commercially available acylphosphine initiator include IRGACURE-819 and DAROCUR-TPO (trade names, all are manufactured by BASF) .
[0066]
More preferred examples of the photopolymerization initiator include oxime compounds. Specific examples of the oxime compound include compounds described in Japanese Patent Laid-Open Nos. 2001-233842, 2000-80068, and 2006- 342166.
[0067]
Examples of the oxime compounds such as oxime derivatives that can be suitably used in the present invention as the photopolymerization initiator include 3- benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3- propionyloxyiminobutan-2-one , 2-acetoxyiminopentan-3-one, 2-acetoxyimino-l-phenylpropan-l-one, 2-benzoyloxyimino-l- phenylpropan-l-one, 3- ( 4-toluenesulfonyloxy) iminobutan-2- one, and 2-ethoxycarbonyloxyimino-l-phenylpropan-l-one .
[0068]
Examples of the oxime ester compounds include compounds described in J.C.S. Perkin II, (1979), pp. 1653-
1660, J.C.S. Perkin II, (1979), pp. 156-162, and Journal of
Photopolymer Science and Technology, (1995), pp. 202-232; and compounds described in Japanese Patent Laid-Open Nos.
2000-66385 and 2000-80068, National Publication of International Patent Application No. 2004-534797, and
Japanese Patent Laid-Open No. 2006-342166.
[0069]
As commercially available oxime ester compounds, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can also be suitably used.
[0070]
Furthermore, as other examples of the oxime ester compound, the followings can be used: compounds described in National Publication of International Patent Application No. 2009-519904, where oxime is linked to the N-position of carbazole; compounds described in U.S. Patent No. 7626957, where a hetero-substituent is introduced into the benzophenone moiety; compounds available from ADEKA as initiators, described in Japanese Patent Laid-Open No. 2010-15025 and U.S. Patent Publication No. 2009-292039, where a nitro group is introduced into the dye moiety; ketoxime compounds described in International Patent No. WO2009/131189; compounds described in U.S. Patent No. 7556910, containing a triazine skeleton and an oxime skeleton within the same molecule; and compounds described in Japanese Patent Laid-Open No. 2009-221114, having an absorption maximum at 405 nm and exhibiting high sensitivity for a g-line light source.
[0071]
More preferably, the cyclic oxime compounds described in Japanese Patent Laid-Open Nos. 2007-231000 and 2007- 322744 can be suitably used. In particular, the cyclic oxime compounds fused to a carbazole dye, described in Japanese Patent Laid-Open Nos. 2010-32985 and 2010-185072, have high light absorptivity, which is preferable from the viewpoint of an increase in sensitivity.
[0072]
In addition, the compounds described in Japanese
Patent Laid-Open No. 2009-242469, having an unsaturated bond at a specific site of the oxime compound, can achieve high sensitivity through regeneration of an active radical from a polymerization inactive radical and therefore can be suitably used.
[0073]
Most preferred are oxime compounds having specific substituents described in Japanese Patent Laid-Open No. 2007-269779 and oxime compounds having thioaryl groups described in Japanese Patent Laid-Open No. 2009-191061.
[0074]
Specifically, the oxime photopolymerization initiator is preferably a compound represented by the following Formula (1), wherein the N-0 bond may be of oxime is an (E)-form, a (Z)-form, or a mixture of the (E)-form and the (Z) -form:
Figure imgf000025_0001
wherein, R and B each independently represent a monovalent substituent; A represents a divalent organic group; and Ar represents an aryl group.
[0075]
The monovalent substituent represented by R is preferably a monovalent nonmetallic atom group.
[0076]
Examples of the monovalent nonmetallic atom group include alkyl, aryl, acyl, alkoxycarbonyl , aryloxycarbonyl , heterocyclic, alkylthiocarbonyl , and arylthiocarbonyl groups. These groups may have one or more substituents .
The substituent may be further substituted by another substituent .
[0077]
Examples of the substituent include halogen atoms, aryloxy, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acyl, alkyl, and aryl groups.
[0078]
The alkyl group that optionally has a substituent is preferably an alkyl group having 1 to 30 carbon atoms, and specific examples thereof include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl , 2-ethylhexyl , phenacyl, 1- naphthoylmethyl , 2-naphthoylmethyl , 4- methylsulfanylphenacyl , 4-phenylsulfanylphenacyl, 4- dimethylaminophenacyl , 4-cyanophenacyl , 4-methylphenacyl , 2-methylphenacyl , 3-fluorophenacyl, 3- trifluoromethylphenacyl, and 3-nitrophenacyl groups.
[0079]
The aryl group that optionally has a substituent is preferably an aryl group having 6 to 30 carbon atoms, and specific examples thereof include phenyl, biphenyl, 1- naphthyl, 2-naphthyl, 9-anthryl, 9-phenanthryl , 1-pyrenyl, 5-naphthacenyl , 1-indenyl, 2-azulenyl, 9-fluorenyl, terphenyl, quaterphenyl, o-, m-, and p-tolyl, xylyl, o-, m-, and p-cumenyl, mesityl, pentalenyl, binaphthalenyl , ternaphthalenyl , quaternaphthalenyl , heptalenyl, biphenylenyl , indacenyl, fluoranthenyl, acenaphthylenyl , aceanthrylenyl , phenalenyl, fluorenyl, anthryl, bianthracenyl, teranthracenyl , quateranthracenyl , anthraquinolyl , phenanthryl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl , pleiadenyl, picenyl, perylenyl, pentaphenyl, pentacenyl, tetraphenylenyl , hexaphenyl, hexacenyl, rubicenyl, coronenyl, trinaphthylenyl, heptaphenyl, heptacenyl, pyranthrenyl , and ovalenyl groups.
[0080]
The acyl group that optionally has a substituent is preferably an acyl group having 2 to 20 carbon atoms, and specific examples thereof include acetyl, propanoyl, butanoyl, trifluoroacetyl, pentanoyl, benzoyl, 1-naphthoyl, 2-naphthoyl, 4-methylsulfanylbenzoyl, 4- phenylsulfanylbenzoyl , 4-dimethylaminobenzoyl , 4- diethylaminobenzoyl, 2-chlorobenzoyl , 2-methylbenzoyl , 2- methoxybenzoyl , 2-butoxybenzoyl , 3-chlorobenzoyl , 3- trifluoromethylbenzoyl , 3-cyanobenzoyl , 3-nitrobenzoyl , 4- fluorobenzoyl , 4-cyanobenzoyl , and 4-methoxybenzoyl groups.
[0081]
The alkoxycarbonyl group that optionally has a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and specific examples thereof include methoxycarbonyl , ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, hexyloxycarbonyl , octyloxycarbonyl , decyloxycarbonyl, octadecyloxycarbonyl , and trifluoromethyloxycarbonyl groups .
[0082]
Specific examples of the aryoxycarbonyl group that optionally has a substituent include phenoxycarbonyl, 1- naphthyloxycarbonyl, 2-naphthyloxycarbonyl , 4- methylsulfanylphenyloxycarbonyl , 4- phenylsulfanylphenyloxycarbonyl , 4- dimethylaminophenyloxycarbonyl , 4- diethylaminophenyloxycarbonyl , 2-chlorophenyloxycarbonyl ,
2-methylphenyloxycarbonyl, 2-methoxyphenyloxycarbonyl , 2- butoxyphenyloxycarbonyl , 3-chlorophenyloxycarbonyl , 3- trifluoromethylphenyloxycarbonyl , 3-cyanophenyloxycarbonyl ,
3-nitrophenyloxycarbonyl , 4-fluorophenyloxycarbonyl , 4- cyanophenyloxycarbonyl , and 4-methoxyphenyloxycarbonyl groups .
[0083]
The heterocyclic group that optionally has a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen, oxygen, sulfur, or phosphorus atom, and specific examples thereof include thienyl, benzo [b] thienyl, naphtho [2, 3-b] thienyl, thianthrenyl , furyl, pyranyl, isobenzofuranyl , chromenyl, xanthenyl, phenoxanthiinyl , 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, 3H-indolyl, indolyl, lH-indazolyl , purinyl, 4H-quinolizinyl , isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxanilyl , quinazolinyl, cinnolinyl, pteridinyl, 4aH-carbazolyl , carbazolyl, β-carbolinyl , phenanthridinyl , acridinyl, perimidinyl, phenanthrolinyl , phenazinyl, phenarsazinyl , isothiazolyl , phenotiazinyl, isoxazolyl, furazanyl, phenoxazinyl, isochromanyl, chromanyl, pyrrolidinyl , pyrrolinyl, imidazolidinyl , imidazolinyl , pyrazolidinyl , pyrazolinyl, piperidyl, piperazinyl, indolinyl, isoindolinyl , quinuclidinyl , morpholinyl, and thioxanetolyl groups .
[0084]
Specific examples of the alkylthiocarbonyl group that optionally has a substituent include methylthiocarbonyl , propylthiocarbonyl , butylthiocarbonyl, hexylthiocarbonyl, octylthiocarbonyl, decylthiocarbonyl , octadecylthiocarbonyl , and trifluoromethylthiocarbonyl groups.
[0085]
Specific examples of the arylthiocarbonyl group that optionally has a substituent include 1-naphthylthiocarbonyl, 2-naphthylthiocarbonyl , 4-methylsulfanylphenylthiocarbonyl , 4-phenylsulfanylphenylthiocarbonyl, 4- dimethylaminophenylthiocarbonyl, 4- diethylaminophenylthiocarbonyl, 2-chlorophenylthiocarbonyl , 2-methylphenylthiocarbonyl , 2-methoxyphenylthiocarbonyl, 2- butoxyphenylthiocarbonyl , 3-chlorophenylthiocarbonyl, 3- trifluoromethylphenylthiocarbonyl, 3- cyanophenylthiocarbonyl , 3-nitrophenylthiocarbonyl , 4- fluorophenylthiocarbonyl, 4-cyanophenylthiocarbonyl, and 4- methoxyphenylthiocarbonyl groups.
[0086]
The monovalent substituent represented by B is an aryl, heterocyclic, arylcarbonyl, or heterocyclic carbonyl group. These groups may have one or more substituents . Examples of the substituent include the substituents described above. These substituents may be further substituted by another substituent .
[0087]
Among these structures, particularly preferred structures are shown below.
[0088]
In the following structures, Y, X, and n respectively have the same definitions as Y, X, and n in Formula (2) described later, and preferred examples thereof are also the same.
Figure imgf000028_0001
[0089]
Examples of the divalent organic group represnted by Ά include alkylene, cyclohexylene , and alkynylene groups having 1 to 12 carbon atoms. These groups may have one or more substituents. Examples of the substituent include the substituents described above. These substituents may be further substituted by another substituent.
[0090]
In particular, from the viewpoints of enhancing the sensitivity and suppressing coloration by heating or aging, A is preferably an unsubstituted alkylene group or an alkylene group substituted by alkyl (e.g., methyl, ethyl, tert-butyl, or dodecyl) , alkenyl (e.g., vinyl or ally), or aryl (e.g., phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthryl, phenanthryl, or styryl) group.
[0091]
The aryl group represented by Ar preferably has 6 to 30 carbon atoms and may have a substituent. Examples of the substituent are the same as those of the substituted aryl groups shown above as specific examples of the aryl group that optionally has a substituent.
[0092]
In particular, the substituent is preferably a substituted or unsubstituted phenyl group, from the viewpoints of enhancing the sensitivity and suppressing coloration by heating or aging.
[0093]
In light of sensitivity, examples of the structure "SAr" formed by Ar and adjoining S in Formula (1) are shown below. In the structures, Me represents a methyl group, and Et reperesents an ethyl group.
Figure imgf000030_0001
[0094]
The oxime compound is preferably represented by Formula (2 ) :
Figure imgf000030_0002
wherein, R and X each independently represent a monovalent substituent; A and Y each independently represent a divalent organic group; Ar represents an aryl group; and n is an integer of 0 to 5. [0095]
In Formula (2), R, A, and Ar respectively have the same definitions as R, A, and Ar in Formula (1), and preferred examples thereof are also the same.
[0096]
Examples of the monovalent substituent represented by X include alkyl, aryl, alkoxy, aryloxy, acyloxy, acyl, alkoxycarbonyl, amino, and heterocyclic groups and halogen atoms. These groups may have one or more substituents . Examples of the substituent include the substituents described above. These substituents may be further substituted by another substituent.
[0097]
In particular, X is preferably an alkyl group, from the viewpoints of solvent solubility and enhancement of absorption efficiency in the long wavelength region.
[0098]
In formula (2), n represents an integer of 0 to 5 and is preferably an integer of 0 to 2.
[0099]
Examples of the divalent organic group represented by Y include structures shown below. In the groups shown below, indicates the bonding site with the carbon atom adjacent to Y in Formula (2) .
Figure imgf000031_0001
[0100]
Among these structures, from the viewpoint of high sensitivity, the structures shown below are preferred.
Figure imgf000032_0001
[0101]
The oxime compound is preferably a compound represented by the following Formula (3) .
Figure imgf000032_0002
wherein, R and X each independently represent a monovalent substituent; A represents a divalent organic group; Ar represents an aryl group; and n is an integer of 0 to 5.
[0102]
In Formula (3) , R, X, A, Ar, and n respectively have the same definitions as R, X, A, Ar, and n in Formula (2), and preferred examples thereof are also the same.
[0103]
Specific examples (C-4) to (C-13) of the oxime compound that can be suitably used are shown below, but the present invention is not limited to these compounds.
Figure imgf000033_0001
[0104]
The oxime compound has a maximum absorption wavelength in the wavelength region of 350 to 500 nm, preferably has an absorption wavelength in the wavelength region of 360 to 480 nm, and further more preferably shows high absorbance at 365 nm and 455 nm.
[0105]
From the viewpoint of sensitivity, the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1000 to 300000, more preferably 2000 to 300000, and further more preferably 5000 to 200000.
[0106]
The molar extinction coefficient of a compound can be measured by a known method. Specifically, for example, the molar extinction coefficient is preferably measured at a concentration of 0.01 g/L in an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Carry-5 spctrophotometer, manufactured by Varian Inc.).
[0107]
In the present invention, a combination of two or more of the photopolymerization initiators is optionally used.
[0108]
The content of the photopolymerization initiator (total content in the case of combined use of two or more photopolymerization initiators) in the photocurable resin composition is preferably in the range of 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and further more preferably 0.5 to 8% by mass, based on the total amount (total mass) of the composition, from the viewpoint of volumetric shrinkage rate. A content in this range can provide high sensitivity and pattern formability.
[0109]
The photocurable resin composition may comprise a sensitizer for the purpose of enhancing the radical- generating efficiency of the photopolymerization initiator and shifting the photosensitive wavelength to the longer wavelength side. The sensitizer used in the present invention sensitizes the photopolymerization initiator in the Compound (C) preferably by an electron transfer mechanism or an energy transfer mechanism.
[0110]
Examples of the sensitizer comprised in the photocurable resin composition include compounds described in paragraphs [0101] to [0154] of Japanese Patent Laid-Open No. 2008-32803.
[0111]
The content of the sensitizer in the photocurable resin composition is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, in terms of the solid content, from the viewpoints of light absorption efficiency at the depth and intiation decomposition efficiency.
[0112]
The sensitizers may be used alone or in combination.
[0113]
The compound that generates an acid by irradiation of active light or radiation (hereinafter also referred to as "acid generator") may be any known acid generator, and preferred examples thereof include the compounds represented by the following Formulae (ZI), (ZII), and (ZIII) .
Figure imgf000035_0001
[0114]
In Formula (ZI), R201/ ϊ¾02 and R203 each independently represent an organic group. The organic groups as R201/ R202, and R203 have 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Two of R2oi to R203 may bond to each other to form a ring structure where the ring contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl bond. The group formed by bonding of two of R2oi to R203 is, for example, an alkylene group (e.g., butylene or pentylene) .
[0115]
Z~ represents a non-nucleophilic anion (having significantly low ability of causing a nucleophilic reaction). Examples of Z" include sulfonate anions (e.g., aliphatic sulfonate anions, aromatic sulfonate anions, and camphorsulfonate anions), carboxylate anions (e.g., aliphatic carboxylate anions, aromatic carboxylate anions, and aralkylcarboxylate anions) , sulfonylimide anions, bis (alkylsulfonyl ) imide anions, and tris (alkylsulfonyl ) raethide anions.
[0116]
The aliphatic moieties of the aliphatic sulfonate anions and the aliphatic carboxylate anions may be alkyl groups or cycloalkyl groups, and preferred examples thereof include linear or branched alkyl groups having 1 to 30 carbon atoms and cycloalkyl groups having 3 to 30 carbon atoms .
[0117]
Preferred examples of the aromatic moieties of the aromatic sulfonate anions and the aromatic carboxylate anions include aryl groups having 6 to 14 carbon atoms, e.g., phenyl, tolyl, and naphthyl groups.
[0118]
The alkyl, cycloalkyl, and aryl groups may have substituents . Specific examples of the substituent include halogens such as fluorine, nitro, carboxyl, hydroxyl, amino, cyano, alkoxy (preferably having 1 to 15 carbon atoms) , cycloalkyl (preferably having 3 to 15 carbon atoms) , aryl (preferably having 6 to 14 carbon atoms), alkoxycarbonyl (preferably having 2 to 7 carbon atoms) , acyl (preferably having 2 to 12 carbon atoms) , alkoxycarbonyloxy (preferably having 2 to 7 carbon atoms) , alkylthio (preferably having 1 to 15 carbon atoms), alkylsulfonyl (preferably having 1 to 15 carbon atoms) , alkyliminosulfonyl (preferably having 2 to 15 carbon atoms) , aryloxysulfonyl (preferably having 6 to 20 carbon atoms) , alkylaryloxysulfonyl (preferably having 7 to 20 carbon atoms) , cycloalkylaryloxysulfonyl (preferably having 10 to 20 carbon atoms), alkyloxyalkyloxy (preferably having 5 to . 20 carbon atoms) , and cycloalkylalkyloxyalkyloxy (preferably having 8 to 20 carbon atoms) groups. The aryl group and the ring structure of each group may further have alkyl (preferably having 1 to 15 carbon atoms) groups as substituents. [0119]
The aralkyl group of the aralkylcarboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, and examples thereof include benzyl, phenethyl, naphthylmethyl, naphthylethyl, and naphthylbutyl groups.
[0120]
Examples of the sulfonylimide anion include saccharin anions .
[0121]
The alkyl groups of the bis (alkylsulfonyl ) imide anion and the tris (alkylsulfonyl ) methide anion are preferably alkyl groups having 1 to 5 carbon atoms. Examples of the substituent of these alkyl groups include halogen atoms, halogenated alkyl, alkoxy, alkylthio, alkyloxysulfonyl , aryloxysulfonyl, and cycloalkylaryloxysulfonyl groups, and preferred substituents are a fluorine atom and fluorinated alkyl groups.
[0122]
Other examples of Z- include phosphorus fluoride, boron fluoride, and antimony fluoride.
[0123]
Z- is preferably an aliphatic sulfonate anion having a substituent of a fluorine atom at least on the a-position of sulfonic acid, an aromatic sulfonate anion having a substituent of a fluorine atom or a fluorine containing group at least on the α-position, a bis (alkylsulfonyl) imide anion of which the alkyl group has a substituent of a fluorine atom, or a tris (alkylsulfonyl) methide anion of which the alkyl group has a substituent of a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably having 4 to 8 carbon atoms) or a benzenesulfonate anion having a fluorine atom, and more preferably a nonafluorobutanesulfonate anion, a perfluorooctanesulfonate anion, a pentafluorobenzenesulfonate anion, or a 3,5- bis (trifluoromethyl) benzenesulfonate anion. The generated acid preferably has an acid strength pKa of -1 or less for the purpose of improving the sensitivity. [0124]
Examples of the organic groups represented by R201/ 202/ and R203 include aryl groups (preferably having 6 to 15 carbon atoms) , linear or branched alkyl groups (preferably having 1 to 10 carbon atoms) , and cycloalkyl groups (preferably having 3 to 15 carbon atoms) .
[0125]
At least one of R2o: R202, and R203 is preferably an aryl group, and more preferably all of them are aryl groups. The aryl group may be not only a group such as phenyl or naphthyl, but also a heteroaryl group such as indole or pyrrole. These aryl groups may further have substituents . Examples of the substituents include, but not limited to, halogens such as fluorine, nitro, carboxyl, hydroxyl, amino, cyano, alkoxy (preferably having 1 to 15 carbon atoms), cycloalkyl (preferably having 3 to 15 carbon atoms) , aryl (preferably having 6 to 14 carbon atoms) , alkoxycarbonyl (preferably having 2 to 7 carbon atoms) , acyl (preferably having 2 to 12 carbon atoms) , and alkoxycarbonyloxy (preferably having 2 to 7 carbon atoms) .
[0126]
Two of R201 R202r and R203 m y bond to each other via a single bond or a linking group. Examples of the linking group include, but not limited to, alkylene groups (preferably having 1 to 3 carbon atoms) , -0-, -S-, -CO-, and -SO2-.
[0127]
Preferred examples of the structure where at least one of R201, R202, and R203 is not an aryl group include cationic structures of compounds described in paragraphs [0047] and [0048] of Japanese Patent Laid-Open No. 2004-233661, compounds described in paragraphs [0040] to [0046] of Japanese Patent Laid-Open No. 2003-35948, compounds represented by Formulae (1-1) to (1-70) in U.S. Patent Publication No. 2003/0224288, and compounds represented by Formulae (IA-1) to (IA-54) and (IB-1) to (IB-24) in U.S. Patent Publication No. 2003/0077540.
[0128] In particular, when at least one of R201, R202, and R203 is not an aryl group, the following cases (1) and (2) are particularly preferred.
[0129]
(1) A case where at least one of R201, R202/ and R2o3 has a structure represented by Ar-CO-X- and the other group or groups are linear or branched alkyl or cycloalkyl: In this case, when the number of the other groups is two, the linear or branched alkyl and/or cycloalkyl of the other groups may bond to each other to form a ring structure.
[0130]
Here, Ar represents an aryl group optionally having a substituent, and specific examples thereof include the same aryl groups as R2oi? R202/ or R2o3- Ar is preferably a phenyl group optionally having a substituent.
[0131]
X represents an alkylene group optionally having a substituent, specifically, an alkylene group having 1 to 6 carbon atoms, preferably a linear or branched alkylene group having 1 to 3 carbon atoms.
[0132]
The linear or branched alkyl or cycloalkyl group being the other group (s) preferably has 1 to 6 carbon atoms. These groups may further have substituents . When the number of the other groups is two, these groups preferably bond to each other to form a ring structure (preferably 5 to 7- membered ring) .
[0133]
(2) A case where one or two of R201/ R202, and R203 are aryl groups optionally having substituents and the other group or groups are linear or branched alkyl or cycloalkyl:
[0134]
Specific examples of the aryl group are the same aryl groups as R2oii R202/ or R203 and the aryl group is preferably a phenyl or naphthyl group. In addition, the aryl group preferably has any of hydroxyl, alkoxy, and alkyl groups as a substituent. The substituent is more preferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms.
[0135]
The linear or branched alkyl or cycloalkyl group as R201/ ¾02, or R203 preferably has 1 to 6 carbon atoms. These groups may further have substituents . When two groups are other than the aryl group, these two groups may bond to each other to form a ring structure.
[0136]
In Formulae (ZII) and (ZIII), R204 to R207 each independently represent an aryl, alkyl, or cycloalkyl group. The aryl, alkyl, and cycloalkyl groups of R2o4 to R2o7 are the same as those of R2oi to R203 in Formula (ZI) .
[0137]
The aryl, alkyl, and cycloalkyl groups of R204 to R207 may have substituents . Examples of the substituent are the same as those of the aryl, alkyl, and cycloalkyl groups of R20i to R203 in Formula (ZI) .
[0138]
Z~ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anions as Z~ in Formula (ZI) .
[0139]
Examples of the acid generator further include the compounds represented by the following Formulae (ZIV) , (ZV), and (ZVI) :
Figure imgf000040_0001
[0140]
In Formulae (ZIV) to (ZVI), Ar3 and Ar4 each independently represent an aryl group; R2os, R209, and R210 each independently represent an alkyl, cycloalkyl, or aryl group; and A represents an alkylene, alkenylene, or arylene group .
[0141]
Particularly preferred examples of the acid generator
Figure imgf000041_0001
Figure imgf000042_0001
The acid generators may be used alone or in combination .
[0143]
The content of the acid generator in the composition is preferably 0.1 to 20% by mass, more preferably 0.1 to 15% by mass, and further more preferably 0.1 to 10% by mass based on the total solid content of the composition.
Polymerization inhibitor (D)
[0144]
The composition of the present invention may comprise one or more polymerization inhibitors. Examples of the polymerization inhibitor include phenolic hydroxyl group- containing compounds, quinones, N-oxide compounds, piperidin-l-oxyl free radical compounds, pyrrolidin-l-oxyl free radical compounds, N-nitrosophenylhydroxylamines , anilines, pyridines, aliphatic tertiary amines, and cationic dyes.
[0145]
Specific examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol , di-t-butyl-p-cresol , pyrogallol, resorcinol, catechol, t-butylcatechol , hydroquinone monoalkyl ethers (e.g., hydroquinone monomethyl ether and hydroquinone monobutyl ether) , benzoquinone, 4, -thiobis ( 3-methyl-6-t-butylphenol ) , 2,2'- methylenebis (4-methyl-6-t-butylphenol) , 2,2,6,6- tetramethylpiperidine and its derivatives, di-t- butylnitroxide, 2, 2, 6, 6-tetramethylpiperidin-N-oxide and its derivatives, piperidine 1-oxyl free radical, 2,2,6,6- tetramethylpiperidine 1-oxyl free radical, 4-oxo-2, 2, 6, 6- tetramethylpiperidine 1-oxyl free radical, 4-hydroxy- 2 , 2 , 6, 6-tetramethylpiperidine 1-oxyl free radical, 4- acetamide-2, 2, 6, 6-tetramethylpiperidine 1-oxyl free radical, 4-maleimide-2 , 2 , 6, 6-tetramethylpiperidine 1-oxyl free radical, 4-phosphonooxy-2 , 2 , 6, 6-tetramethylpiperidine 1-oxyl free radical, 3-carboxy-2 , 2 , 5, 5- tetramethylpyrrolidine 1-oxyl free radical, N- nitrosophenylhydroxylamine primary cerium salts, N- nitrosophenylhydroxylamine aluminium salts, crystal violet, methyl violet, ethyl violet, Victoria pure blue BOH, N,N- diethylaniline, 4-methylaniline , 2 , 6-dimethylpyridine, 4- hydroxypyridine, tributylamine, trioctylamine, and caryophyllene .
[0146]
The content of the polymerization inhibitor in the composition is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and further more preferably 1 to 10% by mass, based on the total amount (total mass) of the composition from the viewpoint of volumetric shrinkage rate .
Additive (E)
[0147]
The curable resin composition of the present invention may further contain additives such as a surfactant and a dissolution modulator.
[0148]
The curable resin composition of the present invention preferably contains 15% by mass or less of components other the components (A) to (D) .
Surfactant
[0149]
The photocurable resin composition of the present invention may contain various surfactants from the viewpoint of further improving the coating properties. Examples of the surfactant include fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.
[0150]
In particular, the photocurable resin composition of the present invention containing a fluorine surfactant can provide a coating solution having improved liquid characteristics (in particularly, fluidity) to further improve the uniformity in application thickness and reduce the necessary volume of the solvent.
[0151]
That is, in the case of forming a film using a coating solution prepared from the photocurable resin composition containing a fluorine surfactant, the interfacial tension between the coating solution and a coated surface is reduced to enhance wettability of the coated surface, resulting in an improvement in coating properties for the coated surface. Consequently, even in formation of a thin film of several micrometers thickness by a small amount of the solution, the solution can effectively form the film with low irregularity in thickness, i.e., with a uniform thickness .
[0152]
The content of fluorine in the fluorine surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and further more preferably 7 to 25% by mass. The fluorine surfactant containing fluorine in this range is effective for improving uniformity in film thickness and reducing the necessary volume of the solvent and also has satisfactory solubility in the photocurable resin composition .
[0153]
Examples of the fluorine surfactant include MEGAFAC
F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, and F781 (all manufactured by DIC Corp.), Fluorad FC430, FC431, and FC171 (all manufactured by Sumitomo 3M Ltd.), and Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (all manufactured by Asahi Glass Co., Ltd. ) .
[0154]
Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate) , polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester (e.g., Pluronic L10, L31, L61, L62, 10R5, 17R2, and 25R2 and Tetronic 304, 701, 704, 901, 904, and 150R1 manufactured by BASF; and Solsperse 20000 manufactured by
The Lubrizol Corp.).
[0155]
Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita & Co., Ltd.), organosiloxane polymers (trade name: KP341, manufactured by Shin-Etsu Chemical Co., Ltd.), and (meth) acrylic acid (co) polymers (trade name: Polyflow No. 75, No. 90, and No. 95, manufactured by Kyoeisha Chemical Co., Ltd., and trade name: 001, manufactured by Yusho Co., Ltd.).
[0156]
Examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.).
[0157]
Examples of silicone surfactant include "ToraySilicone DC3PA" , "ToraySilicone SH7PA", "ToraySilicone DC11PA", "ToraySilicone SH21PA", "ToraySilicone SH28PA",
"ToraySilicone SH29PA", "ToraySilicone SH30PA" , and "ToraySilicone SH8400", manufactured by Dow Corning Toray Co., Ltd.; "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", and "TSF-4452", manufactured by Momentive Performance Materials Inc.; "KP341", "KF6001", and "KF6002", manufactured by Shin-Etsu Chemical Co., Ltd.; and "BYK307", "BYK323", and "BYK330", manufactured by BYK-Chemie GmbH.
[0158]
The surfactants may be used alone or in combination.
[0159]
The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total mass of the photocurable resin composition.
Solvent
[0160]
The composition of the present invention may contain a solvent. The content of the solvent is preferably 10% by mass or less, and more preferably 5% by mass or less from the viewpoint of reducing air bubbles in a molded product.
[0161] However, it is preferred that the photocurable resin composition of the present invention do not substantially contain a solvent. "Not substantially contain" means that, for example, the content of a solvent is 1% by mass or less of the photocurable resin composition.
[0162]
The curable resin composition of the present invention can have a viscosity of 0.1 to 25 Pa-s, further 0.3 to 15 Pa-s, and further 0.3 to 7 Pa-s. In the curable resin composition of the present invention, high optical characteristics and a low volumetric shrinkage rate can be maintained even at such a low viscosity.
[0163]
In the photocurable resin composition of the present invention, the volumetric shrinkage rate during curing is preferably 10% or less, more preferably 5% or less, and further more preferably 3% or less.
[0164]
In curable resin compositions, it is technically difficult to achieve compatibility between a high refractive index and a high Abbe number. Specifically, it is difficult to achieve both a refractive index of 1.5 or more and an Abbe number of 50 or more.
[0165]
Although conventional compositions for forming lenses contain inorganic particles in order to increase the refractive index and the Abbe number, the present invention can achieve a high refractive index and a high Abbe number even if the composition does not substantially contain such inorganic particles (e.g., the content of the inorganic particles is 1% by mass or less of the composition) .
[0166]
In the curable resin composition of the present invention, the haze after curing is preferably 5% or less, more preferably 3% or less.
[0167]
In the photocurable resin composition of the present invention, the glass transition temperature after curing is preferably 200°C or more, and more preferably 260°C or more.
Second Embodiment
[0168]
The photocurable resin composition according to a second embodiment of the present invention comprises a resin (A) having an alicyclic hydrocarbon group, a compound
(B) having an alicyclic hydrocarbon group and a polymerizable group, a compound (C) generating a radical or an acid by irradiation of active light or radiation, and a surfactant (D) .
[0169]
The photocurable resin composition according to the second embodiment of the present invention will now be described in detail.
Resin (A)
[0170]
The resin (A) used in the present invention comprises an alicyclic hydrocarbon group.
[0171]
The alicyclic hydrocarbon group has a main chain composed of carbon atoms and has an alicyclic structure in the main chain or a side chain.
[0172]
Preferably, the resin (A) further has a polymerizable group. The resin (A) of the present invention preferably comprises repeating units each comprising a main chain composed of carbon atoms and an alicyclic structure in the main chain or a side chain and repeating units each comprising a polymerizable group (preferably, repeating units each comprising a polymerizable group in a side chain) ; more preferably, comprises repeating units each comprising a main chain composed of carbon atoms and an alicyclic structure in the main chain or a side chain and repeating units each comprising a main chain composed of carbon atoms and a polymerizable group in a side chain.
[0173]
The resin (A) preferably comprises at least one of the repeating unit represented by Formula (1) and the repeating unit represented by Formula (2) :
Figure imgf000049_0001
wherein, R1 represents a hydrogen atom or a substituent; L1 represents a divalent linking group or a single bond; and represents a monocyclic or polycyclic ring,
Figure imgf000049_0002
wherein, β represents a monocyclic or polycyclic ring.
[0174]
In Formula (1), R1 preferably represents a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further more preferably a hydrogen atom or a methyl group.
[0175]
In Formula (1), L1 preferably represents a divalent linking group selected from -CO-, -0-, -CH2-, and combinations thereof or a single bond, more preferably a divalent linking group selected from -CO-, -0-, -C¾-, and combinations thereof. L1 preferably has -C (=0) -0- on the side bonding to the main chain.
[0176]
In Formula (1) , a is preferably a cyclic skeletal structure composed of 6 to 20 carbon atoms, more preferably a cyclic skeletal structure selected from the following Group (1) :
Group (1)
Figure imgf000050_0001
[0177]
The cyclic structures may have substituents or may not. The substituents are preferably alkyl groups, more preferably alkyl groups having 1 to 3 carbon atoms, further more preferably methyl groups.
[0178]
In Formula (2), β is a cyclic skeletal structure composed of 6 to 20 carbon atoms, preferably a cyclic skeletal structure selected from the following Group (2):
Figure imgf000050_0002
[0179]
The cyclic structures may have substituents or may not. Examples of the substituent include alkyl, allyl, oxo, hydroxy, and cyano groups and halogen atoms, and these substituents may be further substituted by these substituents. The substituent is preferably composed of one or more of carbon, hydrogen, oxygen, and nitrogen atoms. The total number of carbon, oxygen, and nitrogen atoms constituting the substituent is preferably 1 to 10, more preferably 1 to 5.
[0180]
The repeating unit represented by Formula (1) is preferred to the repeating unit represented by Formula (2) .
[0181]
Examples of the polymerizable group of the resin (A) in the present invention include acryloyl, methacryloyl (throughout the specification, acryloyl and methacryloyl groups may be collectively referred to as " (meth) acryloyl group"), vinyl, allyl, isocyanate, and epoxy groups. The polymerizable group is more preferably a (meth) acryloyl , epoxy, or vinyl group; more preferably a (meth) acryloyl or vinyl group; and further more preferably a vinyl group.
[0182]
In particular, the resin (A) of the present invention preferably comprises repeating units represented by Formula (3) :
Figure imgf000051_0001
wherein, R3 to R6 each independently represent a hydrogen atom or a substituent; and L3 represents a divalent linking group or a single bond.
[0183]
R3 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further more preferably a hydrogen atom or a methyl group.
[0184]
R4 and R5 are each preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and further more preferably a hydrogen atom.
[0185]
R6 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further more preferably a hydrogen atom or a methyl group.
[0186]
L3 preferably represents a divalent linking group selected from -CO-, -0-, -CH2-, and combinations thereof and more preferably has a structure represented by -C(=0)-0-.
[0187] The resin (A) can be generally synthesized by a known process using a photocurable resin composition comprising a polymerizable compound, for example, through radical polymerization, ionic polymerization, or ring-opening polymerization.
[0188]
The repeating units represented by Formulae (1) to (3) may be used alone or in combination.
[0189]
Specific examples of the polymerizable compound that can form the repeating unit represented by Formula (1) through polymerization, specific examples of the polymerizable compound that can form the repeating unit represented by Formula (2) through polymerization, and specific examples of the polymerizable compound that can form the repeating unit represented by Formula (3) through polymerization are the same as those in the first embodiment .
Copolymerizable monomers
[0190]
The resin (A) used in the present invention may be produced by copolymerization of a monomer that can form a repeating unit represented by Formula (1), (2), or (3) with another monomer, for example, a monomer described in Polymer Handbook, 2nd ed., J. Brandrup, Wiley Interscience (1975), Chapter 2, pp. 1-483.
[0191]
Specific examples of the monomer are the same as those described in the first embodiment.
[0192]
Other examples of the monomer include crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, and maleylonitrile .
[0193]
The resin (A) is preferably composed of 5 to 100% by mass of a repeating unit represented by Formula (1) and/or a repeating unit represented by Formula (2), 0 to 95% by mass of a repeating unit represented by Formula (3), and 5% by mass or less of a repeating unit derived from any other polymerizable monomer. The content of the repeating unit represented by Formula (1) and/or the repeating unit represented by Formula (2) is preferably 5 to 95% by mass, more preferably 30 to 90% by mass, and further more preferably 40 to 80% by mass. The content of the repeating unit represented by Formula (3) is preferably 5 to 95% by mass, more preferably 10 to 70% by mass, and further more preferably 20 to 60% by mass.
[0194]
The resin (A) preferably has a molecular weight of 40000 or less from the viewpoint of viscosity and more preferably 3000 to 25000 from the viewpoint of volumetric shrinkage .
[0195]
The resin (A) preferably has a molecular weight distribution (Pd) of 1.0 to 6.0, more preferably 1.0 to 3.5.
[0196]
The content of the resin (A) in the photocurable resin composition of the present invention is preferably in a range of 5 to 60% by mass, more preferably 7 to 50% by mass, and further more preferably 10 to 40% by mass.
Polymerizable compound (B)
[0197]
The polymerizable compound (B) used in the present invention comprises an alicyclic hydrocarbon group and a polymerizable group. In this regard, the polymerizable compound (B) is outside the definition of the "resin (A) having an alicyclic hydrocarbon group and having a weight average molecular weight of 40000 or less" and is usually a compound having a molecular weight of 1000 or less and is preferably a monomer or an oligomer.
[0198]
The polymerizable group is preferably acryloyl, methacryloyl, propenyl, vinyl, allyl, isocyanate, or epoxy group and more preferably at least one of a (meth) acryloyl group and an epoxy group from the viewpoint of curing properties. One molecule may contain one polymerizable group or two or more polymerizable groups.
[0199]
The polymerizable compound (B) preferably has an alicyclic structure of 6 to 16 carbon atoms, more preferably 6 to 10 carbon atoms.
[0200]
The polymerizable group and the alicyclic structure are linked to each other directly or via a linking group, preferably directly or via a divalent linking group selected from -CO-, -0-, -CH2-, and combinations thereof.
[0201]
The polymerizable compound (B) preferably has a molecular weight of 100 to 700, more preferably 130 to 600, and further more preferably 150 to 400.
[0202]
Specific examples of the polymerizable compound (B) are shown below, but are not limited to these structures.
Figure imgf000054_0001
[0203]
These polymerizable compounds (B) may be contained alone or in combination (as a mixture) in. the photocurable resin composition. In the present invention, the photocurable resin composition preferably comprises both a polymerizable compound having a (meth) acrylate group and a polymerizable compound having an epoxy group. The content of two or more of the polymerizable compound (B) in the photocurable resin composition of the present invention is preferably in a range of 20 to 90% by mass, more preferably 25 to 80% by mass, and further more preferably 30 to 70% by mass. The ratio of the resin (A) to the polymerizable compound (B) is preferably 1:1.9 to 1:4 from the viewpoint of viscosity, more preferably 1:2.3 to 1:3.5 from the viewpoint of volumetric shrinkage rate.
Compound (C) generating a radical or an acid by irradiation of active light or radiation
[0204]
In the second embodiment, the compound that generates a radical by irradiation of active light or radiation (hereinafter also referred to as " (photo) polymerization initiator") can be selected from, for example, compounds known as radical polymerization initiators within a range that does not depart from the gist of the present invention .
[0205]
The compound (C) that generates a radical or an acid by irradiation of active light or radiation in the second embodiment is the same compound (C) in the first embodiment, and the preferable range of the content thereof is also the same as that in the first embodiment.
Surfactant (D)
[0206]
The photocurable resin composition according to the second embodiment of the present invention comprises a surfactant. Examples of useful surfactants include fluorine surfactants containing fluorine atoms, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants containing silicon atoms. Surfactants containing silicon atoms and/or fluorine atoms are preferred.
[0207]
The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total mass of the photocurable resin composition. The surfactants may be used alone or in combination. [0208]
In particular, the content of the surfactant containing fluorine atoms is preferably 4% by mass or less of the solid content in the photocurable resin composition from the viewpoint of adhesion to glass. The lower limit is not particularly defined, but may be, for example, 0.1% by mass or more.
[0209]
The content of the surfactant containing silicon atoms can be, for example, 0.5 to 10% by mass of the solid content of the photocurable resin composition. A higher content of the surfactant is preferred from the viewpoint of reducing the force for releasing, but from the veiwpoint of disorder or deformation in shape, the content is preferably 0.5 to 5% by mass.
[0210]
However, this does not apply to surfactants containing silicon atoms and fluorine atoms.
[0211]
Examples of the fluorine surfactant include MEGAFAC
F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, and F781 (all manufactured by DIC Corp.), Fluorad FC430, FC431, and FC171 (all manufactured by Sumitomo 3M Ltd.), and Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (all manufactured by Asahi Glass Co., Ltd. ) .
[0212]
The content of fluorine in the fluorine surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and further more preferably 7 to 25% by mass. The fluorine surfactant containing fluorine in this range is effective for improving uniformity in film thickness and reducing the necessary volume of the solvent and also has satisfactory solubility in the photocurable resin composition .
[0213]
Specific examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate and glycerol ethoxylate) , polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester (e.g., Pluronic L10, L31, L61, L62, 10R5, 17R2, and 25R2 and Tetronic 304, 701, 704, 901, 904, and 150R1 manufactured by BASF; and Solsperse 20000 manufactured by The Lubrizol Corp.).
[0214]
Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita & Co., Ltd.), organosiloxane polymers (trade name: KP341, manufactured by Shin-Etsu Chemical Co., Ltd.), and (meth) acrylic acid (co) polymers (trade name: Polyflow No. 75, No. 90, and No. 95, manufactured by Kyoeisha Chemical Co., Ltd., and trade name: W001, manufactured by Yusho Co., Ltd.).
[0215]
Examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.) .
[0216]
Examples of silicone surfactant include "ToraySilicone
DC3PA", "ToraySilicone SH7PA", "ToraySilicone DCllPA", "ToraySilicone SH21PA", "ToraySilicone SH28PA" ,
"ToraySilicone SH29PA", "ToraySilicone SH30PA" , and "ToraySilicone SH8400", manufactured by Dow Corning Toray Co., Ltd.; "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", and "TSF-4452", manufactured by Momentive Performance Materials Inc.; "KP341", "KF6001", and "KF6002", manufactured by Shin-Etsu Chemical Co., Ltd.; and "BYK307", "BYK323", and "BYK330", manufactured by BYK-Chemie GmbH.
Additive (E)
[0217]
The photocurable resin composition according to the second embodiment of the present invention may further contain additives such as a polymerization inhibitor and a dissolution modulator, as in the first embodiment.
[0218]
The curable resin composition according to the second embodiment of the present invention preferably contains 15% by mass or less of components other the components (A) to (D) .
Solvent
[0219]
The composition of the present invention may contain a solvent. The content of the solvent is preferably 10% by mass or less, and more preferably 5% by mass or less from the viewpoint of reducing air bubbles in a molded product.
[0220]
However, it is preferred that the photocurable resin composition of the present invention do not substantially contain a solvent. "Not substantially contain" means that, for example, the content of a solvent is 1% by mass or less of the photocurable resin composition.
[0221]
The curable resin composition of the present invention can have a viscosity of 0.1 to 25 Pa-s, further 0.3 to 15 Pa-s, and further 0.3 to 7 Pa-s. In the curable resin composition of the present invention, high optical characteristics and a low volumetric shrinkage rate can be maintained even at such a low viscosity.
[0222]
In the photocurable resin composition of the present invention, the volumetric shrinkage rate during curing is preferably 10% or less, more preferably 5% or less, and further more preferably 3% or less.
[0223]
In curable resin compositions, it is technically difficult to achieve compatibility between a high refractive index and a high Abbe number. Specifically, it is difficult to achieve both a refractive index of 1.5 or more and an Abbe number of 50 or more.
[0224] Conventional compositions for forming lenses contain inorganic particles in order to increase the refractive index and the Abbe number, but the present invention can achieve a high refractive index and a high Abbe number even if the composition does not substantially contain such inorganic particles (e.g., the content of the inorganic particles is 1% by mass or less of the composition) .
[0225]
In the curable resin composition of the present invention, the haze after curing is preferably 5% or less, more preferably 3% or less.
[0226]
In the photocurable resin composition of the present invention, the glass transition temperature after curing is preferably 200°C or more, and more preferably 260°C or more.
Optical component
[0227]
For example, the cured product of the curable resin composition of the present invention can be preferably used as optical components of, for example, various display devices (e.g., liquid crystal displays and plasma displays), various projectors (e.g., OHPs and liquid crystal projectors), optical fiber communication systems
(e.g., optical waveguides and optical amplifiers), and photographic devices such as cameras and video cameras. The cured product of the present invention can be preferably used as optical components, in particular, lenses.
Wafer level lens array
[0228]
The wafer level lens array of the present invention will now be described. FIG. 1 is a plan view illustrating an example configuration of a wafer level lens array. FIG. 2 is a cross-sectional view of the wafer level lens array shown in FIG. 1 taken along the line A-A.
[0229]
As shown in FIG. 2, the wafer level lens array comprises a substrate 10 and a plurality of lenses 12 arranged on the substrate 10. The lenses 12 are one- dimensionally or two-dimensionally arranged on the substrate 10. A light-shielding film 14 may be provided between adjacent lenses 12 for preventing transmission of light from regions other than the lenses.
[0230]
In this embodiment, a configuration shown in FIG. 1, i.e., a plurality of lenses 12 two-dime sionally arranged on a substrate 10 will be described as an example. The lenses 12 and the substrate 10 are made of a cured product of the photocurable resin composition of the present invention, where the lenses 12 are integrally formed on the substrate 10 or are separately formed and immobilized to the substrate 10. The photocurable resin composition according to the second embodiment of the present invention is preferably used in integral molding of the lenses 12 and the substrate 10.
[0231]
The wafer level lens array of the present invention may have any size, for example, 6 to 12 inches. The curable resin composition of the present invention can advantageously form a satisfactory wafer level lens array even if the size is 8 inches or more. In particular, the composition can be more preferably applied to a wafer level lens array having a size of 8 to 12 inches. Although conventional wafer level lens arrays tend to warp with an increase in size, but the photocurable resin composition of the present invention can form a satisfactory wafer level lens array even if the size is 8 inches or more.
[0232]
Though one example has been described here, the wafer level lens array of the present invention is not limited thereto and can be provided in various forms such as a multi-layer structure or lens modules separated by dicing. Method of producing molded product
[0233]
Molded products such as optical components can be produced using the photocurable resin composition of the present invention by a known method. For example, the photocurable resin composition of the present invention is injected into a mold and is irradiated with active energy and/or heated to be hardened into a molded product. In the present invention, combination of irradiation with active energy and heating is preferred, which can suppress the shrinkage during curing in dies (preferably molding dies) to precisely transfer the mold shape and inhibit leakage to the gap (clearance) between the dies.
Formation of wafer level lens array
[0234]
An example of a method of forming the wafer level lens array will be described. FIG. 3 illustrates supplying of a molding material, i.e., the photocurable resin composition (shown as M in FIG. 3) of the present invention, on a substrate. As shown in FIG. 3, the molding material M is dropped onto a substrate 10 with a dispenser 50 at positions to form lenses. On this occasion, the molding material M is supplied in an amount corresponding to one lens 12 per position.
[0235]
After the supply of the molding material M on the substrate 10, as shown in FIG. 4A, a mold 60 for forming lenses is disposed. The mold 60 has concaves 62 for transferring shapes of lenses 12, the number of concaves corresponding to the required number of lenses 12.
[0236]
As shown in FIG. 4B, the mold 60 is pressed to the molding material M on the substrate 10 to mold the molding material M into shapes along the concaves. Then, when the molding material M is a thermosetting resin or ultraviolet curable resin, the molding material M is cured by being irradiated with heat or ultraviolet rays from the outside of the mold while the mold 60 is being pressed to the molding material M.
[0237]
After the curing of the molding material M, as shown in FIG. 4C, the substrate 10 and lenses 12 are released from the mold 60. [0238]
FIG. 5 illustrates another example configuration of a wafer level lens array. The wafer level lens array shown in FIG. 5 is a monolithic configuration where a substrate 10 and lenses 12 are formed through a one-shot process. In this example, a plurality of concave lenses 12 are formed on one surface (the upper surface in the drawing) of the substrate 10, and a plurality of convex lenses 20 are formed on the other surface (the lower surface) . In this embodiment, a patterned light-shielding film 14 may be formed on the substrate 10 in the region excluding the lens surfaces 12a, i.e., the surfaces of the substrate 10 and the edges 12b.
Examples
[0239]
The present invention will now be described by Examples more specifically. The materials, amounts thereof, proportions, details and orders of treatments, and other factors in the following examples can be appropriately changed within ranges that do not depart from the gist of the present invention. Thus, the scope of the present invention should not be limited to the following specific examples .
Synthetic Example 1
(A) Synthetic example of resin
[0240]
Into a 1-L three-neck flask equipped with a reflux condenser and a gas inlet cock was placed 30.0 g of tricyclo [5, 2, 1, 02'6] deca-8-yl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FA-513M, corresponding to Example Compound Al-1), 20.0 g of ally methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., corresponding to Example Compound A3-1), and 500.0 g of ethyl acetate. After the system was purged with nitrogen twice, 0.6 g of a polymerization initiator, V-65 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was added to the flask. The system was further purged with nitrogen twice, and the mixture was heated at 65°C for 6 hr under a nitrogen flow. Subsequently, the reaction solution was added to 2 L of methanol, and a precipitated white solid was collected by suction filtration. The solid was dried under reduced pressure at 70°C for 5 hr to remove the solvent to give polymer P-l (yield: 60%, weight average molecular weight (Mw) : 40000, molecular weight distribution (Pd) : 2.43) .
[0241]
Other polymers were similarly prepared with other types and blending proportions of the raw material components (a) and (b) shown below.
[0242]
Figure imgf000063_0001
Figure imgf000064_0001
Preparation of raw materials
[0243]
The prepared polymer was put into a glass bottle and was stirred overnight with a stirrer for high viscosity. The resulting solution was filtered through a disk filter having a pore size of 5 μιη. Thus, solutions (Le-IA) to (Le- 19A) were prepared. In Table 2, the numbers show the proportion (% by weight) of each component. [0244]
Figure imgf000065_0001
B-1: Dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
B-2: 1-Adamantyl methacrylate (manufactured by Osaka Organic Chemical Industry Ltd.)
B-3: 3, 4-Epoxycyclohexenylmethyl 3 ' , 4 ' -epoxycyclohexene carboxylate (manufactured by Daicel Corp., Celloxide 2021) B-4: tert-Butyl methacrylate
B-5: 1, 3-Bis (isocyanatomethyl) cyclohexane (Takenate 600, manufactured by Mitsui Chemicals, Inc.)
B-6: Cyclohexyl methacrylate
C-1: IRGACURE 184 (manufactured by BASF)
C-2: WPI-113 (manufactured by WAKO)
D-1: p-Methoxyphenol (manufactured by Tokyo Chemical
Industry Co., Ltd., M0122)
D-2 : β-Caryophyllene (manufactured by Tokyo Chemical
Industry Co., Ltd., C0796)
D-3: Hydroquinone
D-4: Tributylamine
Evaluation
(1) Measurement of refractive index
[0245]
A solution was dropped onto a hydrophobized glass substrate to form a solution layer with a thickness of 1 mm. The layer was exposed to light of 4000 mJ/cm2 to heat at 180°C for 2 hr using a high-pressure mercury lamp HB-50101BY (Ushio Inc.) under a N2 atmosphere. Subsequently, the glass substrate was removed to give a hardened film having a thickness of 1 mm. The refractive index of the resulting film for light of 589 nm wavelength was measured with an Abbe refractometer (DR-M4, manufactured by Atago Co., Ltd.). (2) Measurement of Abbe number (vD)
[0246]
The refractive indices of the hardened film produced in "(1) Measurement of refractive index" were measured for light of 486 nm, 589 nm, and 656 nm wavelengths with an Abbe refractometer (DR-M4, manufactured by Atago Co., Ltd.). The Abbe number was calculated from the following expression using the refractive index nF at a wavelength of 486 nm, the refractive index nD at a wavelength of 589 nm, and the refractive index nC at a wavelength of 656 nm. A higher Abbe number is preferred.
Figure imgf000067_0001
(3) Measurement of viscosity
[0247]
The shear viscosity of the prepared solution was measured with a rheometer (manufactured by Anton Paar, Physica MCR301) to calculate the viscosity.
(4) Volumetric shrinkage rate
[0248]
A prepared solution was poured in an aluminum cup of 0.8 cm diameter and was exposed to light of 4000 mJ/cm2 using a high-pressure mercury lamp HB-50101BY (Ushio Inc.) to obtain about 0.35 g of a molded product. The volume VI of the resulting molded product was measured with a dry- type automatic densitometer (manufactured by Shimadzu Corp., AccuPyc 1330-03) . Subsequently, the molded product was annealed at 180°C for 2 hr under a N2 atmosphere. The volume V2 of this molded product was measured with the dry- type automatic densitometer.
[0249]
Volumetric shrinkage was determined from the following expression :
Volumetric shrinkage rate (%) = [ (V1-V2 ) /VI ] xlOO
A smaller percentage means a lower volumetric shrinkage rate .
(5) Measurement of haze
[0250]
A solution was dropped onto a hydrophobized glass substrate to form a solution layer with a thickness of 1 mm. The layer was exposed to light of 4000 mJ/cm2 to heat at 180°C for 2 hr using a mercury lamp under a N2 atmosphere. Subsequently, the glass substrate was removed to give a hardened film having a thickness of 1 mm.
[0251]
The hardened film was evaluated by visual observation. The evaluation criteria are as follows, where a smaller number means less haze: 1: The film is transparent and clear and does not have air bubbles;
2: The film is transparent, but slightly unclear, without air bubbles;
3: The film is transparent, but slightly unclear, with air bubbles; and
4: The film is colored and unclear with air bubbles. The results are shown in Table 3.
[0252]
Figure imgf000068_0001
[0253]
The results in the table demonstrate that the composition of the present invention can achieve compatibility among a high refractive index, a high Abbe number, low viscosity, a low volumetric shrinkage rate, and low haze.
Synthetic example 2
(A) Synthetic example of resin
[0254]
Into a 1-L three-neck flask equipped with a reflux condenser and a gas inlet cock was placed 45.0 g of tricyclo [ 5 , 2 , 1 , 02' 6] deca-8-yl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FA-513M, corresponding to Example Compound Al-1) , 5.0 g of ally methacrylate (manufactured by Wako Pure Chemical Industries, Ltd. , corresponding to Example Compound A3-1) , and 500.0 g of ethyl acetate. After the system was purged with nitrogen twice, 0.6 g of a polymerization initiator, V-65 (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was added to the flask. The system was further purged with nitrogen twice, and the mixture was heated at 65°C for 6 hr under a nitrogen flow. Subsequently, the reaction solution was added to 2 L of methanol, and a precipitated white solid was collected by suction filtration. The solid was dried under reduced pressure at 70°C for 5 hr to remove the solvent to give polymer P-l (yield: 60%, weight average molecular weight (Mw) : 40000, molecular weight distribution (Pd) : 2.43) .
[0255]
Other polymers were similarly prepared with other types and blending proportions of the raw material components (a) and (b) shown below.
Figure imgf000070_0002
Figure imgf000070_0001
Figure imgf000071_0001
Preparation of raw materials
[0257]
The prepared polymer was put into a glass bottle and was stirred overnight with a stirrer for high viscosity. The resulting solution was filtered through a disk filter having a pore size of 5 μπι. Thus, solutions (Le-IB) to (Le- 14B) were prepared. In Table 5, the numbers show the proportion (% by weight) of each component.
[0258]
Figure imgf000072_0001
B-1' : Dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical Co., Ltd.)
B-2' : 1-Adamantyl methacrylate (manufactured by Osaka Organic Chemical Industry Ltd.)
B-3': 3, 4-Epoxycyclohexenylmethyl 3 ' , 4 ' -epoxycyclohexene carboxylate (manufactured by Daicel Corp., Celloxide 2021) B-4': tert-Butyl methacrylate
B-5': 1, 3-Bis (isocyanatomethyl) cyclohexane (Takenate 600, manufactured by Mitsui Chemicals, Inc.)
B-6' : Cyclohexyl methacrylate
C-1' : IRGACURE 184 (manufactured by. BASF)
C-2' : WPI-113 (manufactured by WAKO) D-l' : KF-6012 (manufactured by Shin-Etsu Chemical Co., Ltd. )
D-2' : KF-6015 (manufactured by Shin-Etsu Chemical Co., Ltd. )
D-3' : FTX-230G (manufactured by Neos Co., Ltd.)
D-4' : FTX-209F (manufactured by Neos Co., Ltd.)
E-l' : p-Methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd., M0122)
E-2': β-Caryophyllene (manufactured by Tokyo Chemical Industry Co., Ltd., C0796)
E-3' : Hydroquinone
E-4' : Tributylamine
Evaluation
(1) Measurement of refractive index
[0259]
Refractive indices were measured as in Example 1A.
(2) Measurement of Abbe number (vD)
[0260]
Abbe numbers were measured as in Example 1A.
(3) Measurement of viscosity
[0261]
Viscosity was measured as in Example 1A.
(4) Measurement of force for releasing
[0262]
A polydimethylsiloxane mold of 2 x 2 cm was set to an air-compression UV imprint apparatus (manufactured by MEPJ) equipped with a function, of measuring force for releasing, and about 1 μL of a prepared solution was applied onto the mold. A glass wafer was placed on the solution such that the distance between the mold and the glass wafer was 200 jim. Subsequently, the glass wafer was exposed to light for 100 sec, and the mold was then removed. On this occasion, the force (N/cm2) for releasing was calculated from the maximum force (N) applied to the mold and the testing area (cm2) .
(5) Adhesion to glass
[0263]
A prepared solution was applied onto a glass substrate of 7 x 7 cm with a spin coater at 1000 rpm. This substrate was exposed to light of 4000 mJ/cm2 using a high-pressure mercury lamp HB-50101BY (Ushio Inc.). The resulting film was used in a Japanese Industrial Standard (JIS) cross-cut tape peeling test.
[0264]
The evaluation criteria are as follows, where a smaller number means higher adhesion to glass:
1: After peeling of tape, the film completely remained;
2: After peeling of tape, the film did not completely remained and did not completely peeled; and
3: After peeling of tape, the film was completely peeled.
[0265]
Figure imgf000074_0001
[0266]
The results in the table demonstrate that the composition of the present invention can achieve compatibility among a high refractive index, a high Abbe number, low viscosity, a low force for releasing, and high adhesion to glass.
[0267]
The present disclosure relates to the subject matter contained in Japanese Patent Application No. 185034/2011 filed on August 26, 2011 and Japanese Patent Application No. 184035/2011 filed on August 26, 2011, which are expressly incorporated herein by reference in their entirety. All the publications referred to in the present specification are also expressly incorporated herein by reference in their entirety.
The foregoing description of preferred embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or to limit the invention to the precise form disclosed. The description was selected to best explain the principles of the invention and their practical application to enable others skilled in the art to best utilize the invention in various embodiments and various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention not be limited by the specification, but be defined claims set forth below.

Claims

1. A photocurable resin composition comprising:
a resin (A) having an alicyclic hydrocarbon group and having a weight average molecular weight of 40000 or less; a compound (B) having an alicyclic hydrocarbon group and a polymerizable group; and
a compound (C) generating a radical or an acid with irradiation of active light or radiation, or
a photocurable reisn composition comprising:
a resin (A) having an alicyclic hydrocarbon group;
a compound (B) having an alicyclic hydrocarbon group and a polymerizable group;
a compound (C) generating a radical or an acid by irradiation of active light or radiation; and
a surfactant (D) .
2. The photocurable resin composition according to Claim 1, comprising:
the resin (A) having an alicyclic hydrocarbon group and having a weight average molecular weight of 40000 or less;
the compound (B) having an alicyclic hydrocarbon group and a polymerizable group; and
the compound (C) generating a radical or an acid by irradiation of active light or radiation.
3. The photocurable resin composition according to Claim 1 or 2, the composition further comprising a polymerization inhibitor (D) . . The photocurable resin composition according to Claim 1, comprising:
the resin (A) having an alicyclic hydrocarbon group; the compound (B) having an alicyclic hydrocarbon group and a polymerizable group;
the compound (C) generating a radical or an acid by irradiation of active light or radiation; and the surfactant (D) .
5. The photocurable resin composition according to Claim 1 or 4, wherein the surfactant (D) contains a silicon atom and/or a fluorine atom.
6. The photocurable resin composition according to any one of Claims 1 to 5, wherein the polymerizable group of the compound (B) is a (meth) acryloyl group and/or an epoxy group .
7. The photocurable resin composition according to any one of Claims 1 to 6, wherein the ratio of the resin (A) to the compound (B) is 1:1.9 to 1:4.
8. The photocurable resin composition according to any one of Claims 1 to 7, wherein the resin (A) comprises a repeating unit having an alicyclic hydrocarbon group and a repeating unit having a polymerizable group.
9. The photocurable resin composition according to any one of Claims 1 to 8, wherein the alicyclic hydrocarbon group of the resin (A) has a hydrocarbon group having 6 or more carbon atoms.
10. The photocurable resin composition according to any one of Claims 1 to 9, wherein the resin (A) has at least one polymerizable group selected from acryloyl, methacryloyl, vinyl, ally, isocyanate, and epoxy groups.
11. The photocurable resin composition according to any one of Claims 1 to 10, wherein the resin (A) comprises a repeating unit represented by Formula (1):
Figure imgf000078_0001
wherein R1 represents a hydrogen atom or a substituent ; L1 represents a divalent linking group or a single bond; and a. represents a monocyclic or polycyclic ring.
12. The photocurable resin composition according to Claim 11, wherein the resin (A) further comprises a repeating unit represented by Formula (3):
Figure imgf000078_0002
wherein R3 to R6 each independently represent a hydrogen atom or a substituent; and L3 represents a divalent linking group or a single bond.
13. The photocurable resin composition according to any one of Claims 1 to 12, being used for a wafer level lens.
14. A lens formed of a photocurable resin composition according to any one of Claims 1 to 13.
15. A wafer level lens formed of a photocurable resin composition according to any one of Claims 1 to 13.
16. A method of producing a lens comprising:
curing a photocurable resin composition according to any one of Claims 1 to 13.
17. A method of producing a wafer level lens comprising: curing a photocurable resin composition according to any one of Claims 1 to 13.
PCT/JP2012/070866 2011-08-26 2012-08-10 Photocurable resin composition, wafer level lens, and method of producing the lens WO2013031550A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006208765A (en) * 2005-01-28 2006-08-10 Matsushita Electric Ind Co Ltd Resist material and pattern forming method using the same
JP2008225162A (en) * 2007-03-14 2008-09-25 Jsr Corp Radiation-sensitive resin composition, interlayer insulation film and microlens, and method for producing the same
WO2011105473A1 (en) * 2010-02-26 2011-09-01 新日鐵化学株式会社 Curable resin composition, cured article thereof, and optical material
WO2012014641A1 (en) * 2010-07-29 2012-02-02 富士フイルム株式会社 Curable resin composition and molded article

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006208765A (en) * 2005-01-28 2006-08-10 Matsushita Electric Ind Co Ltd Resist material and pattern forming method using the same
JP2008225162A (en) * 2007-03-14 2008-09-25 Jsr Corp Radiation-sensitive resin composition, interlayer insulation film and microlens, and method for producing the same
WO2011105473A1 (en) * 2010-02-26 2011-09-01 新日鐵化学株式会社 Curable resin composition, cured article thereof, and optical material
WO2012014641A1 (en) * 2010-07-29 2012-02-02 富士フイルム株式会社 Curable resin composition and molded article

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