WO2014083845A1 - Composition de résine et produit durci (3) correspondant - Google Patents

Composition de résine et produit durci (3) correspondant Download PDF

Info

Publication number
WO2014083845A1
WO2014083845A1 PCT/JP2013/006964 JP2013006964W WO2014083845A1 WO 2014083845 A1 WO2014083845 A1 WO 2014083845A1 JP 2013006964 W JP2013006964 W JP 2013006964W WO 2014083845 A1 WO2014083845 A1 WO 2014083845A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
compound
meth
acrylate
composition according
Prior art date
Application number
PCT/JP2013/006964
Other languages
English (en)
Japanese (ja)
Inventor
伸彦 内藤
潤 木戸場
雄一朗 松尾
Original Assignee
日本化薬株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本化薬株式会社 filed Critical 日本化薬株式会社
Publication of WO2014083845A1 publication Critical patent/WO2014083845A1/fr

Links

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
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/26—Di-epoxy compounds heterocyclic
    • 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
    • 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
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/302—Details of OLEDs of OLED structures
    • H10K2102/3023—Direction of light emission
    • H10K2102/3026—Top emission
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer
    • 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
    • H10K59/871—Self-supporting sealing arrangements
    • H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants

Definitions

  • low moisture permeability materials are important materials in various industries. Particularly in the vicinity of electric and electronic displays, it is an indispensable material for maintaining quality, and a higher performance low moisture permeability material is desired.
  • thin displays called flat panel displays (FPD), in particular, plasma displays (PDP) and liquid crystal displays (LCD) have been put on the market and are widely used.
  • organic EL displays OLEDs are expected as next-generation self-luminous thin film displays, and some commercial products have already been put into practical use.
  • An organic EL element of an organic EL display has a structure in which an element body composed of a thin film laminate including a light emitting layer sandwiched between a cathode and an anode is formed on a glass substrate on which a driving circuit such as a TFT is formed.
  • a layer such as a light emitting layer or an electrode of the element portion is easily deteriorated by moisture or oxygen, and the deterioration of brightness, life, and discoloration occurs due to the deterioration. Therefore, the organic EL element is sealed so as to block moisture or impurities from entering from the outside.
  • a higher-performance sealing material is desired, and various sealing techniques have been studied.
  • Patent Document 1 As a typical sealing method of an organic EL element, a method of fixing a metal or glass sealing cap in which a desiccant is inserted in advance to a substrate of an organic EL element using a sealing adhesive has been studied.
  • Patent Document 1 an adhesive is applied to the outer peripheral portion of the substrate of the organic EL element, a sealing cap is placed thereon, and then the adhesive is solidified to fix the substrate and the sealing cap. It is sealed.
  • sealing with a glass sealing cap is the mainstream.
  • a glass sealing cap is produced by processing a digging for inserting a desiccant into a flat glass substrate, and thus tends to be expensive.
  • the sealing with the sealing cap cannot extract light from the sealing cap side.
  • the light emitted from the light source is extracted from the substrate side of the element, and is limited to the bottom emission type element.
  • a bottom emission type element there are problems of a decrease in aperture ratio due to the drive circuit portion formed on the substrate and a decrease in extraction efficiency due to light being partially blocked by the drive circuit portion. Therefore, development of a sealing method applicable to a top emission type element that extracts light from the opposite side of the substrate of the organic EL element is desired.
  • the thin film sealing method is a method in which a thin film made of an inorganic or organic material is laminated on an organic EL element to form a passivation film (Patent Document 2).
  • Patent Document 2 In order to impart sufficient moisture resistance to the device by this method, it is necessary to sequentially stack a number of thin films on the device. Therefore, in the thin film sealing method, the film forming process is long and expensive, and the initial investment tends to be high due to the introduction of a large vacuum system required for film formation.
  • the solid sealing method is a method in which a passivation film is provided so as to cover the entire element portion of the organic EL element, and a sealing transparent substrate is provided thereon via a sealing material.
  • a passivation film is formed by vapor deposition or sputtering of an inorganic material, and it is often an incomplete film having pinholes or a film having low mechanical strength. Therefore, in the solid sealing method, after providing a passivation film on the element, a sealing transparent substrate such as a glass substrate is provided through a sealing adhesive to improve sealing reliability.
  • a technique for enhancing the reliability of sealing by filling the air gap with heat or photo-curing resin has been studied. Such a solid sealing method is attracting attention as a method capable of sealing a top emission type element simply and at low cost.
  • a heat or photo-curing resin as a sealing adhesive or a surface sealing adhesive. This is very important because it can significantly affect the productivity of the sealing operation. For example, if the water vapor transmission rate of the sealing adhesive is not sufficient, it may enter the element portion from the pinhole of the passivation film and cause deterioration of the element. Further, if the curing reaction of the sealing material is slow, the curing process takes time, and the productivity of the sealing work may be reduced.
  • the sealing adhesive used for these has high transmittance in the visible light region, light resistance that can withstand light emission, stable moldability, low curing shrinkage for suppressing residual stress, and light emitting elements in moisture. For example, a low water vapor transmission rate for protecting from water is required.
  • a sealing adhesive that can be suitably used in the solid sealing method is desired.
  • An object of the present invention is to provide a sealing material for an organic EL device, particularly a resin composition suitable for surface sealing, and has excellent visible light transmittance, light resistance and curability, high Tg, curing shrinkage rate and water vapor transmission rate. It provides a cured product having a low viscosity.
  • the present invention relates to the inventions described in the following (1) to (19).
  • A-1 morpholine, tetrahydrofuran, oxane, dioxane, triazine, carbazole, pyrrolidine and piperidine.
  • B-1 morpholine, tetrahydrofuran, oxane, dioxane, triazine, carbazole, pyrrolidine and piperidine.
  • the resin composition according to item. (6) The resin composition according to any one of (1) to (5), further including a curing agent (C). (7)
  • C-1 sulfonium salt, iodonium salt, phosphonium salt, ammonium salt and antimonate.
  • thermosetting resin composition (9) The resin composition according to (6), wherein the curing agent (C) is a thermosetting agent and the resin composition is a thermosetting resin composition. (10) The thermosetting resin composition according to (9), wherein the thermosetting agent is a compound selected from the group described in (C-2) below,
  • C-2 Amine compound, acid anhydride compound, amide compound, phenol compound, carboxylic acid compound, imidazole compound, isocyanuric acid adduct, metal compound, sulfonium salt, ammonium salt, antimonate, phosphonium Salt and microcapsule type curing agents.
  • the resin composition according to any one of (1) to (14) which is used for sealing an organic EL element.
  • An organic EL display whose surface is sealed with the cured product according to (15).
  • the resin composition of the present invention (hereinafter simply referred to as “resin composition” in the present specification) has a cured product excellent in visible light transmittance and light resistance, high Tg, curing shrinkage rate and water vapor permeability. Is low, it is particularly suitable as a surface sealing material for organic EL elements.
  • heterocyclic compound (A) having an oxetanyl group or an epoxy group contained in the resin composition of the present invention hereinafter also referred to as “heterocyclic compound (A)” or “component (A)”. Any compound may be used as long as the compound has at least one heterocycle consisting of a carbon atom and a hetero atom other than a carbon atom and at least one oxetanyl group or epoxy group in the molecule. it can.
  • heterogeneous atom a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned, for example.
  • the oxetane compound or epoxy compound which has the heterocyclic ring illustrated below is mentioned, for example.
  • heterocyclic compound (A) examples include the group described in the following (A-1): A-1: morpholine skeleton, tetrahydrofuran skeleton, oxane skeleton, dioxane skeleton, triazine skeleton (including isocyanurate ring), carbazole skeleton, pyrrolidine skeleton and piperidine skeleton. And a skeleton selected from.
  • the heterocycle may have a substituent or may not have a substituent. Examples of the substituent in the case where the heterocycle has a substituent include an alkyl group, an alkoxy group, and an alkenyl group, and these groups all preferably have 1 to 4 carbon atoms.
  • the substituent present in the heterocyclic skeleton is more preferably an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 1 to 3 carbon atoms.
  • a skeleton selected from is preferred.
  • the compound which has an oxetanyl group or an epoxy group bifunctional or more is preferable, and the compound which is bifunctional is more preferable.
  • the heterocyclic skeleton and the oxetanyl group or epoxy group are usually connected directly or by a linking group containing a hydrocarbon group, and are preferably connected by the linking group.
  • Examples of the linking group in the case where the skeleton and the oxetanyl group or the epoxy group are linked by a linking group containing the hydrocarbon group include a hydrocarbon group that may include an ether bond. Or an alkylene group having 1 to 10 carbon atoms having an ether bond. More preferable examples of the linking group include a C1-C4 alkylene group and a C1-C4 alkylene group having an ether bond at the terminal of the alkylene group (-oxy-C1-C4 alkylene group).
  • heterocyclic compounds (A) preferred specific examples of the oxetane compound having a heterocyclic ring include a reaction product of isocyanuric acid (CIC acid) and oxetane alcohol.
  • heterocyclic compounds (A) preferred specific examples of the epoxy compound having a heterocyclic ring include 1,3,5-triglycidyl isocyanurate, 1-allyl-3,5-diglycidyl isocyanurate, 1-methyl- Examples include epoxy compounds having an isocyanurate skeleton such as 3,5-diglycidyl isocyanurate and 1-glycidyl-3,5-diallyl isocyanurate; and epoxy compounds having a dioxane glycol skeleton such as dioxane glycol diglycidyl ether.
  • component (A) in the present invention a compound having an isocyanurate skeleton and an oxetanyl group or an epoxy group is more preferable, and a reaction product of CIC acid and oxetane alcohol and 1,3,5-triglycidyl isocyanurate are further included. preferable.
  • 1-allyl-3,5-diglycidyl isocyanurate 1-methyl-3,5-diglycidyl isocyanurate, 1-glycidyl-3,5-diallyl isocyanurate and 1,3,5-triglycidyl isocyanate Nurates are more preferred, with 1-allyl-3,5-diglycidyl isocyanurate, 1-methyl-3,5-diglycidyl isocyanurate and 1-glycidyl-3,5-diallyl isocyanurate being particularly preferred.
  • the preferable content of the component (A) in the resin composition of the present invention is 20 with respect to 100 parts by mass of the total amount of the component (A) which is a reactive compound and the heterocyclic compound (B) (component (B)). -80 parts by mass, more preferably 30-70 parts by mass.
  • the functional group equivalent of component (A) is preferably 10 to 500 g / eq, and preferably 50 to 250 g / eq. Is more preferable.
  • heterocyclic compound (B) having an oxetanyl group or an epoxy group contained in the resin composition of the present invention also referred to as “heterocyclic compound (B)” or “component (B)” in this specification
  • Any compound listed as the heterocyclic compound (A) can be used, but a compound having a structure different from that of the compound used as the heterocyclic compound (A) is used. That is, the resin composition of the present invention contains two different types of “heterocyclic oxetane compounds or epoxy compounds”.
  • a heterocyclic compound (B) the compound which has the same heterocyclic skeleton as the heterocyclic skeleton described in the description regarding the heterocyclic compound (A) can be used.
  • a preferable thing of a heterocyclic compound (B) the compound made preferable in the description regarding the said heterocyclic compound (A) is mentioned. The same applies to more preferable compounds.
  • heterocyclic ring in the heterocyclic compound (B) examples include the group described in the following (B-1): B-1: Morpholine skeleton, tetrahydrofuran skeleton, oxane skeleton, dioxane skeleton, triazine skeleton, carbazole skeleton, pyrrolidine skeleton and piperidine skeleton.
  • a skeleton selected from is preferable, and the group described in (B-2) below: B-2: A skeleton selected from an oxane skeleton, a dioxane skeleton, and a triazine skeleton is more preferable.
  • heterocyclic compound (A) the compound which has an oxetanyl group or an epoxy group bifunctional or more is preferable, and the compound which is bifunctional is more preferable.
  • Specific examples of the heterocyclic compound (B) include the following compounds.
  • heterocyclic compounds (B) preferred specific examples of the oxetane compound having a heterocyclic ring include a reaction product of CIC acid and oxetane alcohol.
  • heterocyclic compounds (B) preferred specific examples of the epoxy compound having a heterocyclic ring include 1,3,5-triglycidyl isocyanurate, 1-allyl-3,5-diglycidyl isocyanurate, 1-methyl- Examples include epoxy compounds having an isocyanurate skeleton such as 3,5-diglycidyl isocyanurate and 1-glycidyl-3,5-diallyl isocyanurate; and epoxy compounds having a dioxane glycol skeleton such as dioxane glycol diglycidyl ether.
  • the component (B) in the present invention is more preferably a compound having an isocyanurate skeleton and an oxetanyl group or an epoxy group, a reaction product of CIC acid and oxetane alcohol, and 1,3,5-triglycidyl isocyanurate. Is more preferable.
  • 1-allyl-3,5-diglycidyl isocyanurate, 1-methyl-3,5-diglycidyl isocyanurate, 1-glycidyl-3,5-diallyl isocyanurate and 1,3,5-triglycidyl isocyanate Nurates are more preferred, with 1-allyl-3,5-diglycidyl isocyanurate, 1-methyl-3,5-diglycidyl isocyanurate and 1-glycidyl-3,5-diallyl isocyanurate being particularly preferred.
  • the preferred content of component (B) in the resin composition of the present invention is 20 to 80 parts by mass, more preferably 100 parts by mass of the total amount of components (A) and (B) as reactive compounds. Is 30 to 70 parts by mass.
  • the functional group equivalent of component (B) is preferably 10 to 500 g / eq, and preferably 50 to 250 g / eq. Is more preferable.
  • the present invention is a curable resin composition containing the component (A) and the component (B).
  • a curable resin composition using any one of the component (A) and the component (B) having a weight average molecular weight of 2000 or less, more preferably 1000 or less, particularly preferably 500 or less. It is preferable that By using such a low molecular weight compound in either component (A) or component (B), the resin composition has a low viscosity while ensuring low hygroscopicity of the cured product, and easily spreads after coating. Therefore, a composition suitable for the production of OLED can be obtained.
  • both the component (A) and the component (B) are the low molecular weight compounds.
  • the resin composition is cured by thermosetting, it is also preferable that either one of the component (A) and the component (B) is an oxetane compound. It is because the resin composition excellent in curability in a short time can be obtained, ensuring the low hygroscopicity of hardened
  • the preferred use ratio of component (A) to component (B) in the resin composition of the present invention is such that (A) / (B) is 8/2 to 2/8 in terms of mass ratio, and 7/3 to 3 / 7 is more preferable.
  • the resin composition of the present invention can contain a commonly used oxetane compound or epoxy compound as an optional component in addition to the component (A) and the component (B), if necessary.
  • a commonly used oxetane compound or epoxy compound as an optional component in addition to the component (A) and the component (B), if necessary.
  • the optional component include an oxetane compound or an epoxy compound having an aromatic ring, and an oxetane compound or an epoxy compound having an aliphatic ring.
  • oxetane compound having an aromatic ring that can be used as an optional component
  • examples of the oxetane compound having an aromatic ring that can be used as an optional component include 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, 3-ethyl-3-phenoxymethyloxetane, 1,4-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,2-bis [(3-ethyl Oxetane-3-yl) methoxy] benzene, 4,4′-bis [(3-ethyloxetane-3-yl) methoxy] biphenyl, 2,2′-bis [(3-ethyl-3-oxetanyl) methoxy] biphenyl 3,3
  • epoxy compound having an aromatic ring that can be used as an optional component
  • epoxy compounds having a phenyl skeleton such as styrene oxide and phenyl glycidyl ether
  • biphenyl glycidyl ether biphenyl diglycidyl ether, p-tert-butylphenyl glycidyl ether
  • Epoxy compounds having a biphenyl skeleton such as 3,3 ′, 5,5′-tetramethyl-4,4′-bis (glycidyloxy) -1,1′-biphenyl and biphenyl aralkyl type epoxy compounds
  • novolac epoxy compounds such as cresol novolac epoxy compounds
  • bisphenol A epoxy compounds such as bisphenol A diglycidyl ether and brominated bisphenol A diglycidyl ether
  • Bisphenol F-type epoxy compounds such as bisphenol F diglycidyl ether and brominated bisphenol F diglycid
  • an epoxy compound having a skeleton selected from the group consisting of phenyl, biphenyl, bisphenol A, bisphenol F, bisphenol S and naphthalene is preferable.
  • An epoxy compound having a skeleton selected from the group consisting of biphenyl, bisphenol A and naphthalene is more preferable in that the viscosity of the resin composition is low, the moisture permeability of the cured product is low, and the light transmittance is excellent.
  • the preferable content of the oxetane compound or epoxy compound having an aromatic ring in the resin composition of the present invention is 20 to 80 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B), and more The amount is preferably 30 to 70 parts by mass.
  • the functional group equivalent of the oxetane compound or epoxy compound having an aromatic ring is preferably 10 to 1000 g / eq, and more preferably 50 to 500 g / eq. .
  • the oxetane compound or epoxy compound which has condensed aromatic ring structures such as fluorene and carbazole, can also be used for the resin composition of this invention in order to provide rigidity to a coating film.
  • These oxetane compounds or epoxy compounds may be used alone or in combination of two or more.
  • oxetane compound or epoxy compound having an aliphatic ring that can be used as an optional component examples include 3 (4), 8 (9) -bis [(1-ethyl-3-oxetanyl) methoxymethyl] -tricyclo [5.2.1.2. .6] decane and the like.
  • Examples of the epoxy compound having an aliphatic ring that can be used as an optional component include alicyclic epoxy compounds shown in the groups described in (b-1a), (b-1b), and (b-1c) described later; Hydrogenated bisphenol A type epoxy compounds such as bisphenol A diglycidyl ether and brominated hydrogenated bisphenol A diglycidyl ether; Hydrogenated bisphenol F type epoxy such as hydrogenated bisphenol F diglycidyl ether and brominated hydrogenated bisphenol F diglycidyl ether Compound: Hydrogenated bisphenol S type epoxy compound such as hydrogenated bisphenol S diglycidyl ether and brominated hydrogenated bisphenol S diglycidyl ether; Epoxy having a tricyclodecane skeleton such as diepoxy tricyclodecane and tricyclodecane diglycidyl ether Compound ; Epoxy compounds having an adamantane skeleton such as an adamantane glycidyl ether.
  • the alicyclic epoxy compound, or an epoxy having a skeleton selected from the group consisting of a tricyclodecane skeleton, an adamantane skeleton, or a hydrogenated bisphenol A skeleton Compounds are preferred. Particularly preferred are alicyclic epoxy compounds having low moisture permeability and excellent light transmittance, and epoxy compounds having a tricyclodecane skeleton or an adamantane skeleton.
  • an alicyclic epoxy compound has a low viscosity
  • the alicyclic epoxy compounds bifunctional alicyclic epoxy compounds are more preferable, and 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate is particularly preferable.
  • a preferred content when using an oxetane compound or an epoxy compound having an aliphatic ring as an optional component is 20 to 80 parts by mass with respect to 100 parts by mass as a total of component (A) and component (B), and more The amount is preferably 30 to 70 parts by mass.
  • the functional group equivalent of the oxetane compound or epoxy compound having an aliphatic ring is preferably 10 to 1000 g / eq, and more preferably 50 to 500 g / eq. preferable.
  • the curing agent (C) contained in the resin composition of the present invention has reactivity with the epoxy compound and the oxetane compound.
  • a compound that initiates a curing reaction with energy rays such as heat or light can be used.
  • any curing agent can be used, but a curing agent (C) that initiates a curing reaction with energy rays is usually preferred.
  • any compound that generates cations upon receiving ultraviolet rays can be used without any limitation.
  • the curing agent (C) that initiates a curing reaction with an energy beam such as light include a cationic polymerization initiator that generates a cation upon receiving an energy beam such as light (hereinafter also referred to as a photocation polymerization initiator).
  • a photocation polymerization initiator examples include sulfonium salts, iodonium salts, phosphonium salts, ammonium salts, and antimonates.
  • sulfonium salt used as the photocationic polymerization initiator examples include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis [diphenylsulfonio Diphenyl sulfide-bishexafluorophosphate, 4,4′-bis [di ( ⁇ -hydroxyethoxy) phenylsulfonio] diphenyl sulfide-bishexafluoroantimonate, 7- [di (p-toluyl) sulfonio] -2- Isopropylthioxanthone hexafluorophosphate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxan
  • Examples of the iodonium salt used as the photocationic polymerization initiator include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and , (Tricumyl) iodonium tetrakis (pentafluorophenyl) borate and the like.
  • Examples of the phosphonium salt used as the photocationic polymerization initiator include tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride.
  • ammonium salts used as the photocationic polymerization initiator include benzyltrimethylammonium chloride, phenyltributylammonium chloride, and benzyltrimethylammonium bromide.
  • Antimonates used as photocationic polymerization initiators include triphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, and bis Examples include [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate and diallyliodonium hexafluoroantimonate.
  • the iodonium salt and the sulfonium salt are preferable, and among them, it is highly sensitive and easily available from the market (Tricumyl).
  • the antimony element-free (tricumyl) iodonium tetrakis (pentafluorophenyl) borate as the curing agent (C) that initiates the curing reaction with the energy rays.
  • Diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate, or tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tris [(trifluoromethyl) sulfonyl] methanide Is most preferred.
  • the preferred content when using the cationic photopolymerization initiator is 0.05 to 5 parts by mass with respect to 100 parts by mass as the total of component (A) and component (B).
  • the amount is preferably 0.1 to 3 parts by mass.
  • a photocationic polymerization initiator may be used independently and may be used in mixture of multiple types.
  • thermosetting agent that initiates a curing reaction with the epoxy compound and the oxetane compound by heat can be used as the curing agent (C).
  • thermosetting agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, carboxylic acid compounds, and the like.
  • thermosetting agents that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a polyamide resin synthesized from linolenic acid and ethylenediamine, imidazole, trifluoroborane- Amines and amide compounds such as amine complexes and guanidine derivatives; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride , Nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride,
  • an acid anhydride having excellent transparency after curing for surface sealing in a sealing material particularly an organic EL element, and among them, methyltetrahydrophthalic anhydride, methyl nadic anhydride, Nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1 ]
  • An acid anhydride having an alicyclic skeleton such as heptane-2,3-dicarboxylic acid anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is preferred.
  • the curing agent that can be used in this case is not particularly limited as long as it is liquid and has a low viscosity.
  • commercially available curing agents include methyl nadic acid anhydride and Guatemalacid HNA-100 containing Nadic anhydride (manufactured by Shin Nippon Rika Co., Ltd.), and Ricacid containing hexahydrophthalic anhydride and methylhexahydrophthalic anhydride.
  • Examples of the curing agent include MH700 (manufactured by Shin Nippon Rika Co., Ltd.).
  • a cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and another curing agent are used in combination as a thermosetting agent
  • a solid or semi-solid cyclohexane-1,3,4-tricarboxylic acid is used in advance.
  • the heating condition at this time is preferably 150 ° C. or less, more preferably 120 ° C., in order to prevent volatilization of the curing agent.
  • the use ratio of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride in the total curing agent is 20 to 90 mass. %, More preferably in the range of 30 to 80% by mass or less.
  • the mixing ratio exceeds 90% by weight, workability as a curing agent is extremely inferior.
  • the amount is less than 20% by mass, the improvement effect may be reduced in terms of the depression of the sealing material.
  • the compounding ratio of the thermosetting agent is the functional group equivalent contained in the said epoxy compound or the said oxetane compound, and the functional group which this thermosetting agent has. It is determined by the equivalent of (for example, a carboxyl group of a carboxylic acid curing agent).
  • the functional group of the thermosetting agent such as a carboxyl group is 0.2 to 5 equivalents, more preferably 0 to 1 equivalent of the epoxy group and oxetanyl group which are the functional groups of the component (A) and the component (B). .5 to 2 equivalents.
  • a curing catalyst (also referred to as a curing accelerator) can be used in combination with the thermosetting agent, and the curing catalyst can be used alone without using the thermosetting agent. it can.
  • the curing accelerator that can be used in the resin composition of the present invention include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino -6 (2′-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-
  • the curing accelerator is preferably a thermal cation initiator, and particularly preferably a phosphonium salt-based thermal cation initiator.
  • a preferable content of the curing accelerator such as a thermal cation initiator is usually in the range of 0.001 to 15 parts by mass, more preferably 0.01 to 100 parts by mass of the total amount of the component (A) and the component (B). Is 5 parts by mass.
  • the resin composition of the present invention is also effective in combination with a cleavage type photopolymerization initiator used in a radical polymerization system and cured by a redox reaction.
  • a cleavage type photopolymerization initiator used in combination, the ease of the one-electron transfer reaction determines the reactivity.
  • the iodonium salt having a low level of LUMO lowest orbital: a measure of the ease with which an electron transfer reaction occurs
  • an iodonium salt may be used as the curing agent (C). preferable.
  • any cleavage photopolymerization initiator can be used, and examples thereof include 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl-phenylketone. .
  • thermosetting agent used in the resin composition of the present invention is preferably a thermosetting agent that initiates thermosetting at 100 ° C. or less in consideration of the reaction rate and the thermal history of the constituent members. More preferably used. In the present invention, it is preferable to use a photocationic polymerization initiator that does not require heat energy in terms of the heat history of the constituent members.
  • the resin composition of this invention can contain other components other than a component (A), a component (B), and a component (C) as needed.
  • the other components include fine particles, dispersants, reactive compounds other than the component (A) and the component (B) (for example, oxetane compounds or epoxy compounds contained as the above optional components, and (meth) acrylates) ), Photopolymerization initiators other than the cationic photopolymerization initiator, and other additives.
  • Fine particles can be used in combination with the resin composition of the present invention as necessary. Examples of the fine particles include organic fine particles and inorganic fine particles. Further, the fine particles can be used alone or in admixture of plural kinds in consideration of light transmittance, hardness, scratch resistance, curing shrinkage rate and refractive index required for the cured product.
  • organic fine particles examples include polystyrene resin beads, acrylic resin beads, urethane resin beads, polycarbonate resin beads, and other organic polymer beads; porous polystyrene resin beads, porous acrylic resin beads, porous Porous organic polymer beads such as urethane resin beads and porous polycarbonate resin beads; resin powder of benzoguanamine-formalin condensate, resin powder of benzoguanamine-melamine-formalin condensate, resin powder of urea-formalin condensate, aspartic acid ester derivative Powder, zinc stearate powder, stearamide powder, epoxy resin powder, polyethylene powder and the like.
  • crosslinked polymethyl methacrylate resin beads crosslinked polymethyl methacrylate / styrene resin beads, and the like are preferable.
  • These organic fine particles can be easily obtained as a commercial product, and can also be prepared with reference to known literature.
  • inorganic fine particles examples include conductive metal oxides, transparent metal oxides, and other inorganic fillers.
  • Examples of the conductive metal oxide that can be used in the present invention include zinc antimonate, tin oxide-doped indium oxide (ITO), antimony-doped tin oxide (ATO), antimony pentoxide, tin oxide, aluminum-doped zinc oxide, and gallium. Examples thereof include doped zinc oxide and fluorine-doped tin oxide.
  • transparent metal oxide examples include silica, titanium oxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, titanium oxide / zirconium oxide / tin oxide / antimony pentoxide composite, and zirconium oxide. / Tin oxide / antimony pentoxide composite and titanium oxide / zirconium oxide / tin oxide composite.
  • inorganic fillers that can be used in the present invention include calcium oxide, calcium chloride, zeolite and silica gel.
  • the fine particles that can be used in the present invention are preferably fine particles having excellent hardness and scratch resistance and a high refractive index, such as titanium oxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, titanium oxide / zirconium oxide / oxidation.
  • a tin / antimony pentoxide composite, a zirconium oxide / tin oxide / antimony pentoxide composite, and a titanium oxide / zirconium oxide / tin oxide composite are preferably used.
  • the primary particle diameter of the fine particles is preferably 100 nm or less.
  • the preferred blending ratio is 1 to 30 parts by weight, more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the total amount of component (A) and component (B). Part.
  • a fine particle dispersant a polycarboxylic acid-based dispersant; a silicone-based dispersant such as a silane coupling agent, a titanate-based coupling agent, or a modified silicone oil; or an organic copolymer system It is also possible to use a dispersant or the like in combination.
  • a preferable blending ratio when the above dispersant is blended with the resin composition of the present invention is about 0.001 to 30% by mass, more preferably 0.05 to 5% by mass with respect to the total mass of the resin composition of the present invention. %.
  • the primary particle size means the smallest particle size of the particles when the aggregation is broken. That is, in the case of elliptical fine particles, the minor axis is the primary particle diameter.
  • the primary particle size can be measured by a dynamic light scattering method, observation with an electron microscope, or the like. Specifically, the primary particle size of the fine particles can be measured using a JSM-7700F field emission scanning electron microscope manufactured by JEOL Ltd. under the condition of an acceleration voltage of 30 kV.
  • these fine particles can be used by being dispersed in a solvent.
  • the inorganic fine particles are readily available as commercial products in a form dispersed in water or an organic solvent.
  • organic solvent used include hydrocarbon solvents, ester solvents, ether solvents, and ketone solvents.
  • the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane and decane; and petroleum ether, white which is a mixture thereof.
  • Examples include gasoline and solvent naphtha.
  • ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, and cyclic esters such as ⁇ -butyrolactone; ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene (Mono or poly) alkylene glycol monoalkyl ether monoacetates such as glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate and butylene glycol monomethyl ether monoacetate; dialkyl glutarate, dialkyl succinate and Alkyl polycarboxylates such as dialkyl adipates Ester, and the like can be mentioned.
  • alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate
  • cyclic esters
  • ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether; glycols such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether.
  • Ethers cyclic ethers such as tetrahydrofuran and the like.
  • the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.
  • the component (A), the component (B), and the component contained as the above optional component Reactive compounds other than oxetane compounds or epoxy compounds other than (A) and component (B) may be used.
  • the reactive compound include (meth) acrylate.
  • the (meth) acrylate monofunctional (meth) acrylate, bifunctional (meth) acrylate, polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in the molecule, polyester (meth) acrylate, and epoxy (Meth) acrylate or the like can be used.
  • Examples of the monofunctional (meth) acrylate include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and cyclohexyl (meth).
  • Alicyclic (meth) acrylates such as acrylate; Tetrahydrofurfuryl (meth) acrylate, Caprolactone-modified tetrahydrofurfuryl (meth) acrylate and morpholine (meth) acrylate and other (meth) acrylates; benzyl (meth) acrylate , Ethoxy modified cresol (meth) acrylate, propoxy modified cresol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, o-phenylphenol (meth) Acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-phenylphenol (meth) acrylate, p-phenylphenol monoethoxy (meth) acrylate, p-phenylphenol polyethoxy (Meth) acrylates having aromatic rings such as (meth) acryl
  • Examples of the (meth) acrylate monomer having the above two functional groups include (meth) acrylate having a heterocycle such as hydropivalaldehyde-modified trimethylolpropane di (meth) acrylate; (poly) ethoxy-modified bisphenol A di (meta) ) Acrylate, (poly) propoxy modified bisphenol A di (meth) acrylate, (poly) ethoxy modified bisphenol F di (meth) acrylate, (poly) propoxy modified bisphenol F di (meth) acrylate, (poly) ethoxy modified bisphenol S di (Meth) acrylates having aromatic rings such as (meth) acrylate, (poly) propoxy-modified bisphenol S di (meth) acrylate, hexahydrophthalic acid di (meth) acrylate and bisphenoxy (poly) ethoxyfluorene A (meth) acrylate having a heteroaromatic ring such as bipheny
  • polyfunctional (meth) acrylate monomers include polyfunctional (meth) acrylates having an isocyanurate ring such as tris (acryloxyethyl) isocyanurate and (poly) caprolactone-modified tris (acryloxyethyl) isocyanurate; pentaerythritol tris (Meth) acrylate, pentaerythritol tetra (meth) acrylate, (poly) ethoxy modified pentaerythritol tetra (meth) acrylate, (poly) propoxy modified pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, (poly ) Caprolactone-modified dipentaerythritol penta (meth) acrylate, (poly) ethoxy-modified dipentaerythritol penta (meth) acryl
  • urethane (meth) acrylate for example, a polyester diol which is a reaction product of a diol compound or the diol compound and a dibasic acid or an anhydride thereof, and an organic polyisocyanate are reacted, and then a hydroxyl group-containing (meth) The reaction product etc. which added the acrylate are mentioned.
  • diol compound examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,8- Octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2 -Ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A polyethoxydiol, bisphenol A polypropoxydiol, and the like.
  • dibasic acid or anhydride thereof examples include dibasic acids such as succinic acid, adipic acid, azelaic acid, dimer acid, isophthalic acid, terephthalic acid, and phthalic acid; or anhydrides thereof.
  • organic polyisocyanate examples include chain saturated hydrocarbon isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; isophorone diisocyanate, Cyclic saturated hydrocarbon isocyanates such as norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate and hydrogenated toluene diisocyanate; 2,4-tolylene diisocyanate, 1,3-xylylene Range isocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-di Isocyanate, aromatic polyisocyanates such as 6-isopropyl-1,3
  • polyester (meth) acrylate examples include a polyester diol which is a reaction product of a diol compound and a dibasic acid or an anhydride thereof, and a reaction product of (meth) acrylic acid.
  • (meth) acrylate that can be used for the resin composition of the present invention, a material having a low curing shrinkage rate is suitably used.
  • (meth) acrylate having a ring structure is preferable, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, Cyclohexyl (meth) acrylate, p-cumylphenol (poly) ethoxy (meth) acrylate, naphthol (poly) ethoxy (meth) acrylate, naphthol (poly) propoxy (meth) acrylate, phenylphenol (poly) ethoxy (meth) acrylate , Phenylphenol (poly) propoxy (meth) acrylate, benzyl (meth) acrylate, tricyclode
  • phenylphenol (poly) ethoxy (meth) acrylate Particularly preferred are phenylphenol (poly) ethoxy (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, hydropivalaldehyde-modified trimethylolpropane di (meth) acrylate having a high Tg of the cured product and a low cure shrinkage rate. And biphenyldimethanol di (meth) acrylate.
  • the resin composition of this invention when using the said (meth) acrylate which is another component, it may be used independently and may be used in mixture of multiple types.
  • a preferable blending amount when (meth) acrylate is used in the resin composition of the present invention is 10 to 200 parts by mass, more preferably 100 parts by mass with respect to the total amount of component (A) and component (B). 50 to 150 parts by mass.
  • photoinitiators other than the said photocationic polymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2- Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl-phenylketone, 2- Acetophenones such as methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and oligo [2-hydroxy-2-methyl-1- [4-
  • Preferred photopolymerization initiators other than the cationic photopolymerization initiator are preferably acetophenones, and more preferably 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl-phenyl ketone. it can.
  • the amount is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylate component. More preferably, it is 1 to 5 parts by mass.
  • a photoinitiator may be used independently and may be used in mixture of multiple types.
  • each component of the resin composition of the present invention is determined in consideration of a desired refractive index, durability, viscosity, adhesion, and the like.
  • the content of component (A) is 20 to 80 parts by mass, preferably 30 to 70 parts by mass.
  • the content of (B) is 20 to 80 parts by mass, preferably 30 to 70 parts by mass.
  • the content of the component (C) is usually 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass in the case of a photocationic polymerization initiator or a thermal cationic polymerization initiator. .
  • the total amount of the component (A) and the component (B) is preferably 50 to 99% by mass, more preferably 70 to 99% by mass, and still more preferably based on the total amount of the resin composition of the present invention. 80 to 99% by mass, optionally 90 to 99% by mass, and further 95 to 99% by mass.
  • the balance is the above component (C) and optional additive components.
  • the resin composition of the present invention includes a mold release agent, an antifoaming agent, a leveling agent, a light stabilizer, an antioxidant, a polymerization inhibitor, and a plasticizer in order to improve convenience during handling.
  • a mold release agent an antifoaming agent
  • a leveling agent e.g., a light stabilizer
  • an antioxidant e.g., a titanium dioxide
  • a polymerization inhibitor e.g., titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium dioxide, titanium sulf
  • a plasticizer may be used in order to obtain durability and flexibility.
  • the plasticizer material used is selected depending on the desired viscosity, durability, transparency, flexibility, and the like.
  • olefin polymers such as polyethylene and polypropylene; dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, dicyclohexyl phthalate, ethyl phthalyl ethyl glycolate Phthalates such as butyl phthalyl butyl glycolate; trimellitic esters such as tris (2-ethylhexyl) trimellitate; dibutyl adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisononyl adip
  • Preferred plasticizers include (poly) ethylene glycol dibenzoate, (poly) propylene glycol dibenzoate, binaphthol, (poly) ethoxy modified binaphthol, (poly) propoxy modified binaphthol and diphenyl sulfide.
  • a coupling agent may be added to the resin composition of the present invention for the purpose of improving the adhesive force.
  • a silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane,
  • Coupling agents other than silane coupling agents include isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate, Titanium coupling agents such as neoalkoxytri (pN- ( ⁇ -aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneodeca Noyl zirconate, neoalkoxy tris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxy tris (ethylenediaminoethyl) zir
  • coupling agents may be used alone or in combination of two or more. Of these coupling agents, silane coupling agents are preferred, and aminosilane coupling agents or epoxysilane coupling agents are more preferred.
  • a coupling agent By using a coupling agent, it is possible to obtain a sealing material that is excellent in moisture resistance reliability and has little decrease in adhesive strength after moisture absorption.
  • the coupling agent is used in the resin composition of the present invention, the content is about 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the resin composition.
  • polymers such as acrylic polymer, polyester elastomer, urethane polymer and nitrile rubber can be further added as necessary.
  • a weight average molecular weight is 10,000 g / mol from a compatible point.
  • An organometallic compound such as alkylaluminum can also be added to reduce the water vapor permeability.
  • a solvent can also be added, what does not add a solvent is preferable.
  • the resin composition of the present invention is preferably a resin composition having a weight average molecular weight of 10,000 g / mol or less, and more preferably 5,000 g / mol or less. Since a component having a large weight average molecular weight does not dissolve with other components, the prepared resin composition becomes a turbid liquid. This is incompatible because it is essential that the resin composition used in the display is uniformly transparent. Further, the resin composition of the present invention is required to have excellent properties with respect to transmittance. Specifically, when the resin composition of the present invention is cured to obtain a cured product having a film thickness of 100 ⁇ m, the light transmittance of each wavelength at a wavelength of 380 to 780 nm of the cured product is preferably 90% or more. The light transmittance can be measured with a measuring instrument such as a spectrophotometer U-3900H manufactured by Hitachi High-Technologies Corporation.
  • the resin composition of the present invention can be prepared by mixing and dissolving each component according to a conventional method.
  • each component can be charged into a round bottom flask equipped with a stirrer and a thermometer and stirred at 40 to 80 ° C. for 0.5 to 6 hours.
  • the viscosity of the resin composition of the present invention is preferably a viscosity suitable for workability in workability when producing a display or the like.
  • the resin composition when used for surface sealing in an organic EL element, preferably has a low viscosity.
  • the organic EL element is usually surrounded by a dam material, on a substrate such as glass, in order from the substrate side, a metal electrode (lower electrode), an organic EL layer including at least an organic light emitting layer, an ITO electrode ( Upper electrode) and a passivation film are stacked, and the passivation film is filled with a fill material (surface sealing resin composition), and the top is further sealed with a sealing substrate such as glass. It has become.
  • the fill material fills the space between the metal electrode side substrate and the sealing substrate on the opposite side and protects the organic light emitting layer from external moisture and the like, and is usually a curable resin.
  • a composition is used. After filling the filling material which is the curable resin composition and placing a sealing substrate such as glass, the resin composition is cured to seal the organic light emitting layer.
  • the resin composition used as the filling material is a resin composition for surface sealing. Therefore, it is preferable that the resin composition for surface sealing has a low viscosity so that the space between the substrates can be completely sealed.
  • the viscosity of the resin composition for surface sealing of the organic EL device of the present invention is preferably 15 Pa ⁇ viscosity measured at 25 ° C.
  • E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.). s or less, more preferably 10 Pa ⁇ s or less, and even more preferably 1000 mPa ⁇ s or less.
  • the lower limit of the viscosity is not particularly limited, but is about 50 mPa ⁇ s.
  • a resin composition containing a curing agent that initiates a curing reaction with energy rays as the curing agent (C) can be easily cured with energy rays.
  • energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays and laser rays; particle rays such as alpha rays, beta rays and electron rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in the present invention.
  • the cured product of the present invention can be obtained by irradiating the resin composition of the present invention with the energy beam.
  • the liquid refractive index of the resin composition of the present invention is usually 1.45 to 1.70, preferably 1.50 to 1.65.
  • the refractive index can be measured with an Abbe refractometer (model number: DR-M2, manufactured by Atago Co., Ltd.).
  • the resin composition of the present invention preferably has a smaller shrinkage ratio upon curing (curing shrinkage ratio), preferably 5% or less, more preferably 4% or less.
  • the cured product of the resin composition of the present invention preferably has a water vapor transmission rate of 60 g / m 2 ⁇ 24 h (measured at 60 ° C.
  • the glass transition temperature (Tg) of the cured product is preferably higher to some extent.
  • the Tg is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, and most preferably 100 ° C. or higher.
  • Component (A) is a compound having a skeleton selected from the group described in (A-1) above and an epoxy group or oxetanyl group
  • Compound (B) is a compound having a skeleton selected from the group described in (B-1) above and an epoxy group or oxetanyl group
  • a compound having a structure different from that of the compound used as component (A) A resin composition is illustrated.
  • Component (A) and Component (B) are 1-allyl-3,5-diglycidyl isocyanurate, 1-methyl-3,5-diglycidyl isocyanurate and 1-glycidyl-3,5-
  • the resin composition according to (VII) above which is a compound selected from the group consisting of diallyl isocyanurate.
  • (IX) The resin composition according to any one of (I) to (VIII) above, wherein the curing agent (C) is a photocationic polymerization initiator or a thermal cationic polymerization initiator.
  • (XII) The resin composition according to any one of (I) to (XI), wherein the viscosity of the resin composition is 10 Pa ⁇ s or less, preferably 1000 mPa ⁇ s or less.
  • (XIII) The resin composition is cured to form a cured product having a thickness of 100 ⁇ m, and the moisture permeability (water vapor permeability) of the cured product measured at 60 ° C. and 90% relative humidity is 60 g / m 2 ⁇ 24 hr or less.
  • (XIV) The resin composition according to any one of (I) to (XIII) above, wherein the glass transition point (Tg) of the cured product of the resin composition is 60 ° C. or higher, more preferably 80 ° C. or higher. .
  • (XV) The resin composition according to any one of the above (I) to (XIV), which has a curing shrinkage rate of 4% or less when the resin composition is cured.
  • (XVI) The resin composition according to any one of (I) to (XV) above, wherein the liquid refractive index of the resin composition is 1.45 to 1.7.
  • (XVII) The resin composition according to any one of the above (I) to (XVI), which is used for sealing an organic EL device.
  • the content of the component (A) is 20 to 80 parts by mass and the content of the component (B) is 20 to 80 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B).
  • the organic EL device solid sealing method includes a step of forming a passivation film on an organic EL device formed on a substrate, a surface sealing resin composition is applied on the passivation film, and sealing is performed. And a step of curing the surface sealing resin composition, and using the curable resin composition according to the present invention described above as the surface sealing resin composition. To do.
  • An organic EL element that is sealed or surface-sealed includes a substrate, a lower electrode, an organic EL layer that includes at least a light-emitting layer, and an element body that includes an upper electrode.
  • the substrate is a flat substrate made of an electrically insulating material such as a glass substrate, a transparent organic material made of cycloolefin, polycarbonate, polymethyl methacrylate, or the like, or an organic / inorganic hybrid transparent substrate made of the transparent organic material made of high-rigidity glass fiber or the like.
  • a simple substrate is used.
  • the following are mentioned as a typical structure of an element part main body.
  • a lower electrode (cathode) made of an Al—Li alloy or the like is deposited on one side of a substrate by resistance heating deposition.
  • an organic EL layer is formed as an organic EL layer by using an electron transport layer made of an oxadiazole derivative or a triazole derivative, a light emitting layer, TPD (N, N'-diphenyl-N, N'-bis (3-methylphenyl ) -1,1-biphenyl-4,4'-diamine), etc., and the upper electrode (anode) are sequentially stacked by thin film formation methods such as resistance heating vapor deposition or ion beam sputtering. Is possible.
  • the layer structure or material of the organic EL element is not particularly limited as long as it functions as a display element.
  • the solid sealing method according to the present invention can be applied to any structure of organic EL elements.
  • the passivation film is formed so as to cover the organic EL element.
  • the passivation film can be formed by a method such as vapor deposition or sputtering of an inorganic material such as silicon nitride or silicon oxide.
  • the passivation film is provided to prevent moisture, ionic impurities, and the like from entering the organic EL element.
  • the thickness of the passivation film is preferably in the range of 10 nm to 100 ⁇ m, and more preferably in the range of 100 nm to 10 ⁇ m.
  • the passivation film may be laminated for the purpose of improving reliability.
  • the passivation film is generally an incomplete film with pinholes or a film with low mechanical strength, although it depends on the film forming method. Therefore, in the solid sealing method, the reliability of sealing is improved by further applying an adhesive on the passivation film, press-bonding using a transparent substrate for sealing, and curing the adhesive.
  • the resin composition of the present invention having the composition shown in Table 1 below and the resin composition of Comparative Example 1 were prepared, and cured products of the respective resin compositions were obtained by the following methods.
  • the obtained resin composition and cured product (cured film) were evaluated by the following evaluation methods and evaluation criteria.
  • Viscosity Using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.), the viscosity at 25 ° C. (unit: mPa ⁇ s) of each resin composition described in Table 1 below was measured. .
  • Liquid refractive index The refractive index (25 ° C.) of each resin composition described in Table 1 below was measured with an Abbe refractometer (DR-M2: manufactured by Atago Co., Ltd.).
  • Tg glass transition point, unit: ° C.
  • Viscoelasticity measurement system EXSTAR DMS-6000 (SII NanoTechnology Co., Ltd.) is used to determine the Tg point of the cured product obtained by curing in the same manner as (3) above. (Manufactured by the company), tensile mode, frequency 1 Hz.
  • Curing shrinkage rate A resin layer made of each resin composition described in Table 1 below was applied on a substrate. Next, the resin compositions of Example 1, Example 2, and Comparative Example 1 were irradiated with ultraviolet rays having an integrated irradiation amount of 3000 mJ / cm 2 with a high-pressure mercury lamp (80 W / cm, ozone-less). With respect to the resin composition, the resin composition was cured by heating at 100 ° C. for 1 hour in a drier to prepare a cured product for film specific gravity measurement. This was measured based on JIS K7112 B method, and the specific gravity (DS) of the cured product was measured.
  • DS specific gravity
  • MA-DGIC manufactured by Shikoku Chemicals Co., Ltd., 1-allyl-3,5-diglycidyl isocyanurate
  • MeDGIC manufactured by Shikoku Chemicals Co., Ltd., 1-methyl-3,5-diglycidyl isocyanurate
  • DA-MGIC Shikoku Chemicals 1-glycidyl-3,5-diallyl isocyanurate GSID 26-1 manufactured by Kogyo Co., Ltd .: (tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tris [(trifluoromethyl) sulfonyl) manufactured by BASF Japan Ltd.
  • Methanide sun aid SI-100 main agent Sanshin Chemical Industry Co., Ltd., benzylmethyl-p-hydroxyphenylsulfonium hexafluoroantimonate epolite 80MF: Kyoeisha Chemical Co., Ltd., glycerin diglycidyl ether epolite 100MF: Kyoeisha Chemical Co., Ltd. stock Trimethylolpropane triglycidyl ether
  • the cured product obtained from the resin composition of the present invention having a specific composition has a high Tg, a low curing shrinkage rate, and a low water vapor transmission rate. Therefore, the hardened
  • the resin composition of the present invention and its cured product are excellent in visible light transmittance and light resistance, have a high Tg, and have a low curing shrinkage and water vapor permeability. Suitable for fastening materials.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Epoxy Resins (AREA)
  • Polyethers (AREA)

Abstract

La présente invention concerne une composition de résine qui inclut : un composé hétérocyclique (A) présentant un groupe oxétanyle ou un groupe époxy ; et un composé hétérocyclique (B) qui présente un groupe oxétanyle ou un groupe époxy et qui présente une structure différente de celle du composé utilisé comme composé hétérocyclique (A). Cette composition de résine présente un excellent indice de réfraction liquide et est durcie par la chaleur ou un rayonnement énergétique tel que la lumière pour obtenir un produit durci présentant une excellente transmission de la lumière visible, une excellente résistance à la lumière, une Tg élevée, un faible retrait au durcissement et un faible taux de transmission de la vapeur d'eau et convient donc pour être utilisée pour différents produits d'étanchéité, comme agent de revêtement pour un film formant une barrière et convient en particulier comme produit d'étanchéité de surface pour un élément électroluminescent organique.
PCT/JP2013/006964 2012-11-28 2013-11-27 Composition de résine et produit durci (3) correspondant WO2014083845A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-259623 2012-11-28
JP2012259623A JP6012433B2 (ja) 2012-11-28 2012-11-28 樹脂組成物及びその硬化物（３）

Publications (1)

Publication Number Publication Date
WO2014083845A1 true WO2014083845A1 (fr) 2014-06-05

Family

ID=50827506

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/006964 WO2014083845A1 (fr) 2012-11-28 2013-11-27 Composition de résine et produit durci (3) correspondant

Country Status (3)

Country Link
JP (1) JP6012433B2 (fr)
TW (1) TW201425372A (fr)
WO (1) WO2014083845A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017126595A (ja) * 2016-01-12 2017-07-20 ポリマテック・ジャパン株式会社 封止材および封止材組成物
JP2018061034A (ja) * 2016-09-29 2018-04-12 東京応化工業株式会社 水素バリア剤、水素バリア膜形成用組成物、水素バリア膜、水素バリア膜の製造方法、及び電子素子
JP2019176020A (ja) * 2018-03-28 2019-10-10 東京応化工業株式会社 水素バリア剤、水素バリア膜形成用組成物、水素バリア膜、水素バリア膜の製造方法、及び電子素子

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015064410A1 (fr) * 2013-10-30 2015-05-07 積水化学工業株式会社 Agent d'étanchéité pour éléments d'affichage électroluminescent (el) organiques
KR102379912B1 (ko) * 2017-03-15 2022-03-29 엘지전자 주식회사 수지 코팅 방법
US11859082B2 (en) * 2020-12-31 2024-01-02 Rohm And Haas Electronic Materials Llc Polymers useful as surface leveling agents

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004217780A (ja) * 2003-01-15 2004-08-05 Shikoku Chem Corp エポキシ樹脂組成物
JP2006228708A (ja) * 2005-01-20 2006-08-31 Mitsui Chemicals Inc 有機ｅｌシール材
WO2012093589A1 (fr) * 2011-01-07 2012-07-12 株式会社ダイセル Composition de résine époxyde durcissable
JP2012153605A (ja) * 2011-01-21 2012-08-16 Idemitsu Kosan Co Ltd アダマンタン化合物及びその製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004217780A (ja) * 2003-01-15 2004-08-05 Shikoku Chem Corp エポキシ樹脂組成物
JP2006228708A (ja) * 2005-01-20 2006-08-31 Mitsui Chemicals Inc 有機ｅｌシール材
WO2012093589A1 (fr) * 2011-01-07 2012-07-12 株式会社ダイセル Composition de résine époxyde durcissable
TW201237059A (en) * 2011-01-07 2012-09-16 Daicel Corp Curable epoxy resin composition
JP2012184394A (ja) * 2011-01-07 2012-09-27 Daicel Corp 硬化性エポキシ樹脂組成物
CN103154073A (zh) * 2011-01-07 2013-06-12 株式会社大赛璐 固化性环氧树脂组合物
JP2012153605A (ja) * 2011-01-21 2012-08-16 Idemitsu Kosan Co Ltd アダマンタン化合物及びその製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017126595A (ja) * 2016-01-12 2017-07-20 ポリマテック・ジャパン株式会社 封止材および封止材組成物
JP2018061034A (ja) * 2016-09-29 2018-04-12 東京応化工業株式会社 水素バリア剤、水素バリア膜形成用組成物、水素バリア膜、水素バリア膜の製造方法、及び電子素子
JP2019176020A (ja) * 2018-03-28 2019-10-10 東京応化工業株式会社 水素バリア剤、水素バリア膜形成用組成物、水素バリア膜、水素バリア膜の製造方法、及び電子素子
JP6999469B2 (ja) 2018-03-28 2022-01-18 東京応化工業株式会社 水素バリア剤、水素バリア膜形成用組成物、水素バリア膜、水素バリア膜の製造方法、及び電子素子

Also Published As

Publication number Publication date
JP6012433B2 (ja) 2016-10-25
TW201425372A (zh) 2014-07-01
JP2014105287A (ja) 2014-06-09

Similar Documents

Publication Publication Date Title
JP6363508B2 (ja) 樹脂組成物及びその硬化物（１）
JP5967654B2 (ja) 樹脂組成物及びその硬化物（２）
TWI654212B (zh) 能量線硬化型樹脂組成物及其硬化物
TWI603963B (zh) 能量線硬化型樹脂組成物及其硬化物
TWI623576B (zh) 有機ｅｌ元件密封用樹脂組成物及其硬化物
TWI618741B (zh) 有機el元件之密封用樹脂組成物及其硬化物
WO2014083845A1 (fr) Composition de résine et produit durci (3) correspondant
KR101563827B1 (ko) 에폭시 중합성 조성물, 및 유기 el 디바이스
JP6112603B2 (ja) エネルギー線硬化型樹脂組成物及びその硬化物
JP2016108512A (ja) 有機ｅｌ素子用樹脂組成物、面封止剤、及びこれを用いた有機ｅｌ装置
JP6474432B2 (ja) エネルギー線硬化型樹脂組成物及びその硬化物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13859279

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13859279

Country of ref document: EP

Kind code of ref document: A1