WO2017170888A1 - 樹脂組成物 - Google Patents

樹脂組成物 Download PDF

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Publication number
WO2017170888A1
WO2017170888A1 PCT/JP2017/013301 JP2017013301W WO2017170888A1 WO 2017170888 A1 WO2017170888 A1 WO 2017170888A1 JP 2017013301 W JP2017013301 W JP 2017013301W WO 2017170888 A1 WO2017170888 A1 WO 2017170888A1
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group
resin composition
compound
formula
weight
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PCT/JP2017/013301
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English (en)
French (fr)
Japanese (ja)
Inventor
江川智哉
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株式会社ダイセル
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Priority to CN201780001410.XA priority Critical patent/CN107531817B/zh
Priority to KR1020177029440A priority patent/KR101878117B1/ko
Priority to JP2017534757A priority patent/JP6211746B1/ja
Publication of WO2017170888A1 publication Critical patent/WO2017170888A1/ja

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C07C321/30—Sulfides having the sulfur atom of at least one thio group bound to two carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • 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
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1458—Monomers containing nitrogen
    • 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
    • C08F228/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur
    • C08F228/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a bond to sulfur or by a heterocyclic ring containing sulfur by a bond to sulfur
    • C08F228/04—Thioethers
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • 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
    • 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
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

  • the present invention relates to a resin composition that can be used as a fill material when an organic electroluminescence element is sealed by a dam and fill method.
  • This application claims the priority of Japanese Patent Application No. 2016-074517 for which it applied to Japan on April 1, 2016, and uses the content here.
  • organic EL device including an organic electroluminescence (hereinafter sometimes referred to as “organic EL”) element is used as a full-color flat panel display or an LED because of high impact resistance, high visibility, and a variety of emission colors. Expected to replace.
  • organic EL devices There are two types of organic EL devices, a top emission type and a bottom emission type, due to differences in light extraction methods.
  • organic EL elements are more susceptible to moisture than other electronic components, and moisture that penetrates into the organic EL elements can cause electrode oxidation or organic modification, resulting in a significant decrease in light emission characteristics.
  • Met As a method for solving this problem, a method of sealing (or covering) the periphery of the organic EL element with a low moisture-permeable resin is known.
  • a method for sealing with the resin As a method for sealing with the resin, a method of sealing by filling the periphery of the organic EL element formed on the substrate with a resin composition that is cured by ultraviolet irradiation, and then curing the resin composition (1) And a method (2) in which a resin composition is applied to a lid (lid) and irradiated with ultraviolet rays, and then bonded to a substrate on which an organic EL element is formed and sealed (2).
  • the method (1) has a problem in that the light emission characteristics are deteriorated by directly exposing the organic EL element to ultraviolet rays.
  • the problem is that the resin composition is difficult to cure because the color filter blocks ultraviolet rays. It was.
  • Patent Document 1 discloses that a resin composition containing an epoxy compound, a cationic photopolymerization initiator, and a crown ether or a polyether as a curing retarder gradually progresses after the ultraviolet irradiation, It is described that when the composition is used in the method (2), the organic EL device can be sealed without being directly exposed to ultraviolet rays.
  • crown ethers and polyethers are decomposed by an acid generated from a photocationic polymerization initiator to generate outgas, and the organic EL element is deteriorated by the outgas.
  • the cured product of the resin composition is required to have a high refractive index in order to make it difficult for light to be reflected at the interface with the organic EL element.
  • a resin for forming a cured product having a high refractive index a bis (4-vinylthiophenyl) sulfide derivative is known (Patent Document 2).
  • the bis (4-vinylthiophenyl) sulfide derivative has a low viscosity, and when the resin composition containing the bis (4-vinylthiophenyl) sulfide derivative is used as a fill material when sealing an organic EL device by, for example, a dam and fill method, the above method (2 ) Is likely to flow out of the dam when bonded to the substrate.
  • a polymer compound for example, petroleum resin
  • a resin composition containing an acetone-insoluble polymer compound is used in a liquid dispensing device such as a dispenser or an inkjet coating device.
  • the viscosity is increased to such an extent that it can be prevented from flowing out of the dam, it may be difficult to discharge using the device, etc., good dischargeability from the device, etc., cleanability inside the device, etc. It was very difficult to combine the prevention of spillage from the dam.
  • an object of the present invention is a resin composition that can be used as a fill material when sealing an organic EL element by a dam and fill method, and is excellent in applicability and acetone solubility, and has a timing of thickening and curing. It is an object to provide a resin composition capable of forming a cured product having a high refractive index, a low moisture permeability, and a low outgassing property. Another object of the present invention is to provide an organic EL device having a configuration in which an organic EL element is sealed with a cured product of the resin composition.
  • Phenyl sulfide compound (A) having two reactive functional groups in a molecule, a specific compound (B) having one polymerizable unsaturated group in one molecule, a photocationic polymerization initiator (C 1) is low in viscosity, excellent in coatability and excellent in acetone solubility.
  • the resin composition is irradiated with ultraviolet rays, the (A) exhibits curing retardation, and at the same time, the (B) exhibits curing properties, so that the curing reaction of the resin composition is moderately thickened.
  • the curing reaction once stopped can be resumed by applying heat treatment, and thereafter a cured product can be formed quickly.
  • the obtained cured product has high refractive index, low moisture permeability, and low outgassing properties.
  • the present invention has been completed based on these findings.
  • this invention provides the resin composition containing the following compound (A), the following compound (B), and a photocationic polymerization initiator (C).
  • a hydroxyalkyl group an amino group optionally protected with a protecting group, a carboxyl group optionally protected with a protecting group, a sulfo group optionally protected with a protecting group, a nitro group, a cyano group, or a protecting group;
  • An acyl group which may be protected R c represents a single bond or a linking group, m represents an integer of 0 to 4, n represents an integer of 0 to 10.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrocarbon group
  • t represents an integer of 0 or more
  • t represents an integer of 2 or more
  • a plurality of R 2 are the same.
  • a plurality of R 2 may be bonded to each other to form a ring together with the carbon atoms constituting the aromatic ring in the formula.
  • the present invention also provides the above resin composition, wherein R a in the formula (a) is a vinyl group or an allyl group.
  • the compound represented by the formula (b-2) is represented by the following formula (b-2-1): (Wherein R 1 represents a hydrogen atom or a methyl group, and L represents a linking group)
  • the resin composition is a compound represented by:
  • the content ratio of the compound (A) to the compound (B) is 60:40 to 95: 5, and the compound (A) and the compound (B) Provided is the above resin composition having a total content of 50% by weight or more of the total amount of the curable compound contained in the resin composition.
  • the present invention also provides the above resin composition having a viscosity at 25 ° C. of 10 mPa ⁇ s or more and less than 30 mPa ⁇ s.
  • the present invention also provides the resin composition as described above, which is an organic electroluminescence device sealant.
  • the present invention also provides a method for producing an organic electroluminescent device, wherein the organic electroluminescent element is sealed through the following steps 1 and 2.
  • Step 1 UV irradiation is performed on the coating film made of the resin composition.
  • Step 2 The UV-irradiated coating film obtained through Step 1 is bonded to the element mounting surface of the substrate on which the organic electroluminescence element is mounted. Heat treatment
  • the present invention also provides an organic electroluminescence device having a structure in which an element is sealed with a cured product of the resin composition.
  • the present invention relates to the following.
  • At least one selected from the compound (A) represented by the formula (a), the compound represented by the formula (b-1), and the compound represented by the following formula (b-2) The resin composition containing a compound (B) and a photocationic polymerization initiator (C).
  • R a in the formula (a) is a cationically polymerizable group.
  • R a in the formula (a) is a group selected from a vinyl group, an allyl group, an epoxy group, a glycidyl group, and an oxetanyl group.
  • Y in formula (b-1) is a divalent hydrocarbon group (preferably a C 1-18 alkylene group, a C 2-8 alkenylene group, a C 6-10 arylene group, and a single bond thereof.
  • [1] to [9] which are groups selected from a group selected from a group linked via a carbonyl group, an ether bond, an ester bond, an amide bond, a carbonate bond, and a group in which a plurality of these groups are linked.
  • At least one compound in which the compound represented by the formula (b-1) is selected from N-vinylcarbazole, N-allylcarbazole, N- (meth) acryloylcarbazole, and N- (vinylbenzyl) carbazole The resin composition according to any one of [1] to [11].
  • L in the formula (b-2) is a divalent hydrocarbon group (preferably a C 1-18 alkylene group, a C 2-8 alkenylene group, a C 6-10 arylene group, or a single bond thereof) A group selected from a group linked through a carbonyl group, an ether bond, a thioether bond, an ester bond, an amide bond, a carbonate bond, and a group in which a plurality of these are linked, [1] -The resin composition as described in any one of [12]. [14] In any one of [1] to [13], the molecular weight of the compound represented by the formula (b-2) is 1000 to 70 (preferably 700 to 100, particularly preferably 400 to 150). The resin composition as described.
  • the content of the compound other than the compound (A), the compound (B), and the photocationic polymerization initiator (C) is 40% by weight or less (preferably 20% by weight or less, particularly preferably 10% by weight) of the total amount of the resin composition. % Or less), the resin composition according to any one of [1] to [15].
  • the total content of the compound (A), the compound (B) and the photocationic polymerization initiator (C) is 60% by weight or more (preferably 80% by weight or more, particularly preferably 90% by weight or more) of the total amount of the resin composition.
  • the content of the polymer compound having a weight average molecular weight of more than 1000 is 5% by weight or less (preferably 3% by weight or less, particularly preferably 1% by weight or less).
  • the content of a compound having a solubility parameter (SP value at 25 ° C .; a value calculated by the formula of Fedors) of 8.5 or more is 5% by weight or less (preferably 3% by weight or less, particularly preferably 1% by weight)
  • the content ratio of the compound (A) to the compound (B) is 60:40 to 95: 5 (preferably 65:35 to 90:10, particularly preferably 70: 30 to 85:15), and the total content of the compound (A) and the compound (B) is 50% by weight or more (preferably 60% by weight or more, more preferably, the total amount of the curable compound contained in the resin composition).
  • the content of the compound (A) is 45 to 95% (preferably 60 to 95% by weight, more preferably 65 to 90% by weight) of the total amount (100% by weight) of the curable compound contained in the resin composition.
  • the content of the compound (B) is 5 to 40% by weight (preferably 10 to 35% by weight, particularly preferably 15 to 30% by weight) of the total amount (100% by weight) of the curable compound contained in the resin composition.
  • the content of the photocationic polymerization initiator (C) is 0.01 to 15 parts by weight (preferably 0.01 to 10 parts by weight, particularly preferably 100 parts by weight of the curable compound contained in the resin composition). Is 0.05 to 5 parts by weight, and most preferably 0.1 to 3 parts by weight).
  • the resin composition according to any one of [1] to [23].
  • the viscosity according to any one of [1] to [24], in which the viscosity at 25 ° C. when not irradiated with ultraviolet rays is 10 mPa ⁇ s or more and less than 30 mPa ⁇ s (preferably 15 to 25 mPa ⁇ s). Resin composition.
  • the degree of increase in viscosity during 30 minutes after ultraviolet irradiation is 1.30 or less (preferably 1.20 or less).
  • Step 1 UV coating is applied to the coating film made of the resin composition according to any one of [1] to [29]
  • Step 2 is applied to the element mounting surface of the substrate on which the organic electroluminescence element is mounted.
  • the device was sealed with a cured product of the resin composition as described in any one of [1] to [29], after the ultraviolet-irradiated coating film obtained through the above was pasted and heat-treated An organic electroluminescence device having a configuration.
  • the moisture permeability (g / m 2 ⁇ day ⁇ atm) of the cured product having a thickness of 100 ⁇ m is 100 or less (preferably 50 or less, particularly preferably 35 or less, most preferably 25 or less).
  • Organic electroluminescence device is
  • the resin composition of the present invention Since the resin composition of the present invention has the above-described configuration, it is low in viscosity and excellent in fluidity until it is irradiated with ultraviolet rays, and can be discharged satisfactorily using a liquid dispensing apparatus or the like. Moreover, since the solubility which was excellent with respect to acetone used as an industrial cleaning agent is shown, the inside of the said apparatus etc. can be easily wash
  • the progress of the curing reaction can be stopped in the semi-cured state until the heat treatment is performed even after irradiation with ultraviolet rays, and the timing for restarting the curing reaction can be arbitrarily set by adjusting the timing for performing the heat treatment. can do.
  • it can harden
  • the resin composition of the present invention includes, in particular, a sealant (in particular, a fill material) for a top emission type organic EL device, a light extraction layer material for a bottom emission type organic EL device, a solar cell material, and a lens material. Etc. can be preferably used.
  • a sealant in particular, a fill material
  • Etc. can be preferably used.
  • an organic EL device having excellent light extraction efficiency, high efficiency, high luminance, and long life can be obtained.
  • the resin composition of the present invention is used as a lens material, a lens having a high refractive index can be obtained, and the lens can be made thinner and lighter, and the design of an electronic device including the lens can be improved. Can do.
  • the compound (A) in the present invention is a compound (curable compound) represented by the above formula (a).
  • Two R a in the above formula (a) represent a reactive functional group (polymerizable functional group).
  • the two R a may be respectively identical or different.
  • the reactive functional group include a cationic polymerizable group such as a vinyl group, an allyl group, an epoxy group, a glycidyl group, and an oxetanyl group.
  • a vinyl group or an allyl group is preferable.
  • a plurality of R b in the formula (a) may be the same or different and may be protected with a halogen atom, an alkyl group, a haloalkyl group, an aryl group, a hydroxyl group which may be protected with a protecting group, or a protecting group.
  • Examples of the halogen atom for R b include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the alkyl group in R b include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, hexyl group, heptyl group, octyl group, and nonyl group.
  • a C 1-10 (preferably C 1-5 ) alkyl group such as a decyl group.
  • haloalkyl group for R b examples include C 1-10 (preferably C 1-5 ) haloalkyl groups such as a chloromethyl group, a trifluoromethyl group, a trifluoroethyl group, and a pentafluoroethyl group. it can.
  • aryl group for R b examples include a phenyl group and a naphthyl group.
  • the aromatic ring of the aryl group includes, for example, a halogen atom such as a fluorine atom, a C 1-4 alkyl group such as a methyl group, a C 1-5 haloalkyl group such as a trifluoromethyl group, a hydroxyl group, and a methoxy group.
  • a halogen atom such as a fluorine atom
  • a C 1-4 alkyl group such as a methyl group
  • a C 1-5 haloalkyl group such as a trifluoromethyl group
  • a hydroxyl group and a methoxy group.
  • C 1-4 alkoxy group an amino group, a dialkylamino group, a carboxyl group, C 1-4 alkoxycarbonyl group such as methoxycarbonyl group, a nitro group, a cyano group
  • an acyl group such as an acetyl group (in particular, C 1-6 aliphatic Group (s
  • hydroxyalkyl group for R b examples include C 1-10 (preferably C 1-5 ) in which at least one hydrogen atom of the C 1-10 alkyl group such as hydroxymethyl group is substituted with a hydroxyl group.
  • a hydroxyalkyl group etc. can be mentioned.
  • a protecting group commonly used in the field of organic synthesis for example, alkyl group (for example, C 1-4 alkyl such as methyl group, t-butyl group, etc.) Alkenyl group (eg, allyl group); cycloalkyl group (eg, cyclohexyl group); aryl group (eg, 2,4-dinitrophenyl group); aralkyl group (eg, benzyl group); A substituted methyl group (eg, methoxymethyl group, methylthiomethyl group, benzyloxymethyl group, t-butoxymethyl group, 2-methoxyethoxymethyl group, etc.), substituted ethyl group (eg, 1-ethoxyethyl group, etc.), tetrahydropyrani Hydroxyl groups, tetrahydrofuranyl groups, 1-hydroxyalkyl groups (for example, 1-hydroxyethyl)
  • Examples of the protecting group for the amino group in R b include protecting groups commonly used in the field of organic synthesis (eg, alkyl groups, aralkyl groups, acyl groups, alkoxycarbonyl groups and the like exemplified as the protecting groups for the hydroxyl group). Can do.
  • Examples of the protecting group for carboxyl group and sulfo group for R b include protecting groups commonly used in the field of organic synthesis [eg, alkoxy groups (eg, C 1-6 alkoxy such as methoxy group, ethoxy group, butoxy group, etc.). Group, etc.), cycloalkyloxy group, aryloxy group, aralkyloxy group, trialkylsilyloxy group, optionally substituted amino group, hydrazino group, alkoxycarbonylhydrazino group, aralkylcarbonylhydrazino group, etc. ] Can be mentioned.
  • alkoxy groups eg, C 1-6 alkoxy such as methoxy group, ethoxy group, butoxy group, etc.
  • Group, etc. cycloalkyloxy group, aryloxy group, aralkyloxy group, trialkylsilyloxy group, optionally substituted amino group, hydrazino group, alkoxycarbonylhydrazino group
  • Examples of the acyl group in R b include C 1-6 aliphatic acyl groups such as formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, and pivaloyl group; aromatic acyl groups such as acetoacetyl group; Groups and the like.
  • As the protecting group for the acyl group a protecting group commonly used in the field of organic synthesis can be used. Examples of the form in which the acyl group is protected include acetal (including hemiacetal).
  • a plurality of R b bonds to one aromatic ring in the formula (a) that is, when m in the formula (a) is 2 to 4
  • two or more selected from the plurality of R b Are bonded together to form a ring together with carbon atoms constituting an aromatic ring (for example, a 5-membered alicyclic carbocyclic ring, a 6-membered alicyclic carbocyclic ring, two or more alicyclic carbocyclic rings (monocyclic)).
  • a alicyclic carbocyclic ring such as a condensed ring of the above; a lactone ring such as a 5-membered lactone ring or a 6-membered lactone ring).
  • R c in the above formula (a) represents a single bond or a linking group (a divalent group having one or more atoms).
  • the linking group include a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), an ester bond (—COO—), an amide bond ( -CONH-), carbonate bond (-OCOO-), and a group in which a plurality of these are linked.
  • the linking group may have a substituent such as a hydroxyl group or a carboxyl group, and examples of such a linking group include a divalent hydrocarbon group having one or more hydroxyl groups.
  • Examples of the divalent hydrocarbon group include linear or branched alkylene groups having 1 to 18 carbon atoms, and divalent alicyclic hydrocarbon groups.
  • Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group.
  • Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclohexene group.
  • the molecular weight of the compound (A) is not particularly limited, but is preferably 1000 or less, particularly preferably 700 or less, and most preferably 500 or less in terms of compatibility with the compound (B).
  • the lower limit of the molecular weight is 302.
  • a plurality of m are the same or different and represent an integer of 0 to 4.
  • N (the number of repeating structural units in parentheses to which n is attached) represents an integer of 0 to 10.
  • n is preferably 0 to 3 and particularly preferably 0 in that the viscosity of the resin composition can be adjusted in a wide range. That is, as the compound (A), a compound represented by the following formula (a ′) is particularly preferable. (Wherein R a , R b and m are the same as above)
  • Examples of the compound (A) include compounds represented by the following formulas (a′-1) to (a′-12).
  • Compound (A) can be produced by a known or conventional method. For example, a method in which 4,4′-thiobisbenzenethiol or the like is used as a raw material and reacted with vinyl halide, allyl halide, halide of (meth) acrylic acid, epihalohydrin, etc. in the presence of a base. Can do.
  • a compound in which R a in formula (a) is a vinyl group can also be produced by a method of reacting 4,4′-thiobisbenzenethiol and dihaloethane, followed by dehydrohalogenation. .
  • Compound (A) has low viscosity and excellent acetone solubility. Moreover, the curing delay property is exhibited by trapping the acid generated from the photocationic polymerization initiator (C) by ultraviolet irradiation. When heat treatment is performed after irradiation with ultraviolet rays, the compound (A) releases the trapped acid and quickly cures to form a cured product having a high refractive index, low moisture permeability, and low outgassing properties. .
  • the compound (B) in the present invention includes at least one compound selected from the compound (b-1) and the compound (b-2).
  • the compound (b-1) in the present invention is a compound (cation and radical polymerizable compound) represented by the following formula (b-1).
  • the compound (b-1) undergoes a rapid polymerization reaction by the acid generated from the photocationic polymerization initiator (C). Therefore, the polymerization reaction can be allowed to proceed in a short time until the compound (A) traps the acid generated from the photocationic polymerization initiator (C). Further, when the photocationic polymerization initiator (C) is irradiated with ultraviolet rays, the photocationic polymerization initiator (C) absorbs the ultraviolet rays and decomposes to form a radical body, and the radical body extracts hydrogen to remove the acid.
  • the compound (b-1) can also react with the radical body to cause a polymerization reaction to proceed. Therefore, the polymerization reaction can proceed to some extent even in the presence of the compound (A) having an action of trapping an acid generated from the photocationic polymerization initiator (C), and the resin composition of the present invention is semi-cured. Can lead to a state. (Wherein Y represents a single bond or a linking group, and R 1 represents a hydrogen atom or a methyl group)
  • Y represents a single bond or a linking group.
  • the linking group include a divalent hydrocarbon group, a carbonyl group (—CO—), an ether bond (—O—), an ester bond (—COO—), an amide bond (—CONH—), a carbonate bond ( -OCOO-) and a group in which a plurality of these are linked.
  • divalent hydrocarbon group examples include, for example, a linear or branched alkylene group having 1 to 18 carbon atoms; vinylene group, propenylene group, 1-butenylene group, 2-butenylene group, butadienylene group, pentenylene group A straight or branched alkenylene group having 2 to 8 carbon atoms such as a hexenylene group, a heptenylene group or an octenylene group; a divalent alicyclic hydrocarbon group having 5 to 6 carbon atoms; Valent aromatic hydrocarbon group (for example, phenylene group, etc.) and a group in which these are linked through a single bond.
  • a linear or branched alkylene group having 1 to 18 carbon atoms vinylene group, propenylene group, 1-butenylene group, 2-butenylene group, butadienylene group, pentenylene group A straight or branched alkenylene group having 2 to 8 carbon atoms such as
  • the molecular weight (or weight average molecular weight) of the compound (b-1) is, for example, about 1000 to 70 (preferably 700 to 100, particularly preferably 400 to 150). It is preferable at the point which can provide the property.
  • the weight average molecular weight is a molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).
  • Examples of the compound (b-1) include N-vinylcarbazole, N-allylcarbazole, N- (meth) acryloylcarbazole, N- (vinylbenzyl) carbazole and the like. These can be used alone or in combination of two or more.
  • the compound (b-2) in the present invention is a compound (radical polymerizable compound) represented by the following formula (b-2).
  • the photocationic polymerization initiator (C) absorbs the ultraviolet rays and decomposes to form radicals, which generate acids by extracting hydrogen.
  • the compound (b-2) undergoes a curing reaction by reacting with the radical body, leading to the semi-cured state of the resin composition of the present invention.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a hydrocarbon group
  • t represents an integer of 0 or more, and when t is an integer of 2 or more, the plurality of R 2 may be the same or different.
  • L represents a linking group.
  • the hydrocarbon group in R 2 includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are bonded.
  • Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a decyl group, and a dodecyl group.
  • An alkyl group having about 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 3 carbon atoms) such as vinyl group, allyl group, 1-butenyl group, etc.
  • an alkenyl group having about 2 to 3 More preferred is an alkenyl group having about 2 to 3); an alkynyl group having about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as an ethynyl group and a propynyl group.
  • Examples of the alicyclic hydrocarbon group include 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group.
  • a cycloalkenyl group of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as a cyclopentenyl group and a cyclohexenyl group; a perhydronaphthalen-1-yl group , Norbornyl group, adamantyl group, tetracyclo [4.4.0.1 2,5 .
  • a bridged cyclic hydrocarbon group such as a 1,7,10 ] dodecan-3-yl group.
  • aromatic hydrocarbon group examples include aromatic hydrocarbon groups having about 6 to 14 (preferably 6 to 10) carbon atoms such as a phenyl group and a naphthyl group.
  • examples of the ring that may be bonded together to form a carbon atom that constitutes the aromatic ring in the formula include 3 to 20
  • examples include a non-aromatic carbocycle having 3 members and a non-aromatic heterocycle having 3 to 20 members.
  • the hydrocarbon group may have one or more substituents.
  • substituents include a halogen atom such as a fluorine atom, a C 1-5 haloalkyl group such as a trifluoromethyl group, a hydroxyl group, an amino group, a dialkylamino group, a carboxyl group, a nitro group, and a cyano group.
  • a halogen atom such as a fluorine atom
  • a C 1-5 haloalkyl group such as a trifluoromethyl group
  • a hydroxyl group such as an amino group, a dialkylamino group, a carboxyl group, a nitro group, and a cyano group.
  • R 2 in the formula (b-2) is preferably an aromatic hydrocarbon group.
  • T in the formula (b-2) represents an integer of 0 or more.
  • t is, for example, an integer of 0 to 3, and is preferably an integer of 1 or more (eg, an integer of 1 to 3).
  • L represents a linking group.
  • the linking group is a divalent group having one or more atoms.
  • a divalent hydrocarbon group a carbonyl group (—CO—), an ether bond (—O—), a thioether bond (—S—), Examples thereof include an ester bond (—COO—), an amide bond (—CONH—), a carbonate bond (—OCOO—), and a group in which a plurality of these are linked.
  • Examples of the divalent hydrocarbon group include the same examples as those in Y in the above formula (b-1).
  • the molecular weight (or weight average molecular weight) of the compound (b-2) is, for example, about 1000 to 70 (preferably 700 to 100, particularly preferably 400 to 150). It is preferable at the point which can provide the property.
  • the weight average molecular weight is a molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).
  • the compound (b-2) is excellent in compatibility with the above-described compound (A), and can form a cured product having a high refractive index, low moisture permeability, and low outgassing property.
  • a compound represented by formula (b-2-1) is preferred. In the following formulae, R 1 and L are the same as described above.
  • the resin composition of the present invention contains at least one compound selected from the compound (b-1) and the compound (b-2) as the compound (B) together with the compound (A).
  • the compound (A) traps an acid generated from the photocationic polymerization initiator (C) and exhibits curing retardation, while the compound (B) Since the curing reaction proceeds to some extent, a combination of these actions results in a semi-cured state.
  • Compound (B) in the present invention has low viscosity and excellent acetone solubility. Moreover, the hardened
  • the cationic photopolymerization initiator is a compound that decomposes by irradiation with ultraviolet rays to form a radical body, and the radical body extracts hydrogen to generate an acid to initiate a curing reaction of the curable compound.
  • the cationic photopolymerization initiator is composed of a cation moiety that absorbs light and an anion moiety that is a source of acid generation.
  • Examples of the photocationic polymerization initiator of the present invention include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, bromine salts. And the like, and the like.
  • a sulfonium salt compound is preferable in that a cured product having excellent curability can be formed.
  • the cation moiety of the sulfonium salt compound include aryls such as (4-hydroxyphenyl) methylbenzylsulfonium ion, triphenylsulfonium ion, diphenyl [4- (phenylthio) phenyl] sulfonium ion, and tri-p-tolylsulfonium ion.
  • aryls such as (4-hydroxyphenyl) methylbenzylsulfonium ion, triphenylsulfonium ion, diphenyl [4- (phenylthio) phenyl] sulfonium ion, and tri-p-tolylsulfonium ion.
  • examples include sulfonium ions (particularly triarylsulfonium ions).
  • anion part of the cationic photopolymerization initiator examples include BF 4 ⁇ , B (C 6 F 5 ) 4 ⁇ , PF 6 ⁇ , [(Rf) k PF 6 ⁇ k ] ⁇ (Rf: 80% of hydrogen atoms)
  • the above is an alkyl group substituted with a fluorine atom, k: an integer of 1 to 5), AsF 6 ⁇ , SbF 6 ⁇ , SbF 5 OH ⁇ and the like.
  • Examples of the photocationic polymerization initiator of the present invention include (4-hydroxyphenyl) methylbenzylsulfonium tetrakis (pentafluorophenyl) borate, 4- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tetrakis (penta Fluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium tetrakis (pentafluorophenyl) borate, diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate, 4- (4-biphenylylthio) phenyl-4 -Biphenylylphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, trade names “Syracure UVI-6970”, “S
  • the resin composition of the present invention may further include, for example, a curable compound (excluding compounds (A) and (B)), a filler, a silane coupling agent, a polymerization inhibitor, an antioxidant, and a light stabilizer, as necessary.
  • a curable compound excluding compounds (A) and (B)
  • Conventional additives such as an agent, a plasticizer, a leveling agent, an antifoaming agent, a pigment, an organic solvent, an ultraviolet absorber, an ion adsorbent, a phosphor, a release agent, and a rheology control agent may be contained.
  • the content thereof is, for example, 40% by weight or less, preferably 20% by weight or less, particularly preferably 10% by weight or less, based on the total amount of the resin composition.
  • the resin composition of the present invention is a polymer compound having a weight average molecular weight of more than 1000 (preferably more than 5000, particularly preferably more than 10,000) and / or a solubility parameter (SP value at 25 ° C .; Fedors formula) May contain a compound having a value of 8.5 or more, but the content thereof is, for example, 5% by weight or less, preferably 3% by weight or less, particularly preferably 1% by weight or less. If the content of the polymer compound exceeds the above range, the acetone solubility is lowered, and it is difficult to wash the inside of the liquid quantitative discharge device or the like with acetone.
  • the resin composition of the present invention may contain a polymerization initiator other than the photocationic polymerization initiator (C) (for example, a radical photopolymerization initiator), but is included in the resin composition of the present invention.
  • the proportion of the photocationic polymerization initiator (C) in the total amount of the polymerization initiator is, for example, 60% by weight or more, preferably 80% by weight or more, and particularly preferably 90% by weight or more.
  • the upper limit is 100% by weight.
  • the content of the photo radical polymerization initiator in the resin composition of the present invention is, for example, 10% by weight or less (in particular, 5% by weight or less, particularly 1% by weight) of the total amount of the polymerization initiator contained in the resin composition of the present invention. Or less), and most preferably not substantially contained.
  • the content of the photo radical polymerization initiator exceeds the above range, the viscosity after ultraviolet irradiation becomes too high, and it tends to be difficult to maintain adhesiveness.
  • the resin composition of the present invention can be produced by uniformly mixing the above-described compound (A), compound (B), photocationic polymerization initiator (C), and other components as necessary.
  • a compound (A), a compound (B), and a photocationic polymerization initiator (C) can each be used individually by 1 type or in combination of 2 or more types.
  • each component is made as uniform as possible by using generally known mixing equipment such as a revolving and stirring agitation / deaerator, a homogenizer, a planetary mixer, a three-roll mill, and a bead mill. It is desirable to perform stirring, dissolution, mixing, dispersion, and the like. Each component may be mixed simultaneously or sequentially.
  • the content of the compound (A) in the resin composition of the present invention is, for example, 45 to 95% by weight, preferably 60 to 95% by weight, more preferably the total amount (100% by weight) of the curable compound contained in the resin composition. Is 65 to 90% by weight, particularly preferably 70 to 85% by weight.
  • the content of the compound (B) in the resin composition of the present invention is, for example, 5 to 40% by weight, preferably 10 to 35% by weight, based on the total amount (100% by weight) of the curable compound contained in the resin composition. Particularly preferred is 15 to 30% by weight.
  • the ratio of the content of the compound (A) and the compound (B) contained in the resin composition of the present invention is, for example, 60:40 to 95: 5, preferably 65:35. ⁇ 90: 10, particularly preferably 70:30 to 85:15.
  • the total content of the compound (A) and the compound (B) in the resin composition of the present invention is, for example, 50% by weight or more, preferably 60% of the total amount (100% by weight) of the curable compound contained in the resin composition.
  • % By weight or more, more preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more.
  • the upper limit is 100% by weight.
  • the content of the cationic photopolymerization initiator (C) in the resin composition of the present invention is preferably 0.01 to 15 parts by weight, more preferably 100 parts by weight with respect to 100 parts by weight of the curable compound contained in the resin composition. 0.01 to 10 parts by weight, particularly preferably 0.05 to 5 parts by weight, and most preferably 0.1 to 3 parts by weight.
  • the resin composition of the present invention contains the compound (A) and the compound (B) as the curable compound in the above range, the fluidity is appropriately reduced by irradiation with ultraviolet rays and led to a semi-cured state, and the state is maintained. can do. Therefore, for example, when the resin composition of the present invention is used as a fill material, the outflow from the dam can be prevented. Moreover, even if it irradiates with ultraviolet rays, it can be kept in a semi-cured state (that is, in a state where adhesion is maintained) until heat treatment is performed, and the curing reaction can be resumed by adjusting the timing of the heat treatment. The time can be set arbitrarily.
  • the viscosity after ultraviolet irradiation becomes too high, and the followability with respect to steps such as elements and electrodes. Decreases, and a gap is formed between the bonded substrate and the sealing accuracy tends to decrease.
  • the content of the compound (A) exceeds the above range (or if the content of the compound (B) is below the above range)
  • the fluidity cannot be lowered even when irradiated with ultraviolet rays.
  • the resin composition of the present invention is used as a fill material, it may be difficult to prevent outflow from a dam.
  • the resin composition of the present invention is excellent in fluidity until it is irradiated with ultraviolet rays, and the viscosity at 25 ° C. is, for example, 10 mPa ⁇ s or more and less than 30 mPa ⁇ s, preferably 15 to 25 mPa ⁇ s. Therefore, it can discharge favorably using liquid fixed-quantity discharge apparatuses, such as a dispenser, an inkjet coating device, etc.
  • the viscosity of the resin composition can be measured using an E-type viscometer or a rheometer.
  • the resin composition of the present invention comprises a compound (A) having an action of trapping an acid generated from the photocationic polymerization initiator (C) and suppressing the progress of the curing reaction, and the acid or photocationic polymerization initiator (C ),
  • the compound (B) that undergoes a curing reaction by a radical body, which is a decomposition product of the compound (B) contains both the compound (B) and the curing reaction of the compound (B) is suppressed to the extent that the fluidity is lowered. Curing does not proceed until disappears. In other words, the curing retardation is exhibited and the semi-cured state is maintained.
  • the resin composition of the present invention can moderately reduce fluidity by irradiating with ultraviolet rays
  • a polymer compound for example, petroleum resin
  • the ultraviolet irradiation is preferably performed by irradiating light of 1000 mJ / cm 2 or more with a mercury lamp or the like.
  • the viscosity of the resin composition immediately after UV irradiation (irradiation amount: 1500 mJ / cm 2 ) at 25 ° C. is, for example, 30 to 2000 mPa ⁇ s, preferably 30 to 1000 mPa ⁇ s.
  • the resin composition of the present invention can maintain a semi-cured state until heat treatment is performed, and the resin composition 30 minutes after irradiation with ultraviolet rays (irradiation amount: 1500 mJ / cm 2 ).
  • the viscosity at 25 ° C. is, for example, 30 to 2500 mPa ⁇ s, preferably 30 to 1500 mPa ⁇ s.
  • the resin composition of the present invention can be subjected to heat treatment after being irradiated with ultraviolet rays to release the acid trapped in the compound (A), whereby the curing reaction is restarted, and a cured product can be quickly formed after the heat treatment. it can.
  • the heat treatment is performed, for example, at a temperature of 50 to 200 ° C. (more preferably 50 to 170 ° C., more preferably 50 to 150 ° C.) for 10 to 600 minutes (more preferably 10 to 360 minutes, still more preferably 15 to 180). Heating for a minute) is preferred.
  • the resin composition of the present invention has the above characteristics, when it is used as a sealant for an organic EL device, the resin composition that has been subjected to ultraviolet irradiation in advance and has reduced fluidity is applied to the organic EL device.
  • the organic EL element can be bonded to the organic EL element while preventing the resin composition from flowing out of the dam, and then the organic EL element can be sealed without being directly exposed to ultraviolet rays by performing a heat treatment.
  • the cured product of the resin composition of the present invention can be obtained by subjecting the resin composition to ultraviolet irradiation under the above-mentioned conditions and further subjecting it to a heat treatment under the above-mentioned conditions.
  • the refractive index of the cured product of the resin composition of the present invention with respect to light having a wavelength of 589.3 nm (sodium D line) at 25 ° C. is, for example, 1.65 or more, preferably 1.68 or more.
  • cured material can be measured by the method based on JISK7142, or the method using a prism coupler, for example.
  • the cured product has low moisture permeability, and the moisture permeability (g / m 2 ⁇ day ⁇ atm) of the cured product (thickness: 100 ⁇ m) is, for example, 100 or less, preferably 50 or less, particularly preferably 35. Hereinafter, it is most preferably 25 or less.
  • the moisture permeation amount is a value obtained by measuring the moisture permeation amount of a cured product adjusted to a thickness of 100 ⁇ m in accordance with JIS L 1099 and JIS Z 0208 under the conditions of 60 ° C. and 90% RH.
  • the cured product has low outgassing properties, and the amount of outgas of the cured product (60 mg) is, for example, 1000 ppm or less (preferably 200 ppm or less, particularly preferably 100 ppm or less).
  • the outgas amount can be measured by the head space GC / MS.
  • the resin composition of the present invention has a low viscosity and excellent coating properties and acetone solubility until it is irradiated with ultraviolet rays. Moreover, by irradiating with ultraviolet rays, the fluidity can be lowered moderately to be in a semi-cured state, and the semi-cured state can be maintained until heat treatment is performed. And after irradiating with ultraviolet rays, the curing reaction can be restarted by further heat treatment, and then cured rapidly to form a cured product having high refractive index, low moisture permeability, and low outgassing properties. be able to.
  • a sealant for example, a sealant (particularly, a fill material) for a top emission type organic EL device, a light extraction layer material for a bottom emission type organic EL device, a solar cell material, a lens material (particularly, a high refractive index lens material) ) And the like.
  • the resin composition of the present invention when used as a sealant in the process of producing an organic EL device, reflection of light at the interface with a high refractive index member can be suppressed, and light extraction efficiency is improved.
  • an organic EL device having high efficiency, high brightness, and long life can be obtained.
  • the method for producing an organic EL device of the present invention is characterized by sealing an organic EL element (particularly, a top emission type organic EL element) through the following steps 1 and 2.
  • Step 1 UV coating is applied to the coating film made of the resin composition described above.
  • Step 2 The coating film after UV irradiation obtained through Step 1 is bonded to the element mounting surface of the substrate on which the organic EL element is mounted. Heat treatment
  • an organic EL device can be sealed while preventing deterioration of the device due to ultraviolet irradiation, and a long-life and highly reliable organic EL device can be provided.
  • the ultraviolet irradiation and heat treatment methods can be performed in the same manner as the ultraviolet irradiation and heat treatment of the above resin composition.
  • the production method of the present invention includes the following method 1.
  • ⁇ Method 1 See FIG. 1>
  • Step 1-1 Applying the above-mentioned resin composition on the lid to form a coating film / lid laminate
  • Step 1-2 Irradiating the coating film with ultraviolet rays
  • Step 2-1 An organic EL element on the substrate Install and bond the UV / irradiated coating film / lid laminate on the organic EL element installation surface so that the coating film surface faces the element installation surface
  • Step 2-2 Heat treatment is performed to cure the coating film
  • a moisture-proof substrate as the lid (lid) or substrate, for example, a glass substrate such as soda glass or non-alkali glass; a metal substrate such as stainless steel or aluminum; Polyfluorinated ethylene polymers such as fluorinated ethylene chloride (PCTFE), polyvinylidene fluoride (PVDF), copolymers of PCTFE and PVDF, copolymers of PVDF and polyfluorinated ethylene chloride, polyimide, polycarbonate, dicyclo Examples thereof include cycloolefin resins such as pentadiene, polyesters such as polyethylene terephthalate, and resin base materials such as polyethylene and polystyrene.
  • PCTFE fluorinated ethylene chloride
  • PVDF polyvinylidene fluoride
  • copolymers of PCTFE and PVDF copolymers of PVDF and polyfluorinated ethylene chloride
  • polyimide polycarbonate
  • dicyclo Examples thereof include cycloolefin resins such
  • the organic EL element includes an anode / light emitting layer / negative electrode laminate. If necessary, a passivation film such as a SiN film may be provided.
  • the coating film made of the resin composition of the present invention forms a dam by applying a dam material on a lid (lid), and uses a liquid dispensing apparatus such as a dispenser or an inkjet coating apparatus in the dam. And can be formed by discharging the resin composition.
  • the thickness of the coating film is not particularly limited as long as the purpose of protecting the organic EL element from moisture and the like can be achieved.
  • the resin composition of this invention is excellent in acetone solubility, the said apparatus etc. can wash
  • the resin composition at the time of bonding is bonded to the organic EL element after the fluidity of the resin composition is appropriately reduced by irradiating the coating film made of the resin composition of the present invention with ultraviolet rays. Things can be prevented from flowing out of the dam.
  • the organic EL element can be sealed without being exposed to ultraviolet rays, and the organic EL elements do not have deterioration due to ultraviolet rays.
  • the curing reaction is resumed by performing the heat treatment after the bonding, even if the bonding work is delayed, the bonding is not difficult.
  • an organic EL element can be sealed with the hardened
  • the viscosity of the resin composition is a value measured at 25 ° C. and a shear rate of 20 (1 / s) using a rheometer (trade name “Physica® MCR301”, manufactured by Anton® Paar).
  • reaction solution was stirred for 6 hours, then cooled to 0 ° C., and then slowly quenched by dropwise addition of water, and transferred to a separatory funnel.
  • the aqueous layer was extracted with ethyl acetate, and the organic layer was washed with saturated brine. Thereafter, the organic layer was separated and dehydrated with anhydrous sodium sulfate, and then the solvent was distilled off to obtain a liquid crude product.
  • Example 1 MPV (82 parts by weight), VCZ (17 parts by weight), and a photocationic polymerization initiator (1 part by weight) were put into a self-revolving stirring and deaerator (model: AR-250, manufactured by Shinky Corporation). And stirred to obtain a resin composition (1).
  • the obtained resin composition (1) was poured into a mold and irradiated with ultraviolet rays from a distance of 10 cm with a 200 W / cm high-pressure mercury lamp (irradiation amount: 1500 mJ / cm 2 ).
  • the viscosity before ultraviolet irradiation, immediately after ultraviolet irradiation, and 30 minutes after ultraviolet irradiation was measured, respectively, and the viscosity raise degree after ultraviolet irradiation was computed from the following formula.
  • Viscosity increase degree after ultraviolet irradiation viscosity 30 minutes after ultraviolet irradiation / viscosity immediately after ultraviolet irradiation
  • the resin composition (1) after ultraviolet irradiation is subjected to heat treatment (100 ° C., 1 hour) to obtain a cured product (1 ) (Thickness: 100 ⁇ m).
  • UV delayed curing dam material (3,4,3 ′, 4′-diepoxy) 30 parts by weight of bicyclohexyl, liquid bisphenol F diglycidyl ether (trade name “YL-983U”, manufactured by Mitsubishi Chemical Corporation) 70 Parts by weight, 2- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate, 1,3,4,6-tetraglycidylglycoluril (trade name "TG-G ”, 2.5 parts by weight, manufactured by Shikoku Kasei Kogyo Co., Ltd., talc (average particle size 1.5 ⁇ m, tabular particles, trade name“ FG-15 ”, manufactured by Nippon Talc Co., Ltd.), 52 parts by weight, spacer particles (Average particle size 15 ⁇ m, trade name “SD-DB”, manufactured by Hayakawa Rubber Co., Ltd.)
  • the viscosity of the obtained UV delayed dam material was 150 Pa ⁇ s. Further, the viscosity immediately after the UV delayed dam material was irradiated with ultraviolet rays from a distance of 10 cm with a 200 W / cm high-pressure mercury lamp (irradiation amount: 1500 mJ / cm 2 ) was 1500,000 Pa ⁇ s. Furthermore, the viscosity for 30 minutes after the ultraviolet irradiation was 1570000 Pa ⁇ s.
  • the viscosity of the dam material is a value measured using a rheometer (trade name “Physica MCR301”, manufactured by Anton Paar) at 25 ° C. and a shear rate of 2.5 (1 / s). .
  • the UV delayed curing dam material was applied to the glass (76 mm ⁇ 52 mm) surface using an auto dispenser to form a 50 mm ⁇ 35 mm dam, and the fill material (obtained in Examples or Comparative Examples) was formed in the dam.
  • a total of 15 drops (80 to 120 mg) of the resin composition) were dropped one by one at a distance of 5 mm or more from the dam so that the drops did not touch.
  • ultraviolet rays were irradiated from a location 10 cm away from the glass surface (irradiation amount: 1500 mJ / cm 2 ).
  • OPP-EO-VE (2-phenylphenoxy) ethyl vinyl ether obtained in Preparation Example 1, molecular weight: 240.16 HRD-01: 2- (o-phenylphenoxy) ethyl acrylate, molecular weight: 268, trade name “HRD-01”, manufactured by Nippon Touch Technofine Chemical Co., Ltd.
  • HRD-01 2- (o-phenylphenoxy) ethyl acrylate
  • SY-OPG o-phenylphenol glycidyl ether, trade name “SY-OPG”, manufactured by Sakamoto Pharmaceutical Co., Ltd.
  • Neopolymer 120 petroleum resin, weight average molecular weight: 1500 SP value at 25 ° C .: 11.2, trade name “Neopolymer 120”, manufactured by JX Nippon Mining & Energy Corporation [Photocationic polymerization initiator (C)] Photocationic polymerization initiator: 4- (4-biphenylylthio) phenyl-4-biphenylylphenylsulfonium tetrakis (pentafluorophenyl) borate
  • the resin composition of the present invention After irradiating the resin composition of the present invention with ultraviolet rays, it is bonded to a substrate provided with an organic EL element, and heat treatment is performed after the bonding, thereby suppressing the outflow from the dam and making it difficult to bond.
  • the organic EL element can be sealed with a cured product having a high refractive index, a low moisture permeability, and a low outgassing property without being directly exposed to ultraviolet rays. . Therefore, the resin composition of the present invention can be preferably used as a sealant for top emission type organic EL devices, a light extraction layer material for bottom emission type organic EL devices, a solar cell material, a lens material, and the like.

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PCT/JP2017/013301 2016-04-01 2017-03-30 樹脂組成物 WO2017170888A1 (ja)

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