Classifications

• • 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
  • C08G59/40—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 curing agents used
  • C08G59/62—Alcohols or phenols
  • C08G59/621—Phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
• • 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
  • C08G59/40—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 curing agents used
  • C08G59/62—Alcohols or phenols
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
  • C08G65/16—Cyclic ethers having four or more ring atoms
  • C08G65/18—Oxetanes
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
• • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • 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
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • 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
  • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
  • C09J201/06—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
• • 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
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/02—Details
  • H05B33/04—Sealing arrangements, e.g. against humidity
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
  • H10K59/80—Constructional details
  • H10K59/87—Passivation; Containers; Encapsulations
  • H10K59/873—Encapsulations

Definitions

• the present invention relates to a curable resin composition having excellent curability and a high refractive index of the cured product.
• the present invention also relates to a sealant for display elements and a sealant for organic EL display elements containing the curable resin composition.
• the present invention relates to an optical adhesive containing the curable resin composition and an optical member containing a cured product of the curable resin composition.
• a cationically curable resin composition containing a cationically polymerizable compound and a cationic polymerization initiator has been used as a curable resin composition for optical members.
• cationically curable resin compositions and cured products thereof are used in sealants and the like used in display elements such as organic electroluminescence (hereinafter also referred to as “organic EL”) display elements.
• An organic EL display element has a laminate structure in which an organic light-emitting material layer is sandwiched between a pair of electrodes facing each other. By injecting holes, electrons and holes combine in the organic light-emitting material layer to emit light. In this way, since the organic EL display element emits light by itself, it has better visibility, can be made thinner, and can be driven with a low DC voltage, compared to a liquid crystal display element that requires a backlight. has the advantage of being
• Organic light-emitting material layers and electrodes that constitute an organic EL display element have a problem that their characteristics are likely to deteriorate due to moisture, oxygen, and the like. Therefore, in order to obtain a practical organic EL display device, it is necessary to isolate the organic light-emitting material layer and the electrodes from the atmosphere to prolong the life of the device.
• a method for shielding the organic light-emitting material layer and electrodes from the atmosphere sealing of an organic EL display element using a sealant is performed (for example, Patent Document 1).
• an inorganic material film called a passivation film is usually provided on a laminate having an organic light-emitting material layer in order to sufficiently suppress the transmission of moisture, oxygen, and the like.
• a method of sealing the material film with a sealant is used.
• the top-emission type organic EL display device in which light is extracted from the upper surface side of the organic light-emitting material layer has been developed.
• An organic EL display device has attracted attention. This system has a high aperture ratio and can be driven at a low voltage, so it has the advantage of extending the life.
• the upper surface side of the light-emitting layer must be transparent. It is sealed by laminating materials (for example, Patent Document 1).
• Cationically curable resin compositions are also used in optical adhesives used for bonding optical materials such as polarizing plates and optical members such as resin lenses (for example, Patent Documents 2 and 3).
• Cationic curable resin compositions used for optical adhesives and optical members are also required to have excellent curability and a higher refractive index.
• An object of the present invention is to provide a curable resin composition having excellent curability and a cured product having a high refractive index.
• Another object of the present invention is to provide a sealant for display elements and a sealant for organic EL display elements containing the curable resin composition.
• a further object of the present invention is to provide an optical adhesive containing the curable resin composition and an optical member containing a cured product of the curable resin composition.
• the present disclosure 1 is a curable resin composition containing a cationic polymerizable compound, a cationic polymerization initiator, and a fluorene compound having a phenolic hydroxyl group in its molecule.
• the present disclosure 2 is the curable resin composition of the present disclosure 1, wherein the fluorene compound having a phenolic hydroxyl group in the molecule has two or more phenolic hydroxyl groups in one molecule.
• Present Disclosure 3 is the curable resin composition of Present Disclosure 1 or 2, wherein the fluorene compound having a phenolic hydroxyl group in the molecule is a compound represented by the following formula (1).
• the present disclosure 4 is the content of the fluorene compound having a phenolic hydroxyl group in the molecule in 100 parts by weight of the curable resin composition is 3 parts by weight or more and 60 parts by weight or less curing of the present disclosure 1, 2 or 3 It is a flexible resin composition.
• the cationically polymerizable compound includes at least one of a compound having a biphenyl skeleton and an epoxy group, and a compound having a biphenyl skeleton and an oxetanyl group Curing of present disclosure 1, 2, 3 or 4 It is a flexible resin composition.
• Present Disclosure 6 is the curable resin composition of Present Disclosure 1, 2, 3, 4 or 5, wherein the cured product has a refractive index of 1.6 or higher for sodium D line at 25°C.
• the present disclosure 7 is the curable resin of the present disclosure 1, 2, 3, 4, 5 or 6 having a viscosity measured at 25 ° C. of 0.1 Pa s or more and 5000 Pa s or less using an E-type viscometer composition.
• the present disclosure 8 is a sealant for display elements containing the curable resin composition of the present disclosure 1, 2, 3, 4, 5, 6 or 7.
• the present disclosure 9 is a sealant for organic EL display elements containing the curable resin composition of the present disclosure 1, 2, 3, 4, 5, 6 or 7.
• Disclosure 10 is an optical adhesive comprising the curable resin composition of Disclosure 1, 2, 3, 4, 5, 6 or 7.
• the present disclosure 11 is an optical member containing a cured product of the curable resin composition of the present disclosure 1, 2, 3, 4, 5, 6 or 7.
• R 1 and R 2 are each hydrogen atoms or combine to represent one oxygen atom
• R 3 to R 8 each independently represent a hydrogen atom having 1 carbon atom. It represents an alkyl group of 6 or less, a phenyl group, or a benzyl group. The present invention will be described in detail below.
• the present inventors have investigated that the cationic curable resin composition containing a cationic polymerizable compound and a cationic polymerization initiator further contains a fluorene compound having a phenolic hydroxyl group in the molecule.
• the present inventors have found that a curable resin composition having excellent curability and a high refractive index of the cured product can be obtained, leading to the completion of the present invention.
• the cured product of the curable resin composition of the present invention has a high refractive index, when it is used as a sealant for a display element such as an organic EL display element, the resulting display element is expected to have excellent light extraction efficiency.
• the curable resin composition of the present invention is excellent in curability and the cured product has a high refractive index, so that it can be suitably used as an optical adhesive or an optical member.
• the curable resin composition of the present invention contains a fluorene compound having a phenolic hydroxyl group in its molecule (hereinafter also referred to as "phenolic hydroxyl group-containing fluorene compound").
• phenolic hydroxyl group-containing fluorene compound a fluorene compound having a phenolic hydroxyl group in its molecule
• the curable resin composition of the present invention has excellent curability and a cured product having a high refractive index.
• the phenolic hydroxyl group in the fluorene compound containing the phenolic hydroxyl group contributes to the improvement of the curability, since the presence or absence of the phenolic hydroxyl group significantly improves the curability.
• the above-mentioned "phenolic hydroxyl group” in this specification means the hydroxyl group which exists on an aromatic substituent.
• the phenolic hydroxyl group-containing fluorene compound preferably has two or more phenolic hydroxyl groups in one molecule.
• the phenolic hydroxyl group-containing fluorene compound preferably has an aromatic ring other than that contained in the fluorene skeleton from the viewpoint of increasing the refractive index of the cured product of the curable resin composition obtained.
• aromatic rings other than those contained in the fluorene skeleton preferably have phenolic hydroxyl groups.
• phenolic hydroxyl group-containing fluorene compound a compound represented by the above formula (1) is preferable.
• Examples of the compound represented by the above formula (1) include 9,9-bis(4-hydroxyphenyl)fluorene (a compound represented by the following formula (2-1)), 9,9-bis(4- Hydroxy-3-methylphenyl)fluorene (compound represented by the following formula (2-2)), spiro[fluorene-9,9'-xanthene]-3',6'-diol (the following formula (2-3) compounds represented by), compounds represented by the following formula (2-4), and the like.
• a preferable lower limit of the content of the phenolic hydroxyl group-containing fluorene compound in 100 parts by weight of the curable resin composition of the present invention is 3 parts by weight, and a preferable upper limit thereof is 60 parts by weight.
• the content of the phenolic hydroxyl group-containing fluorene compound is 3 parts by weight or more, the resulting cured product of the curable resin composition has a higher refractive index.
• the content of the phenolic hydroxyl group-containing fluorene compound is 60 parts by weight or less, the resulting curable resin composition is more excellent in coatability.
• a more preferable lower limit to the content of the phenolic hydroxyl group-containing fluorene compound is 5 parts by weight, and a more preferable upper limit is 50 parts by weight.
• the curable resin composition of the present invention contains a cationic polymerizable compound.
• the cationically polymerizable compound preferably contains at least one of a compound having a biphenyl skeleton and an epoxy group and a compound having a biphenyl skeleton and an oxetanyl group.
• the curable resin composition of the present invention has a higher refractive index. can be higher.
• the compound having a biphenyl skeleton and an epoxy group include o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, 4,4-biphenyldiylbis(glycidyl ether), 4,4'- bis(glycidyloxy)-1,1'-biphenyl, 3,3',5,5'-tetramethyl-4,4'-bis(glycidyloxy)-1,1'-biphenyl and the like.
• o-phenylphenol glycidyl ether is preferable.
• the compound having a biphenyl skeleton and an oxetanyl group include compounds represented by the following formula (3).
• the compound having a biphenyl skeleton and an epoxy group and the compound having a biphenyl skeleton and an oxetanyl group may be used alone, or two or more of them may be used in combination.
• n is the number of repetitions.
• the n is preferably a value that satisfies the oxetanyl equivalent weight range described below for the compound represented by formula (3).
• the preferable lower limit of the epoxy equivalent weight of the compound having the biphenyl skeleton and the epoxy group and the oxetanyl equivalent weight of the compound having the biphenyl skeleton and the oxetanyl group is 110, and the preferable upper limit thereof is 500.
• the epoxy equivalent of the compound having a biphenyl skeleton and an epoxy group and the oxetanyl equivalent of the compound having a biphenyl skeleton and an oxetanyl group are in this range, the obtained curable resin composition has adhesiveness, low outgassing, In addition, it becomes more excellent in coatability.
• the epoxy equivalent of the compound having a biphenyl skeleton and an epoxy group is (molecular weight of the compound having a biphenyl skeleton and an epoxy group)/(the compound having a biphenyl skeleton and an epoxy group per molecule). number of epoxy groups).
• the oxetanyl equivalent of the compound having a biphenyl skeleton and an oxetanyl group is defined as (molecular weight of the compound having a biphenyl skeleton and an oxetanyl group)/(in one molecule of a compound having a biphenyl skeleton and an oxetanyl group) number of oxetanyl groups).
• the preferred lower limit of the molecular weight of the compound having a biphenyl skeleton and an epoxy group and the molecular weight of the compound having a biphenyl skeleton and an oxetanyl group is 200, and the preferred upper limit is 1,000.
• the molecular weight of the compound having a biphenyl skeleton and an epoxy group and the molecular weight of the compound having a biphenyl skeleton and an oxetanyl group are in this range, the obtained curable resin composition has adhesiveness, low outgassing, and It becomes more excellent in coatability.
• the above-mentioned "molecular weight” is the molecular weight obtained from the structural formula for compounds whose molecular structure is specified.
• the "weight-average molecular weight” is a value determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent and converted to polystyrene.
• GPC gel permeation chromatography
• Examples of the column used for measuring the weight average molecular weight by GPC in terms of polystyrene include Shodex LF-804 (manufactured by Showa Denko KK).
• the compound having a biphenyl skeleton and an epoxy group and the compound having a biphenyl skeleton and an oxetanyl group are preferably liquid at 25°C.
• the resulting curable resin composition has excellent coatability.
• Examples of commercially available compounds having a biphenyl skeleton and an epoxy group include OPP-EP (manufactured by Yokkaichi Gosei Co., Ltd.). Examples of commercially available compounds having a biphenyl skeleton and an oxetanyl group include ETERNACOLL OXBP (manufactured by Ube Industries, Ltd.).
• the cationically polymerizable compound may contain other cationically polymerizable compounds in addition to at least one of the compound having a biphenyl skeleton and an epoxy group and the compound having a biphenyl skeleton and an oxetanyl group.
• the other cationically polymerizable compounds include epoxy compounds other than the compound having the biphenyl skeleton and an epoxy group, and compounds other than the compound having the biphenyl skeleton and an oxetanyl group. Examples include oxetane compounds and vinyl ether compounds.
• the preferable lower limit of the content of the compound having a biphenyl skeleton and an epoxy group and the compound having a biphenyl skeleton and an oxetanyl group in 100 parts by weight of the total cationically polymerizable compound is 30 parts by weight, preferably 97 parts by weight.
• the content of the compound having a biphenyl skeleton and an epoxy group and the compound having a biphenyl skeleton and an oxetanyl group is 30 parts by weight or more, the resulting cured product of the curable resin composition has a higher refractive index. become a thing.
• the resulting curable resin composition exhibits curability, low outgassing, and , which is superior in coatability. More preferably, the lower limit of the content of the compound having a biphenyl skeleton and an epoxy group and the compound having a biphenyl skeleton and an oxetanyl group is 50 parts by weight, the upper limit is more preferably 90 parts by weight, and the upper limit is still more preferably 80 parts by weight. is.
• Examples of the other epoxy compounds include 3,4-epoxycyclohexylmethyl(3,4-epoxy)cyclohexane carboxylate, 4,4'-bis(1,2-epoxycyclohexane), bis(3,4-epoxy cyclohexylmethyl)ether, bis(3,4-epoxycyclohexan-1-ylmethyl)adipate, 1,2-epoxy-4-(2-oxiranyl)cyclohexane addition of 2,2-bis(hydroxymethyl)-1-butanol product, [(3,4-epoxycyclohexane)-1-yl]methyl methacrylate, fluorene type epoxy compound, 1,7-octadiene diepoxide, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl Ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glyco
• Examples of the other oxetane compounds include 3-ethyl-3-(((3-ethyloxetane-3-yl)methoxy)methyl)oxetane, 3-ethyl-3-((2-ethylhexyloxy)methyl)oxetane , 3-ethyl-3-((3-(triethoxysilyl)propoxy)methyl)oxetane, phenol novolak oxetane, 1,4-bis(((3-ethyl-3-oxetanyl)methoxy)methyl)benzene and the like. be done.
• vinyl ether compound examples include benzyl vinyl ether, cyclohexanedimethanol monovinyl ether, dicyclopentadiene vinyl ether, 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and dipropylene glycol. divinyl ether, tripropylene glycol divinyl ether, and the like.
• the curable resin composition of the present invention contains a cationic polymerization initiator.
• a cationic polymerization initiator include thermal cationic polymerization initiators and photocationic polymerization initiators.
• the thermal cationic polymerization initiator has an anion moiety of BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , or (BX 4 ) ⁇ (where X is substituted with at least two fluorine or trifluoromethyl groups).
• sulfonium salts, phosphonium salts, ammonium salts, diazonium salts, iodonium salts, etc. composed of a phenyl group represented by a phenyl group). Among them, sulfonium salts are preferred.
• sulfonium salt examples include triphenylsulfonium tetrafluoroborate and triphenylsulfonium hexafluoroantimonate.
• Examples of the phosphonium salts include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.
• ammonium salts include dimethylphenyl(4-methoxybenzyl)ammonium hexafluorophosphate, dimethylphenyl(4-methoxybenzyl)ammonium hexafluoroantimonate, dimethylphenyl(4-methoxybenzyl)ammonium tetrakis(pentafluorophenyl) Borate, dimethylphenyl(4-methylbenzyl)ammonium hexafluorophosphate, dimethylphenyl(4-methylbenzyl)ammonium hexafluoroantimonate, dimethylphenyl(4-methylbenzyl)ammonium hexafluorotetrakis(pentafluorophenyl)borate, methylphenyl Dibenzylammonium hexafluorophosphate, methylphenyldibenzylammonium hexafluoroantimonate, methylphenyldibenzylammonimonium
• thermal cationic polymerization initiators examples include thermal cationic polymerization initiators manufactured by Sanshin Chemical Industry Co., Ltd., and thermal cationic polymerization initiators manufactured by King Industries.
• thermal cationic polymerization initiator manufactured by Sanshin Chemical Industry examples include San-Aid SI-60, San-Aid SI-80, San-Aid SI-B3, San-Aid SI-B3A, and San-Aid SI-B4.
• thermal cationic polymerization initiator manufactured by King Industries examples include CXC-1612 and CXC-1821.
• the photocationic polymerization initiator is not particularly limited as long as it generates a protonic acid or a Lewis acid by light irradiation, and may be an ionic photoacid-generating type or a nonionic photoacid-generating type. may
• anion portion of the ionic photoacid-generating photocationic polymerization initiator examples include BF 4 ⁇ , PF 6 ⁇ , SbF 6 ⁇ , (BX 4 ) ⁇ (wherein X is at least two or more fluorine or a phenyl group substituted with a trifluoromethyl group). Further, as the anion portion, PF m (C n F 2n+1 ) 6-m ⁇ (wherein m is an integer of 0 or more and 5 or less, and n is an integer of 1 or more and 6 or less), etc. mentioned.
• Examples of the ionic photoacid-generating photocationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts, (2,4-cyclo pentadien-1-yl)((1-methylethyl)benzene)-Fe salts and the like.
• aromatic sulfonium salts include bis(4-(diphenylsulfonio)phenyl)sulfide bishexafluorophosphate, bis(4-(diphenylsulfonio)phenyl)sulfide bishexafluoroantimonate, bis(4-( diphenylsulfonio)phenyl)sulfide bistetrafluoroborate, bis(4-(diphenylsulfonio)phenyl)sulfidetetrakis(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, diphenyl-4-( phenylthio)phenylsulfonium hexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfonium tetrafluoroborate, diphenyl
• triarylsulfonium tetrakis(pentafluorophenyl)borate such as triphenylsulfonium tetrakis(pentafluorophenyl)borate is preferable.
• aromatic iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis(pentafluorophenyl)borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis (dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrafluoroborate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexa fluorophosphate, 4-methylphenyl-4-(1-methylethyl)
• aromatic diazonium salts examples include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis(pentafluorophenyl)borate.
• aromatic ammonium salts examples include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl -2-cyanopyridinium tetrakis(pentafluorophenyl)borate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluorophosphate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluoroantimonate, 1-(naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, 1-(naphthylmethyl)-2-cyanopyridinium tetrakis(pentafluorophenyl)borate and the like.
• Examples of the (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe salt include (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene )-Fe(II) hexafluorophosphate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) hexafluoroantimonate, (2,4-cyclopentadiene-1 -yl)((1-methylethyl)benzene)-Fe(II) tetrafluoroborate, (2,4-cyclopentadien-1-yl)((1-methylethyl)benzene)-Fe(II) tetrakis(penta fluorophenyl)borate and the like.
• nonionic photoacid-generating photocationic polymerization initiator examples include nitrobenzyl esters, sulfonic acid derivatives, phosphoric acid esters, phenolsulfonic acid esters, diazonaphthoquinone, and N-hydroxyimide sulfonates.
• Examples of commercially available photocationic polymerization initiators include, for example, a photocationic polymerization initiator manufactured by Midori Chemical Co., Ltd., a photocationic polymerization initiator manufactured by Union Carbide, a photocationic polymerization initiator manufactured by ADEKA, Photocationic polymerization initiators manufactured by 3M, photocationic polymerization initiators manufactured by BASF, photocationic polymerization initiators manufactured by Solvay, and photocationic polymerization initiators manufactured by San-Apro. Examples of the photocationic polymerization initiator manufactured by Midori Kagaku Co., Ltd. include DTS-200 and the like. Examples of photo cationic polymerization initiators manufactured by Union Carbide include UVI6990 and UVI6974.
• Examples of photo cationic polymerization initiators manufactured by ADEKA include SP-150 and SP-170. Examples of photo cationic polymerization initiators manufactured by 3M include FC-508 and FC-512. Examples of photo cationic polymerization initiators manufactured by BASF include IRGACURE261 and IRGACURE290. Examples of photo cationic polymerization initiators manufactured by Solvay include PI2074. Examples of photo cationic polymerization initiators manufactured by San-Apro include CPI-100P, CPI-200K, CPI-210S and the like.
• quaternary ammonium salts whose counter anions are borate-based (hereinafter also referred to as "borate-based quaternary ammonium salts") are preferably used.
• the counter anion of the borate-based quaternary ammonium salt is BF 4 - or (BX 4 )- (wherein X represents a phenyl group substituted with at least two or more fluorine or trifluoromethyl groups). is preferred.
• the content of the cationic polymerization initiator has a preferable lower limit of 0.05 parts by weight and a preferable upper limit of 10 parts by weight based on 100 parts by weight of the cationic polymerizable compound.
• the content of the cationic polymerization initiator is within this range, the resulting curable resin composition is excellent in curability, storage stability, and moisture resistance of the cured product.
• a more preferred lower limit to the content of the cationic polymerization initiator is 0.1 parts by weight, and a more preferred upper limit is 5 parts by weight.
• the curable resin composition of the present invention preferably contains a stabilizer. By containing the stabilizer, the curable resin composition of the present invention becomes more excellent in storage stability.
• stabilizer examples include triethanolamine, benzylamine, triglycidyl-p-aminophenol and the like. These stabilizers may be used alone or in combination of two or more.
• the preferable lower limit of the content of the stabilizer is 0.001 part by weight, and the preferable upper limit is 2 parts by weight with respect to 100 parts by weight of the cationic polymerizable compound.
• the resulting curable resin composition has excellent storage stability while maintaining excellent curability.
• a more preferable lower limit to the content of the stabilizer is 0.005 parts by weight, and a more preferable upper limit is 1 part by weight.
• the curable resin composition of the invention may contain a silane coupling agent.
• the silane coupling agent has a role of improving the adhesiveness between the curable resin composition of the present invention and a substrate or the like.
• silane coupling agent examples include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane and the like. These silane coupling agents may be used alone, or two or more of them may be used in combination.
• the content of the silane coupling agent has a preferable lower limit of 0.1 parts by weight and a preferable upper limit of 10 parts by weight based on 100 parts by weight of the cationic polymerizable compound.
• a more preferable lower limit for the content of the silane coupling agent is 0.5 parts by weight, and a more preferable upper limit is 5 parts by weight.
• the content of the silane coupling agent has a preferable upper limit of 0.5 parts by weight, and a more preferable upper limit of 0.1 parts by weight, relative to 100 parts by weight of the cationically polymerizable compound. parts by weight, and the more preferable upper limit is 0.01 parts by weight.
• the curable resin composition of the present invention may further contain a surface modifier as long as the object of the present invention is not impaired.
• a surface modifier By containing the surface modifier, the flatness of the coating film of the curable resin composition of the present invention can be improved.
• the surface modifier include surfactants and leveling agents.
• Examples of the surface modifier include silicone-based, acrylic-based, and fluorine-based agents.
• Examples of commercially available surface modifiers include surface modifiers manufactured by BYK-Chemie Japan and surface modifiers manufactured by AGC Seimi Chemical.
• Examples of the surface modifier manufactured by BYK-Chemie Japan include BYK-330, BYK-340 and BYK-345.
• Examples of the surface modifier manufactured by AGC Seimi Chemical Co., Ltd. include Surflon S-611.
• the curable resin composition of the present invention is a compound or ion-exchange compound that reacts with the acid generated in the curable resin composition in order to improve the durability of the device electrode, etc., within the range that does not hinder the object of the present invention. It may contain a resin.
• Examples of the compound that reacts with the generated acid include substances that neutralize the acid, such as alkali metal carbonates or hydrogen carbonates, alkaline earth metal carbonates or hydrogen carbonates, and the like.
• substances that neutralize the acid such as alkali metal carbonates or hydrogen carbonates, alkaline earth metal carbonates or hydrogen carbonates, and the like.
• calcium carbonate, calcium hydrogencarbonate, sodium carbonate, sodium hydrogencarbonate and the like are used.
• any of a cation exchange type, an anion exchange type, and an amphoteric ion exchange type can be used. is preferred.
• the curable resin composition of the present invention may contain a solvent for the purpose of adjusting the viscosity, etc., but the remaining solvent may cause outgassing or may cause organic light emission when used as a sealant for an organic EL display element. Since problems such as deterioration of the material layer may occur, it is preferable that the solvent is not contained or the solvent content is 0.05% by weight or less.
• the curable resin composition of the present invention contains various known additives such as curing retarders, reinforcing agents, softening agents, plasticizers, viscosity modifiers, ultraviolet absorbers, and antioxidants. You may
• the curable resin composition of the present invention preferably has a lower limit of 0.1 Pa ⁇ s and a preferred upper limit of viscosity measured at 25° C. using an E-type viscometer of 5000 Pa ⁇ s. When the viscosity is within this range, the resulting curable resin composition will have excellent coatability.
• a more preferable lower limit of the viscosity is 0.2 Pa ⁇ s, and a more preferable upper limit is 2000 Pa ⁇ s.
• the above viscosity can be measured, for example, by using VISCOMETER TV-22 (manufactured by Toki Sangyo Co., Ltd.) as an E-type viscometer. No. 7 rotor can be used for measurement at 1.0 rpm.
• the preferable lower limit of the refractive index for the sodium D line at 25° C. of the cured product is 1.6. Since the refractive index is 1.6 or more, when it is used as a sealant for a display element such as an organic EL display element, the refractive index difference between the electrode and the passivation film is small, and as a result, the obtained The resulting display device has excellent light extraction efficiency.
• a more preferable lower limit of the refractive index is 1.61. Although there is no particular upper limit for the refractive index, the practical upper limit is 1.9.
• the "sodium D line refractive index" can be measured using an Abbe refractometer.
• the cured product for measuring the refractive index for example, a measurement piece having a length of 20 mm, a width of 10 mm, and a thickness of 100 ⁇ m is used.
• the cured product for measuring the refractive index can be obtained by irradiating ultraviolet rays of about 1500 mJ/cm 2 for a photocurable resin composition, and for a thermosetting resin composition at 150° C. for 10 minutes. It can be obtained by heating, and if it is a photothermosetting resin composition, it can be obtained by heating at 150° C. for 10 minutes after irradiating ultraviolet rays of about 1500 mJ/cm 2 .
• the curable resin composition of the present invention preferably has a cure shrinkage of 7.0% or less.
• the cure shrinkage rate is 7.0% or less, the curable resin composition of the present invention can prevent the adherend from warping and peeling.
• a more preferable upper limit of the cure shrinkage rate is 5.0%, a further preferable upper limit is 4.0%, a particularly preferable upper limit is 3.5%, and the most preferable upper limit is 2.5%.
• the practical lower limit is 1.0%.
• the cured product used for measuring the density can be obtained by irradiating ultraviolet rays of about 1500 mJ/cm 2 for a photocurable resin composition, and for a thermosetting resin composition at 150° C. for 10 minutes. It can be obtained by heating, and if it is a photothermosetting resin composition, it can be obtained by heating at 150° C. for 10 minutes after irradiating ultraviolet rays of about 1500 mJ/cm 2 .
• the curable resin composition of the present invention can be suitably used as a sealant for display elements, and can be particularly suitably used as a sealant for organic EL display elements.
• a sealant for display elements and a sealant for organic EL display elements containing the curable resin composition of the present invention are also included in the present invention.
• the sealant for an organic EL display element of the present invention is particularly suitably used as an in-plane sealant for covering and sealing a laminate having an organic light-emitting material layer. Moreover, the sealant for organic EL display elements of the present invention is suitably used for sealing top emission type organic EL display elements.
• the sealant for an organic EL display element of the present invention is applied by a printing method, a dispensing method, an inkjet method, or the like.
• a method including a step of applying to a substrate and a step of curing the applied sealant for organic EL display element by at least one of heating and light irradiation.
• the sealant for organic EL display elements of the present invention may be applied to the entire surface of the base material, or may be applied to a part of the base material. You can apply it.
• the shape of the sealing portion of the sealing agent for an organic EL display element of the present invention formed by coating is not particularly limited as long as it is a shape capable of protecting the laminate having the organic light-emitting material layer from the outside air. It may be a shape that completely covers the body, a closed pattern may be formed in the peripheral portion of the laminate, or a pattern having a shape with a partial opening provided in the peripheral portion of the laminate. may be formed.
• the sealant for an organic EL display element When the sealant for an organic EL display element is cured by heating, it is preferable to heat at a temperature of 50° C. or higher and 120° C. or lower from the viewpoint of sufficiently curing while reducing damage to the laminate having the organic light emitting material layer. .
• the sealant for organic EL display elements of the present invention When the sealant for organic EL display elements of the present invention is cured by light irradiation, the sealant for organic EL display elements of the present invention has a wavelength of 300 nm to 400 nm and a wavelength of 300 mJ/cm 2 to 3000 mJ/cm 2 . It can be suitably cured by irradiating the integrated light amount.
• Examples of light sources used for light irradiation include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, excimer lasers, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, sodium lamps, halogen lamps, and xenon. lamps, LED lamps, fluorescent lamps, sunlight, electron beam irradiation devices, and the like. These light sources may be used alone or in combination of two or more. These light sources are appropriately selected according to the absorption wavelength of the photocationic polymerization initiator.
• Examples of means for irradiating the sealant for an organic EL display element of the present invention with light include simultaneous irradiation with various light sources, sequential irradiation with a time lag, combined irradiation of simultaneous and sequential irradiation, and the like. Any irradiation means may be used.
• the cured product obtained by the step of curing the sealant for an organic EL display element by at least one of heating and light irradiation may be further coated with an inorganic material film.
• an inorganic material film conventionally known materials can be used, and examples thereof include silicon nitride (SiN x ) and silicon oxide (SiO x ).
• the inorganic material film may be a single layer, or may be a laminate of a plurality of types of layers. Alternatively, the inorganic material film and the resin film composed of the sealant for an organic EL display element of the present invention may be alternately repeated to coat the laminate.
• the method for producing the organic EL display element includes a step of bonding a base material coated with the sealant for an organic EL display element of the present invention (hereinafter also referred to as "one base material") and the other base material. may have.
• the one base material may be a base material on which a laminate having an organic light-emitting material layer is formed, or may be a base material on which the laminate is not formed.
• the one base material is a base material on which the laminate is not formed
• the other base material is bonded, the one base material of the present invention is attached to the one base material so that the laminate can be protected from the outside air.
• the organic EL display element sealant of the above may be applied.
• a closed pattern of the encapsulant portion may be formed in a shape that fits within.
• a so-called dam-fill sealing method may be used. That is, first, a curable paste is applied on the substrate of the organic EL display element so as to surround the periphery of the display portion. Next, the sealant for an organic EL display element of the present invention is applied to the inside of the applied curable paste, and the facing sealing substrates are attached while preventing the sealant from oozing out due to the curable paste on the periphery. After that, a method of curing the curable paste on the peripheral edge and the sealant for an organic EL display element of the present invention pushed and spread inward by at least one of heating and light irradiation may be used.
• the step of curing the sealant for an organic EL display element by at least one of heating and light irradiation may be performed before the step of bonding the one base material and the other base material together. You may carry out after the process of bonding one base material and the said other base material together.
• the organic EL display element of the present invention It is preferable that the sealant for EL display elements has a pot life of 1 minute or more, from the time when at least one of heating and light irradiation is performed until the curing reaction progresses and adhesion becomes impossible. When the pot life is 1 minute or longer, a higher adhesive strength can be obtained without excessive curing before bonding the one base material and the other base material together.
• the method of bonding the one base material and the other base material together is not particularly limited, but bonding under a reduced pressure atmosphere is preferable.
• a preferable lower limit of the degree of vacuum under the reduced pressure atmosphere is 0.01 kPa, and a preferable upper limit thereof is 10 kPa. Since the degree of vacuum under the reduced-pressure atmosphere is within this range, the one substrate and the other substrate can be separated from each other without spending a long time to achieve a vacuum state due to the airtightness of the vacuum device and the capacity of the vacuum pump. Air bubbles in the sealant for an organic EL display element of the present invention can be removed more efficiently when the material is attached.
• the curable resin composition of the present invention can also be suitably used as an optical adhesive.
• An optical adhesive containing the curable resin composition of the present invention is also one aspect of the present invention.
• Examples of adherends of the optical adhesive of the present invention include optical members such as optical lenses, optical sheets, filters, diffraction gratings, prisms, and optical fibers.
• the optical adhesive of the present invention is preferably used for bonding optical members such as optical lenses, optical sheets, filters, diffraction gratings, prisms and optical fibers.
• a cured product of the curable resin composition of the present invention can also be suitably used as an optical member.
• An optical member containing a cured product of the curable resin composition of the present invention is also one aspect of the present invention.
• the optical member of the present invention is preferably a molded body.
• Examples of the optical member of the present invention include optical lenses, optical device members, display device members, and the like.
• ADVANTAGE OF THE INVENTION According to this invention, it is excellent in curability and can provide the curable resin composition with a high refractive index of hardened
• Examples 1 to 10, Comparative Examples 1 to 3 According to the compounding ratio described in Tables 1 and 2, each material was stirred and mixed at a stirring speed of 2000 rpm using a stirring mixer, Examples 1 to 10, Comparative Examples 1 to 3 Each curable resin composition. was made. AR-250 (manufactured by Thinky Corporation) was used as a stirring mixer.
• Viscosity and storage stability Using an E-type viscometer, the viscosity (initial viscosity) of each curable resin composition obtained in Examples and Comparative Examples was measured at 25° C. and 1.0 rpm.
• VISCOMETER TV-22 manufactured by Toki Sangyo Co., Ltd.
• the rotor No. 7 rotor was used.
• the viscosity of each curable resin composition obtained in Examples and Comparative Examples was measured in the same manner as the initial viscosity when stored at 40 ° C.
• the densities of the curable resin compositions and the cured products obtained in Examples and Comparative Examples were measured using a dry density meter (manufactured by Shimadzu Corporation, "Accupic II 1345").
• the curable resin compositions obtained in Examples 1 to 4, 8 to 10, and Comparative Examples 1 to 3 were heated at 150 ° C. for 10 minutes, and the curability obtained in Examples 5 to 7
• a cured product was obtained by irradiating 1500 mJ/cm 2 of ultraviolet rays with a wavelength of 365 nm using a UV-LED. From the obtained densities, the curing shrinkage rate was calculated by the above formula.
• JMS-Q1050 (manufactured by JEOL Ltd.) was used as a gas chromatograph mass spectrometer. If the outgassing amount was less than 100 ppm, " ⁇ ”, if it was 100 ppm or more and less than 200 ppm, “ ⁇ ", if it was 200 ppm or more and less than 400 ppm, “ ⁇ ", if it was 400 ppm or more, “ ⁇ ” ” and evaluated the low outgassing property.
• a mold was prepared by cutting a silicone rubber sheet having a thickness of 100 ⁇ m into a rectangle having a length of 20 mm and a width of 10 mm. After placing this mold on a release PET film and filling the mold with each curable resin composition obtained in Examples and Comparative Examples, cover another release PET film so that no air bubbles remain. By stacking, a laminate was obtained. The obtained laminate was sandwiched and fixed between two glass plates, and the curable resin composition was cured. The curable resin compositions obtained in Examples 1 to 4, 8 to 10, and Comparative Examples 1 to 3 were cured by heating at 150 ° C.
• the flexible resin composition was cured by irradiating 1500 mJ/cm 2 of ultraviolet rays with a wavelength of 365 nm using a UV-LED. After that, the PET film was peeled off and the cured sealant was removed from the silicone rubber sheet to obtain a test piece having a length of 10 mm, a width of 20 mm and a thickness of 100 ⁇ m.
• the obtained test piece was measured for the sodium D line refractive index at 25° C. using an Abbe refractometer. NAR-4T (manufactured by Atago Co., Ltd.) was used as the Abbe refractometer.
• the refractive index was evaluated as " ⁇ " when the refractive index was 1.60 or more, " ⁇ " when it was 1.58 or more and less than 1.60, and " ⁇ " when it was less than 1.58. bottom.
• a mold made of a PET film with a thickness of 100 ⁇ m was placed on a glass substrate, and each curable resin composition obtained in Examples and Comparative Examples was filled in the mold.
• the curable resin composition was cured to obtain a test piece.
• the curable resin compositions obtained in Examples 1 to 4, 8 to 10, and Comparative Examples 1 to 3 were cured by heating at 100 ° C. for 30 minutes, and the cured products obtained in Examples 5 to 7
• the flexible resin composition was cured by irradiating 1500 mJ/cm 2 of ultraviolet rays with a wavelength of 365 nm using a UV-LED.
• the obtained test piece was measured for transmittance at a wavelength of 430 nm at 25° C.
• ADVANTAGE OF THE INVENTION According to this invention, it is excellent in curability and can provide the curable resin composition with a high refractive index of hardened

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