Classifications

• • 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
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
  • C08F20/10—Esters
  • C08F20/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3415—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J201/00—Adhesives based on unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers

Definitions

• the present invention relates to a photocurable resin composition, an adhesive, a sealant or coating agent containing the same, a cured product thereof, a semiconductor device or electronic component containing the cured product, and a curing method, an adhesion method, a sealing method, and a coating method using the photocurable resin composition.
• Adhesives that are temporarily fixed by ultraviolet (UV) irradiation and then fully cured by heat are used in many fields (for example, Patent Documents 1 and 2). If the adhesive contains a filler, the filler can block the UV light, or if the area to which the adhesive is applied has a complex shape, the UV light can be blocked, resulting in areas in the adhesive that the UV light does not reach. In such cases, those areas will remain uncured, making it difficult to achieve the desired degree of curing. For this reason, this type of adhesive is used for the purpose of fully curing by heat in applications where there are areas that are not reached by UV light and remain uncured.
• UV ultraviolet
• the present invention aims to provide a photocurable resin composition that does not require full curing by heat, an adhesive, a sealant or coating agent containing the same, a cured product thereof, a semiconductor device or electronic component containing the cured product, and a curing method, an adhesion method, a sealing method and a coating method that use the photocurable resin composition.
• aspects of the present invention include the following curable resin composition, adhesive, encapsulant or coating agent, cured product, semiconductor device or electronic component, method for producing a cured product, method for curing a photocurable resin composition, use of the photocurable resin composition, adhesion method, encapsulation method, and coating method.
• (1) polymerizable compound, (B) a photocurable resin composition comprising a photopolymerization initiator; and (C) a photon upconversion material.
• the emission wavelength of the photon upconversion material (C) includes a wavelength of 500 nm or less.
• a semiconductor device or electronic part comprising the cured product according to (9) above.
• a method for producing a cured product comprising irradiating the photocurable resin composition according to any one of (1) to (7) above, or the adhesive, sealant, or coating agent according to (8) above, with light having a wavelength of more than 500 nm.
• a method for curing a photocurable resin composition comprising irradiating the photocurable resin composition according to any one of (1) to (7) above with light having a wavelength of more than 500 nm.
• a method for bonding at least two parts with a photocurable resin composition comprising the steps of: A step of applying the photocurable resin composition according to any one of (1) to (7) to at least one of the at least two parts; and A step of irradiating at least one of the at least two parts, the photocurable resin composition, or both of them with light having a wavelength of more than 500 nm. Gluing method.
• a method for sealing a gap between or within components with a photocurable resin composition comprising the steps of: A step of applying or injecting the photocurable resin composition according to any one of (1) to (7) into the gap between or within the components, and a step of irradiating the photocurable resin composition with light having a wavelength of more than 500 nm.
• Sealing method (16)
• a method for coating a surface of an object with a photocurable resin composition comprising the steps of: A coating method comprising the steps of: applying the photocurable resin composition according to any one of (1) to (7) to the object; and irradiating the photocurable resin composition with light having a wavelength of more than 500 nm.
• a photocurable resin composition that does not require full curing by heat, an adhesive, a sealant or coating agent containing the same, a cured product thereof, a semiconductor device or electronic component containing the cured product, and a curing method, an adhesion method, a sealing method and a coating method that use the photocurable resin composition.
• ultraviolet light refers to light with a wavelength of 200 nm to 380 nm
• visible light refers to light with a wavelength of 380 nm to 780 nm
• near-infrared light refers to light with a wavelength of 780 nm to 2500 nm
• (mid-) infrared light refers to light with a wavelength of 2.5 ⁇ m to 25 ⁇ m.
• the term "(meth)acryloyl group” includes both methacryloyl groups and acryloyl groups
• the term “(meth)acrylate compound” includes both acrylate compounds and methacrylate compounds.
• the "photocurable resin composition” may be simply referred to as the "resin composition”.
• the photocurable resin composition according to one embodiment of the present invention comprises: (A) polymerizable compound,
• the photocurable resin composition includes (B) a photopolymerization initiator, and (C) a photon upconversion material. According to this aspect, it is possible to provide a photocurable resin composition that does not require main curing by heat.
• the present inventors focused on photon upconversion materials that can convert long-wavelength light to short-wavelength light. When irradiated with specific light, photon upconversion materials generate high-energy states through multiphoton excitation, triplet-triplet annihilation, etc., and emit light with a shorter wavelength than the incident light during the relaxation process.
• the present inventors considered that by including this photon upconversion material in a resin composition and irradiating the resin composition with long-wavelength light, the photon upconversion material would perform wavelength conversion inside the resin composition, generating short-wavelength light to activate the photopolymerization initiator.
• the present inventors confirmed that the curing of the resin composition proceeds due to photon upconversion emission.
• the present inventors also confirmed that even if an object blocking UV irradiation light is present, the curing of the resin composition proceeds due to photon upconversion emission, making main curing by heat unnecessary.
• the photocurable resin composition of this embodiment contains (A) a polymerizable compound (hereinafter also referred to as "component (A)").
• the (A) polymerizable compound imparts curability and adhesiveness to the resin composition.
• the (A) polymerizable compound can be appropriately selected from a radical polymerizable compound, a cationic polymerizable compound, an anionic polymerizable compound, or any combination thereof, depending on the type of the (B) photopolymerization initiator described later.
• radically polymerizable compounds include, but are not limited to, compounds having an unsaturated double bond such as (meth)acrylate compounds, (meth)acrylamide compounds, cyanoacrylate compounds, maleimide compounds, vinyl ether compounds, styrene compounds, and methylene malonates (2-methylene-1,3-dicarbonyl compounds and their derivatives), or mixtures of compounds having an unsaturated double bond and thiol compounds (mixtures capable of ene-thiol reaction).
• compounds having an unsaturated double bond such as (meth)acrylate compounds, (meth)acrylamide compounds, cyanoacrylate compounds, maleimide compounds, vinyl ether compounds, styrene compounds, and methylene malonates (2-methylene-1,3-dicarbonyl compounds and their derivatives
• thiol compounds mixtures capable of ene-thiol reaction.
• the (meth)acrylate compound refers to a compound having at least one (meth)acryloyl group in the molecule, and includes a monofunctional (meth)acrylate compound having one (meth)acryloyl group and a polyfunctional (meth)acrylate compound having two or more (meth)acryloyl groups.
• Examples of the monofunctional (meth)acrylate compound include: -ethyl (meth)acrylate, trifluoroethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate , stearyl (meth)acrylate, lauryl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth
• polyfunctional (meth)acrylate compounds include diacrylate and/or dimethacrylate of tris(2-hydroxyethyl)isocyanurate; tris(2-hydroxyethyl)isocyanurate triacrylate and/or trimethacrylate; trimethylolpropane triacrylate and/or trimethacrylate, or an oligomer thereof; pentaerythritol triacrylate and/or trimethacrylate, or an oligomer thereof; polyacrylate and/or polymethacrylate of dipentaerythritol; tris(acryloxyethyl)isocyanurate; caprolactone-modified tris(acryloxyethyl)isocyanurate; caprolactone-modified tris(methacryloxyethyl)isocyanurate; polyacrylate and/or polymethacrylate of alkyl-modified dipentaerythritol; caprolactone-
• any one of the above-mentioned (meth)acrylate compounds may be used alone, or two or more of them may be used in combination.
• Examples of commercially available (meth)acrylate compounds include polyester acrylate (product name: EBECRYL810) manufactured by Daicel-Allnex Corporation, ditrimethylolpropane tetraacrylate (product name: EBECRYL140) manufactured by Daicel-Allnex Corporation, polyester acrylate (product name: M7100) manufactured by Toagosei Co., Ltd., dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A) manufactured by Kyoeisha Chemical Co., Ltd., and neopentyl glycol modified trimethylolpropane diacrylate (product name: Kayarad R-604) manufactured by Nippon Kayaku Co., Ltd., but are not limited thereto.
• a (meth)acrylamide compound is a compound having at least one acrylamide group (H 2 C ⁇ CHCONH—) or methacrylamide group ((H 2 C ⁇ C(CH 3 )CONH—).
• Examples of (meth)acrylamide compounds include, but are not limited to, N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, 1,2-di(meth)acrylamide ethylene glycol, and the like.
• the cyanoacrylate compound may be a known compound represented by the formula H 2 C ⁇ C(CN)—COOR.
• R is an ester residue such as an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, or an aryl group.
• the number of carbon atoms in the ester residue is not particularly limited, but typically, one having 1 to 8 carbon atoms may be used.
• Ester residues consisting of substituted hydrocarbon groups such as alkoxyalkyl groups and trialkylsilylalkyl groups may also be used.
• cyanoacrylate compounds include, but are not limited to, alkyl and cycloalkyl cyanoacrylates such as methyl cyanoacrylate, ethyl cyanoacrylate, propyl cyanoacrylate, butyl cyanoacrylate, and cyclohexyl cyanoacrylate; alkenyl and cycloalkenyl cyanoacrylates such as allyl cyanoacrylate, methallyl cyanoacrylate, and cyclohexenyl cyanoacrylate; alkynyl cyanoacrylates such as propangyl cyanoacrylate; aryl cyanoacrylates such as phenyl cyanoacrylate and toluyl cyanoacrylate; heteroatom-containing methoxyethyl cyanoacrylate, ethoxyethyl cyanoacrylate, and furfuryl cyanoacrylate; silicon-containing trimethylsilylmethyl cyanoacrylate, trimethylsilylethyl
• a maleimide compound is a compound having at least one maleimide group.
• Maleimide compounds include monofunctional maleimide compounds having one maleimide group, and polyfunctional maleimide compounds having two or more maleimide groups, and maleimide compounds having two maleimide groups in particular are sometimes called bismaleimide compounds.
• bismaleimide compounds include N,N'-(4,4'-diphenylmethane)bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, bis-(3-ethyl-5-methyl-4-maleimidophenyl)methane, m-phenylene bismaleimide (N,N'-1,3-phenylene bismaleimide), and 1,6-bismaleimide.
• dimaleimide examples include, but are not limited to, hexane, 1,2-bismaleimideethane (N,N'-ethylene dimaleimide), N,N'-(1,2-phenylene) bismaleimide, N,N-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, N,N'-(sulfonyldi-p-phenylene) dimaleimide, N,N'-[3,3'-(1,3-phenylenedioxy)diphenyl]bismaleimide, N,N'-[4,4'-(1,3-phenylenedioxy)diphenyl]bismaleimide, and 4,4'-dimaleimide phenyl ether. These may be used alone or in combination of two or more.
• a bismaleimide compound having a hydrocarbon group derived from a dimer acid can be used as the bismaleimide compound.
• Such bismaleimide compounds are described, for example, in JP 2015-193725 A.
• Commercially available bismaleimide compounds having a hydrocarbon group derived from a dimer acid include, but are not limited to, products named "BMI-689", “BMI-1500”, and “BMI-1700", which are liquid at 25°C, and "BMI-3000", which is solid at 25°C (all manufactured by Designer Molecules Inc.). These may be used alone or in combination of two or more types.
• monofunctional maleimide compounds include monofunctional aliphatic maleimide compounds such as N-n-butylmaleimide, N-hexylmaleimide, 2-maleimidoethyl-ethyl carbonate, 2-maleimidoethyl-propyl carbonate, and N-ethyl-(2-maleimidoethyl) carbamate; alicyclic monofunctional maleimide compounds such as N-cyclohexylmaleimide, N-arylmaleimide such as N-phenylmaleimide; and N-aralkylmaleimide such as N-benzylmaleimide, but are not limited thereto.
• monofunctional aliphatic maleimide compounds such as N-n-butylmaleimide, N-hexylmaleimide, 2-maleimidoethyl-ethyl carbonate, 2-maleimidoethyl-propyl carbonate, and N-ethyl-(2-maleimidoethyl) carb
• the aliphatic maleimide and alicyclic maleimide may have a substituent, and examples of the substituent include a phenyl group, a benzyl group, and a hydroxy group.
• the N-arylmaleimide and N-aralkylmaleimide may have a substituent, and examples of the substituent include an alkyl group, a nitro group, a hydroxy group, an alkoxy group, a carboxyl group, and a halogeno group, but are not limited thereto. These may be used alone or in combination of two or more.
• monofunctional maleimides include, but are not limited to, Imilex®- C and Imilex®- P (both manufactured by Nippon Shokubai Co., Ltd.) and O-CPMI (manufactured by Daiwa Kasei Kogyo Co., Ltd.).
• a vinyl ether compound is a compound having at least one vinyl ether group (H 2 C ⁇ CH—O—).
• vinyl ether compounds include, but are not limited to, ethyl vinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether, cyclohexyl vinyl ether, 1,4-butanediol divinyl ether, nonanediol divinyl ether, cyclohexanediol divinyl ether, cyclohexanedimethanol divinyl ether, and the like. These may be used alone or in combination of two or more.
• the styrene compound is a compound having at least one styrene group (H 2 C ⁇ CH—C 6 H 5 —).
• examples of the styrene compound include, but are not limited to, styrene, ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, N,N-diethyl-4-aminoethylstyrene, and 4-methoxystyrene. These may be
• Methylene malonates are malonates having at least one methylene group in the molecule, and include monofunctional methylene malonates having one methylene group and polyfunctional methylene malonates having two or more methylene groups.
• the molecular weight of the methylene malonates is preferably 220 or more.
• the methylene malonates may be used alone or in combination of two or more types.
• the thiol compound in the mixture of the compound having an unsaturated double bond and the thiol compound is a compound containing at least one thiol group, and the thiol group can undergo a radical addition reaction (ene-thiol reaction) with the unsaturated double bond of the compound having an unsaturated double bond.
• Thiol compounds are broadly classified into thiol compounds having a hydrolyzable partial structure such as an ester bond in the molecule (i.e., hydrolyzable) and thiol compounds not having such a partial structure (i.e., non-hydrolyzable).
• hydrolyzable thiol compounds include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (manufactured by SC Organic Chemical Co., Ltd.: TEMPIC), pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: PEMP), and tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: EGMP- 4), dipentaerythritol hexakis(3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd.: DPMP), pentaerythritol tetrakis(3-mercaptobutyrate) (
• non-hydrolyzable polyfunctional thiol compounds include 1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril (manufactured by Shikoku Chemical Industry Co., Ltd.: TS-G), 1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril (manufactured by Shikoku Chemical Industry Co., Ltd.: C3 TS-G), 1,3,4,6-tetrakis(mercaptomethyl)glycoluril, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methylglycoluril, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methylglycoluril, 1,3,4,
• Cationically polymerizable compounds are compounds that have one or more cationically polymerizable groups in the molecule.
• cationically polymerizable groups include, but are not limited to, epoxy groups, oxetanyl groups, vinyl ether groups, etc.
• cationically polymerizable compounds include, but are not limited to, epoxy compounds, oxetane compounds, polystyrene compounds, vinyl ether compounds, etc.
• Epoxy compounds include monofunctional epoxy compounds that have one epoxy group and polyfunctional epoxy compounds that have two or more epoxy groups.
• Polyfunctional epoxy compounds are broadly divided into aromatic polyfunctional epoxy compounds and polyfunctional epoxy compounds that do not have an aromatic ring.
• Epoxy resins having an aromatic ring structure include, specifically, polyfunctional epoxy resins such as bisphenol A type epoxy resins (EPICLON (registered trademark) 850, 850-S, EXA-850CRP, EXA-8067, etc., manufactured by DIC Corporation), special epoxy resins containing compounds in which a polyalkylene oxide structure is added to an epoxy resin and bisphenol A structure (AER9000 manufactured by Asahi Kasei Corporation, EP-4000S, EP-4003S, EP-4010S, manufactured by ADEKA Corporation), and bisphenol F type epoxy resins (EP-4000S, EP-4003S, EP-4010S, manufactured by ADEKA Corporation).
• polyfunctional epoxy resins such as bisphenol A type epoxy resins (EPICLON (registered trademark) 850, 850-S, EXA-850CRP, EXA-8067, etc., manufactured by DIC Corporation), special epoxy resins containing compounds in which a polyalkylene oxide structure is added to an epoxy resin and bisphenol A
• polyfunctional epoxy resin examples include EPICRON (registered trademark) 830-S, EXA-830LVP, etc., manufactured by DIC Corporation), bisphenol AD type epoxy resin, bisphenol S type epoxy resin, naphthalene type epoxy resin (EPICLON (registered trademark), HP-4032D, HP-720H, etc., manufactured by DIC Corporation), phenol novolac type epoxy resin (EPICLON (registered trademark) N-740, N-770, etc., manufactured by DIC Corporation), cresol novolac type epoxy resin (EPICLON (registered trademark), N-660, N-670, N-655-EXP-S, etc., manufactured by DIC Corporation).
• polyfunctional epoxy compound contained in the polyfunctional epoxy resin examples include glycidyl ether of tetra(hydrophenyl)alkane, glycidyl ether of tetrahydroxybenzophenone, epoxidized polyvinylphenol, etc.
• compounds contained in monofunctional epoxy resins include p-tert-butylphenyl glycidyl ether (ADEKA Glycirol (registered trademark), ED-509E, ED-509S, etc., manufactured by ADEKA Corporation).
• the epoxy resin having an alicyclic skeleton may be any that has an alicyclic skeleton in one molecule, and includes a cycloalkylene oxide compound in which an epoxy group is formed by two carbon atoms and one oxygen atom that form an alicyclic structure.
• the epoxy resin having an alicyclic skeleton may also include an epoxy compound having an alicyclic skeleton.
• Examples of epoxy compounds having an alicyclic skeleton include cyclohexane-based, cyclohexyl methyl ester-based, cyclohexyl methyl ether-based, spiro-based, and tricyclodecane-based epoxy compounds.
• epoxy resins having an alicyclic skeleton include 3',4'-epoxycyclomethyl 3,4-epoxycyclohexane carboxylate (Celloxide (registered trademark) 2021P manufactured by Daicel Corporation, etc.), (3,3',4,4'-diepoxy)bicyclohexyl (Celloxide (registered trademark) 8010 manufactured by Daicel Corporation, etc.), 1,2:8,9-diepoxylimonene, 1,2-epoxy-4-vinylcyclohexane, and 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (EHPE3150 manufactured by Daicel Corporation, etc.).
• Aliphatic epoxy resins include polyglycidyl ethers of polyhydric alcohols or their alkylene oxide adducts.
• Specific examples of aliphatic epoxy compounds contained in aliphatic epoxy resins include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether (such as Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.), and polyethylene glycol diglycidyl ether.
• examples of aliphatic cyclic epoxy resins include hydrogenated bisphenol A diglycidyl ether (such as jER YX8000 manufactured by Mitsubishi Chemical Corporation).
• the epoxy group equivalent of the epoxy compound is preferably 90 g/eq to 1000 g/eq.
• the epoxy group equivalent of the epoxy compound may be 800 g/eq or less, 600 g/eq or less, 500 g/eq or less, 400 g/eq or less, 120 g/eq or more, 130 g/eq or more, 150 g/eq or more, 180 g/eq or more, or 200 g/eq or more.
• oxetane compounds include 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol) (OXT-101 manufactured by Toagosei Co., Ltd., etc.), 2-ethylhexyloxetane (OXT-212 manufactured by Toagosei Co., Ltd., etc.), xylylene bisoxetane (OXT-121 manufactured by Toagosei Co., Ltd., etc.), 3-ethyl-3 ⁇ [(3-ethyloxetan-3-yl)methoxy]methyl ⁇ oxetane (OXT-221 manufactured by Toagosei Co., Ltd., etc.), oxetanyl silsesquioxetane (OXT-191 manufactured by Toagosei Co., Ltd., etc.), phenol novolac oxetane (PHOX manufactured by Toagosei Co., etc.
• vinyl ether compounds include, but are not limited to, ethyl vinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, hydroxybutyl vinyl ether, vinyl ether of 1,4-cyclohexane dimethanol, dodecyl vinyl ether, and cyclohexyl vinyl ether. These may be used alone or in combination of two or more.
• anionically polymerizable compounds examples include the epoxy compounds given as examples of the cationic polymerizable compounds above, and their curing agents, such as thiol-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and amine-based curing agents.
• methylene malonates given as examples of the radically polymerizable compounds above can also be given as anionically polymerizable compounds.
• (meth)acrylate compounds given as examples of the radically polymerizable compounds above can also be given as anionically polymerizable compounds when used in combination with thiol compounds. These may be used alone, or two or more of them may be used in combination.
• the polymerizable compound (A) may be any one of a radically polymerizable compound, a cationic polymerizable compound, and an anionic polymerizable compound, or any combination of these.
• the content of the polymerizable compound (A) in the resin composition may be 1 to 99 parts by mass relative to 100 parts by mass of the total resin composition. In one embodiment, it is preferably 5 to 50 parts by mass, more preferably 7 to 30 parts by mass, relative to 100 parts by mass of the total resin composition.
• the resin composition of this embodiment can be cured only by photocuring even if a large amount of shielding material such as filler is present.
• the content of the polymerizable compound (A) in the resin composition is preferably 30 to 99 parts by mass, more preferably 50 to 99 parts by mass, and even more preferably 60 to 99 parts by mass, relative to 100 parts by mass of the total resin composition.
• the content of the polymerizable compound (A) in the resin composition is preferably 75 to 99 parts by mass, more preferably 80 to 99.5 parts by mass, and even more preferably 85 to 98 parts by mass, relative to 100 parts by mass of the total organic matter (excluding low-stress-imparting materials such as organic fillers and elastomers) contained in the resin composition. Furthermore, the amount of component (A) is preferably 75 to 99.9 parts by mass, more preferably 80 to 99.5 parts by mass, and even more preferably 85 to 99 parts by mass, relative to 100 parts by mass of the total of components (A), (B), and (C).
• the resin composition of this embodiment contains (B) a photopolymerization initiator (hereinafter also referred to as "component (B)").
• the photopolymerization initiator is a reactant that absorbs light to generate active species such as radicals, cations, and anions, and promotes polymerization of the polymerizable compound.
• the (B) photopolymerization initiator is preferably a photopolymerization initiator that is activated by light having a wavelength of 500 nm or less (i.e., generates active species), and is activated by light having a wavelength of 500 nm or less that has been wavelength-converted by the (C) photon upconversion material described below.
• the (B) photopolymerization initiator is more preferably activated by light having a wavelength of 450 nm or less, even more preferably activated by light having a wavelength of 440 nm or less, and particularly preferably activated by light having a wavelength of 430 nm or less.
• the (B) photopolymerization initiator can be appropriately selected from a photoradical polymerization initiator, a photoacid generator, a photobase generator, or any combination thereof.
• the photoradical polymerization initiator absorbs light to generate radicals as active species, which then advances the polymerization of the radically polymerizable compound.
• photoradical polymerization initiators include, but are not limited to, alkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, and compounds having a photosensitive site and a peroxide structure.
• alkylphenone compounds include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one (commercially available as Omnirad 651 from IGM Resins B.V.); ⁇ -aminoalkylphenones such as 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one (commercially available as Omnirad 907 from IGM Resins B.V.); 1-hydroxycyclohexylphenyl ketone (commercially available as Omnirad 907 from IGM Resins B.V.); Examples of the ⁇ -hydroxyalkylphenone include, but are not limited to, ⁇ -hydroxyalkylphenones such as Omnirad 184 manufactured by IGM Resins B.V.; 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (commercially available as Omnirad 379EG manufactured by IGM Resins B.V
• acylphosphine oxide compounds include, but are not limited to, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (commercially available as Omnirad TPO H, manufactured by IGM Resins B.V.), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available as Omnirad 819, manufactured by IGM Resins B.V.), etc. These may be used alone or in combination of two or more.
• oxime ester compounds include, but are not limited to, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)] (product name: Irgacure OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (product name: Irgacure OXE-02, manufactured by BASF), methanone, ethanone, 1-[9-ethyl-6-(1,3-dioxolane, 4-(2-methoxyphenoxy)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (product name: ADEKA OPT-N-1919, manufactured by ADEKA Corporation). These may be used alone or in combination of two or more.
• Examples of compounds having a photosensitive moiety and a peroxide structure or commercially available products thereof include, but are not limited to, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone (BTTB), Perdual TA, and Perdual TX (all manufactured by NOF Corporation).
• BTTB 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone
• Perdual TA Perdual TA
• Perdual TX all manufactured by NOF Corporation.
• examples of photoradical polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyl dimethyl
• examples of the benzoyl ketal include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phen
• photoradical polymerization initiators Any one of the photoradical polymerization initiators may be used, or two or more of them may be used in combination.
• the content of the photoradical polymerization initiator in the resin composition is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 8 parts by mass, per 100 parts by mass of the total radical polymerizable compounds, from the viewpoint of photoirradiation reactivity.
• the photoacid generator absorbs light to generate an acid as an active species, and promotes polymerization of the cationically polymerizable compound.
• various onium salts having BF 4 - , SbF 6 -, AsF 6 - , B(C 6 F 5 ) 4 - , Ga(C 6 F 5 ) 4 - , C(CF 3 SO 2 ) 3 - , [P(R 1 ) a F 6-a ] - , [C(R 1 SO 2 ) 3 ] - or [N(R 1 SO 2 ) 2 ] - (wherein R 1 is each independently an alkyl group in which at least a portion of the hydrogen atoms is substituted with fluorine atoms, a is an integer of 0 to 5, and when a is an integer of 2 or more, a plurality of R 1s may be the same or different), as the counter anion, and a sulfonium cation, iodonium c
• iodonium cations include iodonium ions such as diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)phenyliodonium, bis(4-decyloxy)phenyliodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, and 4-isobutylphenyl(p-tolyl)iodonium.
• iodonium ions such as diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphen
• Sulfonium ions include, for example, triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenyl
• ammonium cations include pyrrolidiniums such as N,N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, and N,N-diethylpyrrolidinium; imidazoliniums such as N,N'-dimethylimidazolinium, N,N'-diethylimidazolinium, N-ethyl-N'-methylimidazolinium, 1,3,4-trimethylimidazolinium, and 1,2,3,4-tetramethylimidazolinium; tetrahydropyrimidiniums such as N,N'-dimethyltetrahydropyrimidinium; and morpholiniums such as N,N'-dimethylmorpholinium.
• Examples include fluorinium, piperidinium such as N,N'-diethylpiperidinium, pyridinium such as N-methylpyridinium, N-benzylpyridinium and N-phenacylpyridium, imidazolium such as N,N'-dimethylimidazolium, quinolium such as N-methylquinolium, N-benzylquinolium and N-phenacylquinolium, isoquinolium such as N-methylisoquinolium, thiazonium such as benzylbenzothiazonium and phenacylbenzothiazonium, acridium such as benzylacridium and phenacylacridium, etc.
• Examples of phosphonium cations include tetraarylphosphoniums such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis(2-methoxyphenyl)phosphonium, tetrakis(3-methoxyphenyl)phosphonium, and tetrakis(4-methoxyphenyl)phosphonium; triarylphosphoniums such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, and triphenylbutylphosphonium; and tetraalkylphosphoniums such as triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacylphosphonium, and tributylphenacylphospho
• iodonium salt-based photoacid generators include: photoacid generators which are arsenate-based iodonium salts, such as diphenyliodonium hexafluoroarsenate, di(4-chlorophenyl)iodonium hexafluoroarsenate, di(4-bromophenyl)iodonium hexafluoroarsenate, and phenyl(4-methoxyphenyl)iodonium hexafluoroarsenate; photoacid generators which are phosphate-based iodonium salts such as 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tri(pentafluoroethyl)trifluorophosphate (e.g., IK-1 manufactured by San-Apro Co.
• sulfonium salt photoacid generators include, but are not limited to, borate-based sulfonium salt photoacid generators (e.g., San-Apro Ltd. product names: CPI-110B, CPI-310B, CPI-410B, etc., and IGM Resins B.V. product name: Omnirad 290, etc.), phosphate-based sulfonium salt photoacid generators (San-Apro Ltd. product names: CPI-210S, VC-1S, CPI-410S, etc.), and other sulfonium salt photoacid generators (San-Apro Ltd. product names: CPI-310FG, VC-1FG, etc.), etc.
• borate-based sulfonium salt photoacid generators e.g., San-Apro Ltd. product names: CPI-110B, CPI-310B, CPI-410B, etc., and IGM Resins B.V. product name: Omnirad 290,
• photoacid generators Any one of the photoacid generators may be used, or two or more may be used in combination.
• the content of the photoacid generator in the resin composition is preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the total of the cationic polymerizable compounds.
• a photobase generator absorbs light to generate a base as an active species, which promotes the polymerization of an anionic polymerizable compound.
• photobase generators include, but are not limited to, various compounds that generate bases such as amines, amidines, guanidines, phosphazenes, and carbenes.
• photobase generators include, for example, 2-benzyl-2-(dimethylamino)-1-[4-(morpholino)phenyl]-1-butanone, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, 2-nitrobenzyl 4-hydroxypiperidine-1-carboxylate, 4,5-dimethoxy-2-nitrobenzyl 2,6-dimethylpiperidine-1-carboxylate, 1-(9,10-dioxo-9,10-dihydroanthracen-2-yl)ethylcyclohexylcarbamate, and 1-(9,10-dioxo-9,10-dihydroanthracen-2-yl)ethylcyclohexylcarbamate.
• photobase generators Any one of the photobase generators may be used, or two or more may be used in combination.
• the content of the photobase generator in the resin composition is preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass, per 100 parts by mass of the total anionic polymerizable compounds.
• the photopolymerization initiator may be any one of a photoradical polymerization initiator, a photoacid generator, and a photobase generator, or any combination of these may be used.
• the resin composition of this embodiment contains (C) photon up-conversion material (hereinafter also referred to as "component (C)").
• the photon up-conversion material generates a high energy state by multiphoton excitation, triplet-triplet annihilation process, etc., by irradiating specific light, and emits light with a shorter wavelength than the incident light in the process of relaxing them.
• the photon up-conversion material By including this photon up-conversion material in a resin composition and irradiating the resin composition with light of a long wavelength, the photon up-conversion material performs wavelength conversion inside the resin composition.
• the photon up-conversion material can generate light with a wavelength of 500 nm or less to activate the photopolymerization initiator and cure the resin composition.
• the emission wavelength of the photon up-conversion material (C) preferably includes a wavelength of 500 nm or less, more preferably includes a wavelength of 450 nm or less, even more preferably includes a wavelength of 430 nm or less, and particularly preferably includes a wavelength of 400 nm or less.
• the emission wavelengths of component (C) include ultraviolet light wavelengths (200 nm to 380 nm).
• Photon upconversion is a technology that converts low-energy (long-wavelength) light into high-energy (short-wavelength) light.
• Mechanisms of photon upconversion include triplet-triplet annihilation (TTA), multi-photon excitation of rare-earth element-containing materials, and two-photon absorption.
• TTA triplet-triplet annihilation
• a photon upconversion material based on any of the photon upconversion mechanisms can be used, but it is preferable that the (C) photon upconversion material is a (C1) triplet-triplet annihilation type photon upconversion material, a (C2) multi-photon excitation type photon upconversion material, or a combination of these.
• the photon upconversion material is a triplet-triplet annihilation type photon upconversion material (hereinafter also referred to as "component (C1)").
• component (C1) a triplet-triplet annihilation type photon upconversion material
• a combination of a donor and an acceptor is used.
• the triplet-triplet annihilation type photon upconversion material for example, those described in JP-A-2021-080335 and JP-A-2020-056030 can be used.
• the acceptor is not particularly limited as long as it is a compound (light emitter) that can become excited into a singlet state after receiving triplet energy transfer from the donor and generate photon upconversion emission.
• the acceptor include, but are not limited to, compounds having a naphthalene structure, anthracene structure, tetracene structure, pyrene structure, perylene structure, biphenyl structure, terphenyl structure, perylene diimide structure, naphthalene diimide structure, and BODIPY (boron dipyrromethene; 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) structure.
• acceptors include, but are not limited to, 9,10-diphenylanthracene (DPA), tetra-tert-butylperylene, anthracene (An), 2,5-diphenyloxazole (PPO), rubrene, 2-chloro-bis-phenylethynylanthracene (2CBPEA), 9,10-bis(phenylethynyl)anthracene (BPEA), 9,10-bis(phenylethynyl)naphthacene (BPEN), perylene, coumarin 343 (C343), 9,10-dimethylanthracene (DMA), pyrene, tert-butylpyrene, and boron dipyrromethene (BODIPY) derivatives with iodophenyl groups BD-1 and BD-2, as well as halogenated derivatives of these compounds.
• Other specific examples of the acceptor include the acceptors described in JP
• the donor is not particularly limited as long as it absorbs incident light, becomes an excited triplet state by intersystem crossing from an excited singlet state, and causes triplet-triplet energy transfer to the acceptor.
• Examples of the donor include, but are not limited to, metal atoms such as Pt, Pd, Zn, Ru, Re, Ir, Os, Cu, Ni, Co, Cd, Au, Ag, Sn, Sb, Pb, P, and As, and compounds containing organic moieties such as a porphyrin structure, a phthalocyanine structure, a fullerene structure, and a 2-phenylpyridinato structure.
• donors include palladium octabutoxyphthalocyanine (PdOBuPc), platinum tetraphenyltetranaphthoporphyrin (PtTPTNP), palladium(II)-meso-tetraphenyl-tetrabenzoporphyrin (PdTPTBP), [Ru(dmb) 3 ] 2+ (dmb is 4,4'-dimethyl-2,2'-bipyridine), palladium(II) tert-anthraporphyrin (PdTAP), platinum(II) tetraphenyltetrabenzoporphyrin (PtTPBP), palladium meso-tetraphenyltetrabenzoporphyrin (PdPh4TBP), palladium octaethylporphyrin (PdOEP), 11,15,18,22,25 octabutoxyphthalocyanine (PdPc(
• the wavelength of the incident light and the emission can be controlled.
• the combination of the donor and the acceptor may be one set or two or more sets.
• energy transfer from one photon upconversion material to another photon upconversion material in the resin composition is possible.
• the emission wavelength of the photon upconversion material can be adjusted from the desired incident light so as to finally include a wavelength of 500 nm or less, and thus the resin composition can be photocured using the desired incident light.
• the emission wavelength of the (C1) triplet-triplet annihilation type photon upconversion material that is emitted by irradiation with light having a wavelength of more than 500 nm can be adjusted to include a wavelength of 500 nm or less.
• the wavelength range of the excitation light that causes such a triplet-triplet annihilation type photon upconversion material (C1) to emit upconversion light is preferably a wavelength of more than 500 nm, for example, a wavelength in the range of more than 500 nm to 2000 nm.
• the wavelength of the upconversion light emitted by component (C1) preferably includes a wavelength of 500 nm or less, more preferably includes a wavelength of 450 nm or less, even more preferably includes a wavelength of 430 nm or less, and particularly preferably includes a wavelength of 400 nm or less.
• the emission wavelength of component (C1) includes the wavelength of ultraviolet light (200 nm to 380 nm).
• Any one of the donors may be used, or two or more of them may be used in combination.
• Any one of the acceptors may be used, or two or more of them may be used in combination.
• the content of component (C1) in the resin composition is, from the viewpoint of the curability of the resin composition, preferably 0.001 to 10 parts by mass, more preferably 0.005 to 10 parts by mass, and even more preferably 0.01 to 10 parts by mass, relative to 100 parts by mass of the total amount of the resin composition.
• the amount of component (C1) is preferably 0.001 to 20 parts by mass, more preferably 0.005 to 15 parts by mass, and even more preferably 0.01 to 10 parts by mass, relative to 100 parts by mass of the total of components (A), (B), and (C).
• the amount of component (C1) is 0.001 to 1 part by mass relative to 100 parts by mass of the total of components (A), (B), and (C).
• the amount of component (C1) is preferably 1 mmol/L to 6 mol/L, more preferably 2 mmol/L to 5 mol/L, even more preferably 6 mmol/L to 4 mol/L, particularly preferably 10 mmol/L to 3 mol/L, and most preferably 50 mmol/L to 2 mol/L.
• the photon up-conversion material is a multiphoton excitation type photon up-conversion material (hereinafter also referred to as "component (C2)").
• a multiphoton excitation type photon up-conversion material is a material that emits up-conversion light by multiphoton excitation.
• the wavelength of the up-conversion light of the component (C2) preferably includes a wavelength of 500 nm or less, more preferably includes a wavelength of 450 nm or less, even more preferably includes a wavelength of 430 nm or less, and particularly preferably includes a wavelength of 400 nm or less.
• the emission wavelength of the component (C2) includes a wavelength of ultraviolet light (200 nm to 380 nm).
• the component (C2) may have an emission peak in the red region and the green region in addition to the UV-A, purple, or blue region.
• the red region means a wavelength region of 600 to 800 nm
• the green region means a wavelength region of 500 to 600 nm
• the blue region means a wavelength region of 400 to 500 nm.
• the component (C2) preferably has an emission intensity in the wavelength region of 500 nm or less.
• component (C2) a rare earth element is doped into an optically inactive base material, which results in upconversion luminescence characteristics.
• type and amount (doping amount) of rare earth element contained in component (C2) it is possible to obtain upconversion luminescence of any wavelength.
• the rare earth element is not particularly limited as long as it is a rare earth element capable of upconversion emission, but generally includes rare earth elements that become trivalent ions. Among them, it is preferable to use a combination of at least two or more rare earth elements selected from the group consisting of erbium (Er), holmium (Ho), praseodymium (Pr), thulium (Tm), neodymium (Nd), gadolinium (Gd), europium (Eu), ytterbium (Yb), samarium (Sm) and cerium (Ce).
• Er erbium
• Ho holmium
• Pr praseodymium
• Tm thulium
• Nd neodymium
• Gd gadolinium
• Eu europium
• Yb ytterbium
• Sm samarium
• Ce cerium
• examples of the combination of rare earth elements include a combination of ytterbium (Yb), erbium (Er) and thulium (Tm), a combination of praseodymium (Pr), erbium (Er) and thulium (Tm), a combination of erbium (Er) and thulium (Tm), and the like.
• the combinations of ytterbium (Yb), erbium (Er) and thulium (Tm), and ytterbium (Yb) and thulium (Tm) are preferred.
• a rare earth element combination that has strong upconversion emission at blue light wavelengths is, for example, Yb 3+ /Tm 3+ .
• the wavelength range of the excitation light that causes such component (C2) to emit upconversion light is preferably a wavelength of more than 500 nm, for example, a wavelength in the range of more than 500 nm and not more than 2000 nm.
• the host material is not particularly limited as long as it supports a rare earth element and supports the rare earth element in a state capable of upconversion emission, and may be an organic substance that reacts with the rare earth element to form a complex, dendrimer, etc., or an inorganic substance. Inorganic substances are preferred because it is easy to incorporate the rare earth element in a state capable of emitting light.
• halides such as fluorides and chlorides, oxides, sulfides, oxysulfides, etc. are preferably used.
• halides include, but are not limited to, barium chloride (BaCl 2 ), lead chloride (PbCl 2 ), lead fluoride (PbF 2 ), cadmium fluoride (CdF 2 ), lanthanum fluoride (LaF 3 ), yttrium fluoride (YF 3 ), etc.
• oxides include, but are not limited to, yttrium oxide (Y 2 O 3 ), cerium oxide (CeO 2 ), aluminum oxide (Al 2 O 3 ), silicon dioxide (SiO 2 ), tantalum oxide (Ta 2 O 5 ), etc.
• a coating material may be formed around the component (C2) having a halide as a base material.
• the coating material may be any of the oxides listed above.
• Component (C2) can be produced by known methods, such as gas evaporation methods including high-frequency plasma methods, sputtering methods, glass crystallization methods, chemical precipitation methods, reverse micelle methods, sol-gel methods and similar methods, precipitation methods including hydrothermal synthesis and coprecipitation methods, spray methods, etc.
• gas evaporation methods including high-frequency plasma methods, sputtering methods, glass crystallization methods, chemical precipitation methods, reverse micelle methods, sol-gel methods and similar methods, precipitation methods including hydrothermal synthesis and coprecipitation methods, spray methods, etc.
• Component (C2) may be a commercially available product.
• Hefei Fluonano Biotech Co., Ltd. is selling core-shell upconversion phosphor nanoparticles with an excitation wavelength of 975 nm and an emission wavelength of 365 nm under the product code 201-30-365.
• Component (C2) may be used alone or in combination of two or more.
• the use of two or more components (C2) in combination enables energy transfer from one photon upconversion material to another photon upconversion material in the resin composition.
• Such stepwise energy transfer allows the emission wavelength of the photon upconversion material from the desired incident light to be adjusted to ultimately include a wavelength of 500 nm or less, thereby allowing the resin composition to be photocured using the desired incident light.
• the content of component (C2) in the resin composition is, for example, 0.1 to 60 parts by mass, preferably 0.1 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, and even more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the total amount of the resin composition, from the viewpoints of light conversion efficiency and photocuring degree.
• either the triplet-triplet annihilation type photon upconversion material (C1) or the multiphoton excitation type upconversion material (C2) may be used alone or in any combination.
• the use of a combination of component (C1) and component (C2) enables energy transfer from component (C1) to component (C2) or from component (C2) to component (C1) in the resin composition.
• Such stepwise energy transfer allows the emission wavelength of the photon upconversion material from the desired incident light to be adjusted to ultimately include a wavelength of 500 nm or less, thereby allowing the resin composition to be photocured using the desired incident light.
• the resin composition of this embodiment may contain optional components other than the components (A) to (C), such as those described below.
• the resin composition of this embodiment may contain a filler within a range that does not impair the object of this embodiment.
• a filler in the resin composition, the linear expansion coefficient of the cured product obtained by curing the resin composition can be reduced, and the thermal cycle resistance can be improved.
• the filler has a low elastic modulus, the stress generated in the cured product can be alleviated, and long-term reliability can be improved.
• Fillers are broadly classified into inorganic fillers and organic fillers.
• the inorganic filler is not particularly limited as long as it is made of granular material formed from an inorganic material and has the effect of lowering the linear expansion coefficient when added.
• silica, talc, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, boron nitride, etc. may be used. Any one of the inorganic fillers may be used, or two or more types may be used in combination.
• silica filler it is preferable to use silica filler because it is possible to increase the loading amount.
• silica amorphous silica is preferable.
• the inorganic filler may be surface-treated with a coupling agent such as a silane coupling agent. This allows the thixotropic index (TI) of the resin composition to fall within an appropriate range.
• a coupling agent such as a silane coupling agent.
• organic fillers examples include polytetrafluoroethylene (PTFE) fillers, silicone fillers, acrylic fillers, styrene fillers, etc.
• PTFE polytetrafluoroethylene
• silicone fillers examples include silicone fillers, acrylic fillers, styrene fillers, etc.
• the organic fillers may be surface-treated.
• the shape of the filler is not particularly limited and may be spherical, flaky, needle-like, irregular, etc.
• the average particle size of the filler is preferably 0.01 to 15 ⁇ m, and more preferably 0.01 to 10 ⁇ m. From the viewpoint of the transparency of the long-wavelength light irradiated to the resin composition, the maximum particle size of the filler is preferably 50 ⁇ m or less, and more preferably 30 ⁇ m or less.
• the average particle size is the particle size at 50% of the cumulative value in the particle size distribution on a volume basis, measured by the laser diffraction/scattering method.
• the maximum particle size is the maximum particle size in the particle size distribution on a volume basis, measured by the laser diffraction/scattering method.
• the filler content is preferably 0.5 to 80 mass % relative to the total mass of the resin composition, and more preferably 1 to 70 mass %.
• the resin composition of this embodiment may contain a thixotropic agent within a range that does not impair the effects of this embodiment.
• a thixotropic agent include colloidal silica, hydrophobic silica, fine silica, silica such as nanosilica, bentonite, acetylene black, ketjen black, etc., and nanosilica is preferred from the viewpoint of shape retention after application.
• the thixotropic agent is more preferably nanosilica having an average particle size of 10 to 750 nm, and even more preferably nanosilica having an average particle size of 20 to 600 nm, from the viewpoint of preventing the resin composition from being bitten during bonding and moisture-resistant adhesion.
• Examples of commercially available products include hydrophobic fumed silica manufactured by CABOT (product name: CAB-O-SIL (registered trademark) TS720, average particle size: 12 nm), hydrophobic fumed silica manufactured by Nippon Aerosil (product name: R805, average particle size: 20 nm), amorphous silica manufactured by Nippon Shokubai (product name: Sea Hoster KE-P10, average particle size 100 nm), etc., but are not limited thereto.
• the average particle size of the nanosilica particles is measured by a dynamic light scattering type Nanotrack particle size analyzer.
• the thixotropic agents may be used alone or in combination of two or more kinds.
• the content of the thixotropic agent is preferably 0.01 to 30 mass %, more preferably 0.05 to 25 mass %, and even more preferably 0.1 to 20 mass %, relative to the total mass of the resin composition.
• the resin composition of this embodiment may contain a light-shielding agent within a range that does not impair the effect of this embodiment. Depending on the application of the cured product of the resin composition, light-shielding properties may be required. In that case, the resin composition of this embodiment may contain a light-shielding agent. Long-wavelength light can be transmitted through the light-shielding agent that blocks ultraviolet light. The resin composition of this embodiment may be cured by irradiating it with long-wavelength light without or with minimal influence of the light-shielding agent. Examples of light-shielding agents include, but are not limited to, carbon black and titanium black. In addition, these light-shielding agents can also be used as light-heat conversion materials that convert long-wavelength light into heat.
• the resin composition of this embodiment may further contain other additives, such as a photosensitizer, a conductive filler, a stabilizer, a radical polymerization inhibitor, an anionic polymerization inhibitor, a coupling agent, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a viscosity modifier, a flame retardant, a colorant, a plasticizer, a solvent, etc., within the scope of the present embodiment.
• additives such as a photosensitizer, a conductive filler, a stabilizer, a radical polymerization inhibitor, an anionic polymerization inhibitor, a coupling agent, an ion trapping agent, a leveling agent, an antioxidant, an antifoaming agent, a viscosity modifier, a flame retardant, a colorant, a plasticizer, a solvent, etc.
• additives such as a photosensitizer, a conductive filler, a stabilizer, a radical poly
• the viscosity of the resin composition of this embodiment is preferably 0.1 to 100 Pa ⁇ s.
• the viscosity can be adjusted appropriately depending on the application and location of the resin composition.
• the resin composition of this embodiment is excellent for application to locations with complex shapes where UV light irradiation is difficult, and for application to narrow areas.
• viscosity is expressed as a value measured in accordance with Japanese Industrial Standard JIS K6833, unless otherwise specified. Specifically, it can be determined by measuring using an E-type viscometer at a rotation speed of 10 rpm. There are no particular restrictions on the equipment, rotor, or measurement range used.
• the photocurable resin composition of this embodiment can be a one-component resin composition that is contained in a single container, or a two-component (or multi-component) resin composition that is divided into two or more containers, depending on the application, etc.
• a two-component (or multi-component) resin composition the two components (or multiple components) are mixed to form a photocurable resin composition in the form of use.
• the components (A) to (C) and other optional components as required can be selected in the same way as for the one-component type.
• each liquid may contain one or more selected from the components (A) to (C) and other optional components as required, or the components (A) to (C) and other optional components as required may be contained in one liquid, or a liquid may consist of only the components (A) to (C) and/or other optional components as required.
• the method of division may be liquid A: component (A), liquid B: component (B) and component (C), liquid A: component (A) and component (B), liquid B: component (C), or liquid A: component (A) and component (C), and liquid B: component (B).
• liquid B may contain one or more selected from the components (A) to (C).
• components other than the components (A) to (C) may be contained in both or either of the liquid A and the liquid B in the above combination.
• liquid A When the components (A) to (C) are contained in liquid A and the other components are contained in liquid B, only liquid A or a combination of liquid A and liquid B can be considered as the resin composition of this embodiment.
• the components (A) to (C) are each contained in a separate liquid, the respective liquids can be considered as the resin composition of this embodiment.
• An example of a case in which the components (A) to (C) are each contained in a separate liquid is, for example, a resin composition in which the components (A) to (C) are separated into two or more containers, specifically, a kit composed of multiple liquids containing any of the components (A) to (C).
• the method for producing the resin composition of this embodiment is not particularly limited.
• components (A) to (C) and, if necessary, other optional components can be introduced simultaneously or separately into an appropriate mixer, and then stirred and mixed to form a homogeneous composition, thereby obtaining the resin composition of this embodiment.
• This mixer is not particularly limited, but a Raikai mixer, Henschel mixer, triple roll mill, ball mill, planetary mixer, bead mill, or the like equipped with a stirring device and a heating device can be used. These devices may also be used in appropriate combination.
• the resin composition thus obtained is cured by irradiation with light of a long wavelength (for example, longer than 500 nm), and does not require main curing by heat.
• Conventionally used UV-curable adhesives are generally photocured using high-energy short-wavelength light (e.g., 365 nm UV light). For this reason, when the adhesive contains fillers, etc., there is a problem that the penetration distance of light into the UV-curable adhesive is short when irradiated with short-wavelength light, and curing does not proceed in areas where the light does not reach due to shielding, etc.
• the penetration distance of ultraviolet light of 380 nm or less into the silicon substrate is several to several tens of nm
• the penetration distance of visible light of 380 to 780 nm is several hundreds of nm to several microns
• the penetration distance of infrared light of 780 nm or more is several tens of microns to the order of millimeters
• the resin composition of this embodiment can be used, for example, as an adhesive, sealant, or coating agent for fixing, joining, or protecting semiconductor devices or electronic components, or components that constitute these, or as a raw material thereof.
• the photocurable resin composition of this embodiment can be used for curing by irradiation with light having a wavelength of more than 500 nm.
• the photocurable resin composition of this embodiment can be used as an adhesive, sealant, or coating agent for semiconductor devices or electronic components.
• Another aspect of the present invention is a method for bonding at least two components with a photocurable resin composition, the method comprising the steps of: The method includes the steps of: applying the photocurable resin composition of the present embodiment to at least one of the at least two parts; and irradiating at least one of the at least two parts, the photocurable resin composition, or both of them with light having a wavelength of more than 500 nm.
• the photocurable resin composition of the above embodiment is applied to at least one of at least two parts.
• the parts are preferably parts constituting a semiconductor device or electronic part, such as, but not limited to, a semiconductor element, a substrate, etc.
• the material of the parts may be any of engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, metals (e.g., copper, nickel), etc.
• the method of applying the resin composition is not particularly limited, and for example, the resin composition can be applied to a desired portion of a component such as a substrate by a known printing method, dispensing method, or coating method.
• printing methods include, but are not limited to, inkjet printing, screen printing, lithographic printing, carton printing, metal printing, offset printing, gravure printing, flexographic printing, and the like.
• dispensing methods include, but are not limited to, methods using a jet dispenser, an air dispenser, and the like.
• coating methods include, but are not limited to, dip coating, spray coating, bar coater coating, gravure coating, reverse gravure coating, spin coater coating, and the like.
• the other part is attached to the part to which the photocurable resin composition has been applied via the photocurable resin composition, or the part to which the photocurable resin composition has been applied is attached to the other part via the photocurable resin composition.
• Any known method may be used for attachment. If necessary, after attachment, pressure may be applied while pressure is applied.
• the photon upconversion material performs wavelength conversion inside the resin composition, generating light having a wavelength of 500 nm or less, preferably light having a wavelength of 450 nm or less, more preferably light having a wavelength of 430 nm or less, and particularly preferably light having a wavelength of 400 nm or less to activate the photopolymerization initiator and cure the polymerizable compound, thereby bonding the at least two parts.
• the wavelength of the irradiated light may be, for example, 532 nm, 980 nm, 1064 nm, or 1550 nm, but is not limited to these wavelengths.
• the light source may be an LED, a laser, an LD module, or other coherent light source.
• the integrated dose of the irradiated light may be 1 mJ/cm 2 to 2000 J/cm 2.
• the irradiation intensity may be 1 mW/cm 2 to 1000 W/cm 2 .
• the cumulative amount of irradiation and the irradiation intensity of the irradiation light can be adjusted appropriately according to the desired degree of curing.
• either spot irradiation in which light is irradiated to a local area or area irradiation in which light is irradiated to a wide area can be performed. Since the resin composition used in this embodiment can be cured even in the shadowed part of the part, in the bonding method of this embodiment, the resin composition can be irradiated with light not only directly but also through the part.
• another aspect of the present invention is a method for sealing a gap between or within components with a photocurable resin composition, the sealing method comprising the steps of:
• the method includes the steps of applying or injecting the photocurable resin composition of the above aspect into the gap between or within the components, and irradiating the photocurable resin composition with light having a wavelength of more than 500 nm.
• the parts and the light irradiation were the same as those in the above-mentioned bonding method.
• Examples of the coating or injection method include the coating method in the bonding method and a potting method, but are not limited to these.
• the resin composition used in this embodiment can achieve a high cure depth, and therefore the sealing method of this embodiment can cure the resin composition present deep in gaps that are difficult for ultraviolet light to reach, thereby achieving suitable sealing.
• Yet another aspect of the present invention is a method for coating a surface of an object with a curable composition, the method comprising: The method includes the steps of: applying the photocurable resin composition of the above aspect to the object; and irradiating the photocurable resin composition with light having a wavelength of more than 500 nm.
• the object may be a semiconductor device or electronic component, or a component constituting the same. Examples of the semiconductor device or electronic component include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, other semiconductor modules, integrated circuits, etc. Examples of components constituting the semiconductor device or electronic component include, but are not limited to, semiconductor elements, substrates, etc.
• the material of the component may be any of engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, or metals (e.g., copper, nickel), etc.
• the coating method is the same as that in the above-mentioned adhesion method.
• the light irradiation method is the same as that in the above-mentioned bonding method.
• an adhesive, sealant, or coating agent contains the resin composition of the above embodiment.
• This adhesive, sealant, or coating agent enables good fixing, bonding, or protection of engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, and metals (e.g., copper, nickel, etc.), and can be used to fix, bond, or protect semiconductor devices or electronic components, or components that constitute these.
• engineering plastics e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.
• ceramics e.g., copper, nickel, etc.
• metals e.g., copper, nickel, etc.
• semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, other semiconductor modules, integrated circuits, and the like.
• the adhesive, sealant, or coating agent of this embodiment can be completely cured by irradiation with light of a long wavelength (e.g., longer than 500 nm), and therefore has high productivity and is suitable for use, for example, in the manufacture of semiconductor devices and electronic components.
• a long wavelength e.g., longer than 500 nm
• a cured product according to another embodiment of the present invention is a cured product obtained by curing the resin composition, adhesive, sealant, or coating agent according to the above embodiment.
• semiconductor devices Another embodiment of the present invention, a semiconductor device or electronic component, contains the cured product of the above embodiment, and therefore has high reliability.
• semiconductor device refers to any device that can function by utilizing semiconductor characteristics, and includes electronic components, semiconductor circuits, modules incorporating these, electronic devices, etc. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, other semiconductor modules, integrated circuits, etc.
• Another aspect of the present invention is a method for producing a cured product, comprising irradiating the photocurable resin composition of the above-mentioned aspect, or the adhesive, sealant, or coating agent of the above-mentioned aspect, with light having a wavelength of more than 500 nm.
• Yet another aspect of the present invention is a method for curing a photocurable resin composition, comprising irradiating the photocurable resin composition of the above-mentioned aspect with light having a wavelength of more than 500 nm.
• the photon upconversion material By irradiating light having a wavelength of more than 500 nm, for example, light having a wavelength in the range of more than 500 nm and less than 2000 nm, the photon upconversion material performs wavelength conversion inside the resin composition, and generates light having a wavelength of 500 nm or less, preferably light having a wavelength of 450 nm or less, more preferably light having a wavelength of 430 nm or less, and particularly preferably light having a wavelength of 400 nm or less, to activate the photopolymerization initiator and cure the polymerizable compound.
• the details of the irradiation with light having a wavelength of more than 500 nm in these methods are the same as those in the adhesion method, sealing method, and coating method. In this aspect, either spot irradiation in which light is irradiated to a local area or area irradiation in which light is irradiated to a wide area can be performed.
• Example 1 The resin compositions of Examples 1 to 18 and Comparative Examples 1 to 6 were prepared by mixing predetermined amounts of each component according to the formulation shown in Table 1.
• the triplet-triplet annihilation photon up-conversion material (C1) was mixed with a polymerizable compound and a photopolymerization initiator to obtain a resin composition.
• a predetermined amount of component (C2) was mixed into the resin composition.
• the amount of each component is expressed in mass %.
• the components used in the examples and comparative examples are as follows.
• A Polymerizable compound
• A-1 Dimethylol-tricyclodecane diacrylate (product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.)
• A-2) Bisphenol A type/bisphenol F type mixed epoxy resin (product name: EPICLON 835LV, manufactured by DIC Corporation)
• A-3) Alicyclic epoxy resin (product name: Celloxide 2021P, manufactured by Daicel Corporation)
• A-4) Water-added BisA type epoxy resin (product name: YX8000, manufactured by Mitsubishi Chemical Corporation)
• B-1) 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one
• B-2 1-hydroxycyclohexyl phenyl ketone (product name: Omnirad 184, manufactured by I
• C2 Multiphoton excitation photon up-conversion material (C2-1): CeO 2 /3.0Er 3+ , 0.6Yb 3+ (synthesis method shown below) Er2O3 (FUJIFILM Wako Pure Chemicals, 99.0% or more) and Yb2O3 (FUJIFILM Wako Pure Chemicals, 98.0% or more) were weighed out and ground and mixed in a mortar so that CeO2 (FUJIFILM Wako Pure Chemicals, special grade chemical) was doped with 3.0 mol % of Er3 + and 0.6 mol% of Yb3 + , respectively.
• This powder was pre-fired at 1200°C (heating rate: 600°C/hour, firing time: 2 hours), re-ground in a mortar, and then fired at 1500°C (heating rate: 600°C/hour, firing time: 4 hours) to obtain CeO2 /3.0Er3 + , 0.6Yb3 + .
• the absence of unreacted materials was confirmed by XRD.
• This powder was pre-fired at 1400°C (heating rate: 600°C/hour, firing time: 2 hours), re-ground in a mortar, and then fired at 1600°C (heating rate: 600°C/hour, firing time: 4 hours) to obtain Y2O3 / 2.0Er3 + , 2.0Yb3 + .
• the absence of unreacted materials was confirmed by XRD.
• D Filler (D-1): High-purity synthetic spherical silica (product name: SE-2300, manufactured by Admatechs Co., Ltd., volume average particle size: 0.6 ⁇ m)
• E Thixotropic agent (E-1): Hydrophobic fumed silica (product name: CAB-O-SIL (registered trademark) TS720, manufactured by CABOT Corporation, average particle size: 12 nm)
• F Light-shielding agent (F-1): Carbon black (product name: Special Black 4, manufactured by Orion Engineered Carbons Co., Ltd.)
• F-2) Titanium Black (product name: Titanium Black 13M, manufactured by Mitsubishi Materials Corporation)
• the ultraviolet light had a wavelength of 365 nm and an irradiation intensity of 500 mW/ cm2. The irradiation was continued until the accumulated light amount reached 2000 mJ/ cm2 (measured with an ultraviolet accumulator UIT-250 and a UVD-S365 receiver (manufactured by Ushio Inc.)).
• the visible light irradiation conditions were as follows: a semiconductor pumped solid-state laser (Class 3R green laser pointer LP-GL1016BK, manufactured by Sanwa Supply Co., Ltd.) was used to continuously irradiate the glass slide with visible light having a wavelength of 532 nm and an irradiation intensity of 1 mW/ cm2 at a position 4 cm above the light source, until the accumulated light amount reached 720 mJ/ cm2 .
• a semiconductor pumped solid-state laser (Class 3R green laser pointer LP-GL1016BK, manufactured by Sanwa Supply Co., Ltd.) was used to continuously irradiate the glass slide with visible light having a wavelength of 532 nm and an irradiation intensity of 1 mW/ cm2 at a position 4 cm above the light source, until the accumulated light amount reached 720 mJ/ cm2 .
• an infrared semiconductor laser (Lab Laser System, manufactured by CiviLaser) was used to continuously irradiate the slide glass with infrared light having a wavelength of 980 nm at a position 4 cm above the light source, with an irradiation intensity of 200 mW/ cm2 , until the accumulated light amount reached 720 kJ/ cm2 .
• one of the slide glasses was peeled off from the test piece, and the photocurability was evaluated based on the appearance and palpation with a bamboo skewer using three levels: cured ( ⁇ ), partially uncured ( ⁇ ), and uncured ( ⁇ ). The results are shown in Tables 1-1, 1-2, and 1-3.
• Comparative Examples 1, 5, and 6 are resin compositions consisting of a polymerizable compound (A) and a photopolymerization initiator (B) that do not contain an upconversion material (C1), and do not cure with visible light irradiation, but cure only with ultraviolet light irradiation.
• Comparative Examples 2 and 3 are resin compositions containing only either a donor or acceptor molecule of a triplet-triplet annihilation photon upconversion material (C1), and do not cure with visible light irradiation, but cure only with ultraviolet light irradiation, as in Comparative Example 1.
• Comparative Example 4 is a resin composition consisting of a polymerizable compound (A) and an upconversion material (C1) that do not contain a photopolymerization initiator (B), and does not cure with ultraviolet light or visible light irradiation.
• a resin composition consisting of a polymerizable compound (A), a photopolymerization initiator (B), and an upconversion material (C1) containing both donor and acceptor molecules cures not only with ultraviolet light but also with visible light irradiation.
• the resin composition containing the filler (D), the thixotropic agent (E), the light-shielding agent (F), or a combination thereof was cured by both ultraviolet light and visible light irradiation.
• the resin composition was cured by both ultraviolet light and visible light irradiation.
• the resin composition was cured by both ultraviolet light and visible light irradiation.
• Examples 15 and 16 are resin compositions containing a polymerizable compound (A), a photopolymerization initiator (B), a triplet-triplet annihilation photon upconversion material (C1) and a multiphoton excitation upconversion material (C2), and were cured by irradiation with infrared light in addition to ultraviolet light and visible light.
• A polymerizable compound
• B photopolymerization initiator
• C1 triplet-triplet annihilation photon upconversion material
• C2 multiphoton excitation upconversion material
• Example 2 In the evaluation of the curability of the resin composition of Example 7, the two slide glasses were changed to various substrate materials shown in Table 2, and ultraviolet light and visible light were irradiated. The results are shown in Table 2.
• the resin composition was cured by irradiation with ultraviolet light and visible light on a 1.0 mm thick Pyrex glass substrate. On an FR4 substrate, the resin composition was cured by irradiation with ultraviolet light up to a thickness of 2.0 mm, but was not cured at thicknesses greater than that. On the other hand, the resin composition was completely cured by irradiation with visible light up to a thickness of 5.0 mm on an FR4 substrate. Furthermore, the resin composition was not cured by irradiation with ultraviolet light on a 0.125 mm thick polyimide film, but was cured by irradiation with visible light.

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