WO2018151002A1 - Photocurable resin composition, sealing agent for organic el display elements, organic el display element, sealing agent for quantum dot devices, and quantum dot device - Google Patents

Photocurable resin composition, sealing agent for organic el display elements, organic el display element, sealing agent for quantum dot devices, and quantum dot device Download PDF

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Publication number
WO2018151002A1
WO2018151002A1 PCT/JP2018/004353 JP2018004353W WO2018151002A1 WO 2018151002 A1 WO2018151002 A1 WO 2018151002A1 JP 2018004353 W JP2018004353 W JP 2018004353W WO 2018151002 A1 WO2018151002 A1 WO 2018151002A1
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meth
weight
resin composition
photocurable resin
parts
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PCT/JP2018/004353
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French (fr)
Japanese (ja)
Inventor
穣 末▲崎▼
康雄 渡邊
真理子 武知
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積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to CN201880004317.9A priority Critical patent/CN109937214B/en
Priority to KR1020227000585A priority patent/KR102549655B1/en
Priority to JP2018510529A priority patent/JPWO2018151002A1/en
Priority to CN202210169452.7A priority patent/CN114539479A/en
Priority to KR1020197003092A priority patent/KR20190018731A/en
Priority to KR1020197035290A priority patent/KR102355058B1/en
Publication of WO2018151002A1 publication Critical patent/WO2018151002A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/08—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms
    • C08F255/10—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having four or more carbon atoms on to butene polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • 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
    • C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • 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
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
    • 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
    • H10K50/842—Containers
    • H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Definitions

  • the present invention relates to a photocurable resin composition having excellent storage stability, coating properties, adhesiveness, and barrier properties.
  • the present invention also provides an organic EL display element sealant and a quantum dot device sealant comprising the photocurable resin composition, an organic EL display element using the organic EL display element sealant,
  • the present invention relates to a quantum dot device using the encapsulant for quantum dot devices.
  • organic electroluminescence (hereinafter, also referred to as “organic EL”) display element has a laminated structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other, and the organic light emitting material layer is formed from one electrode on the organic light emitting material layer.
  • organic EL organic electroluminescence
  • the organic EL display element performs self-emission, it has better visibility than a liquid crystal display element that requires a backlight, can be reduced in thickness, and can be driven by a DC low voltage. Has the advantage.
  • the organic light-emitting material layer and electrodes constituting the organic EL display element have a problem that the characteristics are easily deteriorated by moisture, oxygen, and the like. Therefore, in order to obtain a practical organic EL display element, it is necessary to extend the life by blocking the organic light emitting material layer and the electrode from the atmosphere.
  • a method for blocking the organic light emitting material layer and the electrode from the atmosphere for example, in Patent Document 1, the upper part of the laminate having the organic light emitting material layer arranged on the substrate is covered with a sealing member, and the periphery thereof is a sealing agent.
  • a method of surrounding with a sealing wall formed by (peripheral sealing agent) is disclosed.
  • Such a peripheral sealing agent has a high barrier property to block moisture, oxygen, etc., applicability when applied on a substrate by dispensing, etc., after bonding a substrate and a sealing member, light irradiation or The curability at the time of curing by heating, and the adhesiveness and toughness for maintaining the sealing without causing defects due to peeling or cracking by bonding and fixing the substrate and the sealing member are required.
  • Patent Document 2 discloses a composition containing a high molecular weight polyisobutylene resin and a polyfunctional (meth) acrylate monomer as a curable resin composition that can be used as a peripheral sealing agent.
  • the conventional sealant as disclosed in Patent Document 2 requires solvent dilution at the time of application, and the organic EL display element is damaged by heating in the drying process for removing the solvent itself or the solvent after application. There was a problem that it was easy to generate.
  • the shape of the sealing agent is likely to be non-uniform in the drying step, and it has been difficult to use the sealing agent as a peripheral sealing agent that seals the periphery of the laminate having the organic light emitting material layer.
  • the quantum size effect is a phenomenon in which when a semiconductor crystal is reduced to nanometer-sized particles, the electrons are confined in the minute region and cannot move freely, and the energy that the electrons can take is quantized. is there. Particles in which electrons are confined in a minute region are called quantum dots, and the light absorption wavelength and the like can be controlled by adjusting the particle diameter of the quantum dots and changing the band gap.
  • a quantum dot device using such a quantum size effect for example, a liquid crystal display element that has realized excellent color display capability by arranging a wavelength conversion sheet using quantum dots on a backlight has been developed. .
  • Patent Document 3 discloses a wavelength conversion sheet in which a phosphor layer using quantum dots and a barrier film are laminated. However, it has been difficult to sufficiently block the quantum dots from moisture and the like by sealing using a conventional barrier film.
  • An object of this invention is to provide the photocurable resin composition excellent in storage stability, applicability
  • the present invention also provides an organic EL display element sealant and a quantum dot device sealant comprising the photocurable resin composition, an organic EL display element using the organic EL display element sealant, And it aims at providing the quantum dot device which uses this sealing agent for quantum dot devices.
  • the present invention provides a monomer having a repeating unit represented by the following formula (1) in the main chain, a polymer having a weight average molecular weight of 5,000 to 100,000, an alicyclic skeleton, and a (meth) acryloyl group. And a radical radical polymerization initiator, a water-absorbing filler, no solvent, a repeating unit represented by the following formula (1) in the main chain, and a weight average molecular weight of 5,000 to 100,000.
  • the content of the monomer having the alicyclic skeleton and the (meth) acryloyl group is 30 with respect to a total of 100 parts by weight of the following polymer, the monomer having the alicyclic skeleton and the (meth) acryloyl group.
  • the content of the water-absorbing filler is not less than 5 parts by weight and not more than 200 parts by weight, and is measured using an E-type viscometer at 25 ° C. and 2.5 rpm.
  • 1P viscosity ⁇ S or more and 1000 Pa ⁇ s or less is a photocurable resin composition.
  • the present invention is described in detail below.
  • a low molecular weight polyisobutylene polymer By adding a low molecular weight polyisobutylene polymer to a (meth) acrylic monomer or epoxy monomer as a resin component, and further blending a water-absorbing filler, the present inventors have excellent coating properties without using an organic solvent. Then, the production of a sealant having excellent barrier properties was studied. However, the obtained sealant is easy to phase-separate and is inferior in storage stability, or the polyisobutylene polymer bleeds out when the heat resistance test of the cured product is performed and the adhesiveness is lowered. There was a problem.
  • the inventors of the present invention have a specific content ratio of a polyisobutylene polymer having a weight average molecular weight in a specific range, a monomer having an alicyclic skeleton and a (meth) acryloyl group, and a water-absorbing filler. And the viscosity was considered to be within a specific range. As a result, it was found that a photocurable resin composition excellent in all of storage stability, applicability, adhesion, and barrier properties can be obtained, and the present invention has been completed.
  • the “(meth) acryloyl” means acryloyl or methacryloyl.
  • the photocurable resin composition of the present invention comprises a polymer having a repeating unit represented by the above formula (1) in the main chain and a weight average molecular weight of from 5,000 to 100,000 (hereinafter referred to as “polyester according to the present invention”). It is also referred to as “isobutylene polymer”.
  • the polyisobutylene polymer according to the present invention has a hydrophobic and bulky skeleton composed of repeating units represented by the above formula (1) in the main chain, so that the excluded volume is large while being amorphous. This photocurable resin composition is excellent in barrier properties.
  • the polyisobutylene polymer according to the present invention may have a structural unit other than the repeating unit represented by the above formula (1). That is, if the polyisobutylene polymer according to the present invention has a repeating unit represented by the above formula (1), a reactive functional group such as a (meth) acryloyl group is added to the terminal as the above other structural unit. You may have, and the copolymer which has the said other structural unit as a repeating unit in addition to the repeating unit represented by the said Formula (1) may be sufficient.
  • the polyisobutylene polymer according to the present invention preferably contains 80% by weight or more of the repeating unit represented by the above formula (1), and is 90% by weight or more. More preferably.
  • the lower limit of the weight average molecular weight of the polyisobutylene polymer according to the present invention is 5000, and the upper limit is 100,000.
  • the weight average molecular weight of the polyisobutylene polymer according to the present invention is within this range, the compatibility with the monomer having an alicyclic skeleton and a (meth) acryloyl group described later is excellent. Therefore, the photocurable resin composition obtained is excellent in storage stability, and the bleed-out of the polyisobutylene polymer according to the present invention from the cured product is suppressed, resulting in excellent adhesion.
  • the preferable lower limit of the weight average molecular weight of the polyisobutylene polymer according to the present invention is 20,000, the preferable upper limit is 80,000, the more preferable lower limit is 30,000, and the more preferable upper limit is 60,000.
  • the said weight average molecular weight is a value calculated
  • GPC gel permeation chromatography
  • Examples of the column for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK). Moreover, tetrahydrofuran etc. are mentioned as a solvent used by GPC.
  • Examples of commercially available polyisobutylene polymers according to the present invention include, for example, polyisobutylene polymers manufactured by Kaneka, polyisobutylene polymers manufactured by JX Nippon Oil & Energy, and polyisobutylene polymers manufactured by BASF. Etc.
  • Examples of the polyisobutylene polymer manufactured by Kaneka Corporation include Epion 200A (weight average molecular weight 6900), Epion 400A (weight average molecular weight 13000), Epion 600A (weight average molecular weight 19000), and the like.
  • Examples of the polyisobutylene polymer manufactured by JX Nippon Oil & Energy Corporation include Tetrax 3T (weight average molecular weight 49000), Tetrax 4T (weight average molecular weight 59000), Tetrax 5T (weight average molecular weight 69000), Tetrax. 6T (weight average molecular weight 80000), Hymor 4H (weight average molecular weight 5000 to 100,000), Hymor 5H (weight average molecular weight 5000 to 100,000), Hymor 5.5H (weight average molecular weight 5000 to 100,000) ), Hymol 6H (weight average molecular weight 5000 or more and 100,000 or less), and the like.
  • Examples of the polyisobutylene polymer manufactured by BASF include Oppanol B10 (weight average molecular weight 36000), Oppanol B11 (weight average molecular weight 46000), Oppanol B12 (weight average molecular weight 51000), Oppanol B13 (weight average molecular weight 60,000). , Opanol B14 (weight average molecular weight 65000), Oppanol B15 (weight average molecular weight 75000), and the like.
  • the polyisobutylene polymer according to the present invention may be used alone or in combination of two or more.
  • the photocurable resin composition of the present invention may contain a polymer other than the polyisobutylene polymer according to the present invention as long as the object of the present invention is not impaired.
  • Examples of the other polymer include a polybutene polymer, a polyisoprene polymer, a hydrogenated polyisoprene polymer, a polybutadiene polymer, a hydrogenated polybutadiene polymer, a polyisobutylene polymer having a weight average molecular weight exceeding 100,000, and These copolymers, modified products and the like can be mentioned.
  • a polyisobutylene polymer having a weight average molecular weight exceeding 100,000 is preferable from the viewpoint of barrier properties, and a polybutadiene polymer having a (meth) acryloyl group at the terminal and a terminal ( A polyisoprene-based polymer having a (meth) acryloyl group is preferred.
  • these other polymers may be used independently and 2 or more types may be used in combination.
  • Examples of commercially available polyisobutylene polymers having a weight average molecular weight exceeding 100,000 include, for example, Opanol B30SF, Opanol B50, Opanol B50SF, Opanol B80, Opanol B100, Opanol B150, Oppanol B200 (all BA Manufactured) and the like.
  • Examples of commercially available polybutadiene-based polymers having a (meth) acryloyl group at the terminal include CN307, CN9014NS (all manufactured by Arkema), BAC-45 (manufactured by Osaka Organic Chemical Industry), TE- 2000, TEAI-1000 (all manufactured by Nippon Soda Co., Ltd.) and the like.
  • Examples of commercially available polyisoprene polymers having a (meth) acryloyl group at the terminal include Claprene UC-102M (manufactured by Kuraray Co., Ltd.).
  • the photocurable resin composition of the present invention contains a monomer having an alicyclic skeleton and a (meth) acryloyl group (hereinafter also referred to as “(meth) acrylic monomer according to the present invention”).
  • the (meth) acrylic monomer according to the present invention is excellent in compatibility with the polyisobutylene polymer according to the present invention. Therefore, by containing the (meth) acrylic monomer according to the present invention, bleeding out of the polyisobutylene polymer according to the present invention from the cured product is suppressed, and the resulting photocurable resin composition has excellent adhesiveness. In addition, the storage stability is also excellent.
  • the “(meth) acryl” means acryl or methacryl.
  • the alicyclic skeleton of the (meth) acrylic monomer according to the present invention is preferably a bridged alicyclic skeleton from the viewpoint of barrier properties and the like.
  • the (meth) acryl monomer concerning this invention has a methacryl group as a (meth) acryloyl group from a viewpoint of barrier property.
  • the upper limit with preferable molecular weight of the (meth) acryl monomer concerning this invention is 1000.
  • the molecular weight of the (meth) acrylic monomer according to the present invention is 1000 or less, the resulting photocurable resin composition is more excellent in photocurability.
  • a more preferred upper limit of the molecular weight of the (meth) acrylic monomer according to the present invention is 500.
  • the substantial lower limit is 150.
  • (meth) acrylic monomer according to the present invention examples include bornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyl.
  • the content of the (meth) acrylic monomer according to the present invention is such that the lower limit is 30 parts by weight and the upper limit is 90 parts out of a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention. Parts by weight.
  • the content of the (meth) acrylic monomer according to the present invention is 30 parts by weight or more, the resulting photocurable resin composition is excellent in applicability, curability, and adhesiveness.
  • the content of the (meth) acrylic monomer according to the present invention is 90 parts by weight or less, the resulting photocurable resin composition has excellent barrier properties.
  • the minimum with preferable content of the (meth) acryl monomer concerning this invention is 35 weight part, a preferable upper limit is 80 weight part, a more preferable minimum is 40 weight part, and a more preferable upper limit is 70 weight part.
  • the photocurable resin composition of the present invention contains other polymerizable monomers as long as the compatibility is not impaired. May be.
  • other polymerizable monomer other (meth) acryl monomers other than the (meth) acryl monomer concerning this invention are preferable.
  • Examples of the other (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, Stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate
  • Said other polymerizable monomer may be used independently and 2 or more types may be used in combination.
  • the photocurable resin composition of the present invention contains a photoradical polymerization initiator.
  • the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, benzyl, thioxanthone, and the like. These radical photopolymerization initiators may be used alone or in combination of two or more.
  • the radical photopolymerization initiator by BASF As what is marketed among the said radical photopolymerization initiators, the radical photopolymerization initiator by BASF, the radical photopolymerization initiator by Tokyo Chemical Industry, etc. are mentioned, for example.
  • the radical photopolymerization initiator manufactured by BASF include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucyrin TPO.
  • the photo radical polymerization initiator manufactured by Tokyo Chemical Industry Co., Ltd. include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
  • the content of the radical photopolymerization initiator is preferably 0.1 parts by weight, preferably the upper limit with respect to 100 parts by weight of the total of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention. Is 10 parts by weight.
  • the content of the radical photopolymerization initiator is within this range, the resulting photocurable resin composition is more excellent in curability, storage stability, and barrier properties.
  • the more preferable lower limit of the content of the radical photopolymerization initiator is 0.2 parts by weight, the more preferable upper limit is 5 parts by weight, the still more preferable lower limit is 0.5 parts by weight, and the still more preferable upper limit is 3 parts by weight.
  • the photocurable resin composition of the present invention contains a water-absorbing filler. By containing the water-absorbing filler, the photocurable resin composition of the present invention has excellent barrier properties.
  • the minimum with a preferable average primary particle diameter of the said water absorbing filler is 0.5 micrometer, and a preferable upper limit is 5 micrometers.
  • the average primary particle diameter of the water-absorbing filler is within this range, the resulting photocurable resin composition is more excellent in barrier properties while suppressing panel peeling when used as a sealing agent for organic EL display elements. It will be a thing.
  • the minimum with a more preferable average primary particle diameter of the said water absorbing filler is 0.8 micrometer, and a more preferable upper limit is 3 micrometers.
  • the “average primary particle size” can be measured by a dynamic light scattering type particle size measuring device (“ELSZ-1000S” manufactured by Otsuka Electronics Co., Ltd.) or the like.
  • the preferable lower limit of the specific gravity of the water-absorbing filler is 1.5 g / cm 3
  • the preferable upper limit is 3.3 g / cm 3
  • the resulting photocurable resin composition is superior in barrier properties while suppressing panel peeling when used as a sealing agent for organic EL display elements.
  • a more preferable lower limit of the specific gravity of the water-absorbing filler is 2.0 g / cm 3
  • a more preferable upper limit is 3.0 g / cm 3 .
  • the “specific gravity” means a value measured by a method according to JIS Z8807.
  • the preferable lower limit of the average specific surface area of the water-absorbing filler is 5 m 2 / g, and the preferable upper limit is 20 m 2 / g.
  • the average specific surface area of the water-absorbing filler is within this range, the resulting photocurable resin composition has excellent barrier properties while suppressing panel peeling when used as a sealing agent for organic EL display elements. It becomes.
  • the minimum with a more preferable average specific surface area of the said water absorbing filler is 10 m ⁇ 2 > / g, and a more preferable upper limit is 18 m ⁇ 2 > / g.
  • the “average specific surface area of the water-absorbing filler” can be measured by a BET method using nitrogen gas with a specific surface area measuring apparatus (for example, “ASAP-2000” manufactured by Shimadzu Corporation).
  • a preferable lower limit of the total surface area of the water-absorbing filler per 100 g of the photocurable resin composition of the present invention is 10 m 2 , and a preferable upper limit is 100 m 2 .
  • the total surface area of the water-absorbing filler is within this range, the resulting photocurable resin composition has excellent barrier properties while suppressing panel peeling when used as a sealing agent for organic EL display elements.
  • a more preferable lower limit of the total surface area of the water-absorbing filler is 20 m 2
  • a more preferable upper limit is 80 m 2 .
  • the “total surface area of the water-absorbing filler” can be calculated from the content of the water-absorbing filler and the average specific surface area of the water-absorbing filler.
  • the minimum with the preferable water absorption rate of the said water absorptive filler is 10 weight%.
  • the water absorption rate of the water-absorbing filler is 10% by weight or more, the resulting photocurable resin composition is more excellent in barrier properties.
  • a more preferable lower limit of the water absorption rate of the water-absorbing filler is 20% by weight.
  • there is no particular upper limit for the water absorption rate of the water-absorbing filler but the substantial upper limit is 65% by weight.
  • the “water absorption rate” means the rate of change in weight when a high temperature and high humidity test is performed for 24 hours in an atmosphere at a temperature of 85 ° C. and a humidity of 85%.
  • Examples of the material constituting the water-absorbing filler include alkaline earth metal oxides such as calcium oxide, strontium oxide, and barium oxide, magnesium oxide, and molecular sieve. Among these, from the viewpoint of water absorption, an alkaline earth metal oxide is preferable, and calcium oxide is more preferable. These water-absorbing fillers may be used alone or in combination of two or more.
  • the content of the water-absorbing filler is such that the lower limit is 5 parts by weight and the upper limit is 200 parts by weight with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention. .
  • the resulting photocurable resin composition has an excellent effect of achieving both barrier properties and adhesiveness.
  • the preferable lower limit of the content of the water-absorbing filler is 10 parts by weight, the preferable upper limit is 100 parts by weight, the more preferable lower limit is 15 parts by weight, the more preferable upper limit is 60 parts by weight, and the further preferable upper limit is 50 parts by weight.
  • the photocurable resin composition of the present invention may contain a filler other than the water-absorbing filler for the purpose of further improving the barrier property and coating property.
  • the other fillers include inorganic fillers such as talc, silica, and alumina, and organic fillers such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles.
  • it is preferable to contain a talc and / or silica and it is more preferable to contain a talc and / or fumed silica.
  • These other fillers may be used independently and 2 or more types may be used in combination.
  • the preferred lower limit of the average primary particle diameter of the talc is 5 ⁇ m
  • the preferred upper limit is 50 ⁇ m
  • the more preferred upper limit is 12 ⁇ m from the viewpoint of barrier properties and coatability.
  • the preferred lower limit of the average primary particle diameter of the silica is 7 nm
  • the preferred upper limit is 10 ⁇ m
  • the more preferred lower limit is 10 nm
  • the more preferred upper limit is 1 ⁇ m.
  • Examples of commercially available talc include MICRO ACE P-4, MICRO ACE P-6, and MICRO ACE P-8 (all manufactured by Nippon Talc Co., Ltd.).
  • Examples of commercially available silica include Aerosil 200, Aerosil 300, Aerosil 380 (all manufactured by Nippon Aerosil Co., Ltd.) and the like.
  • the content of the talc is preferably 5% by weight with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention. Parts, and the preferred upper limit is 50 parts by weight.
  • the content of the talc is within this range, the resulting photocurable resin composition is more excellent in the effect of achieving both adhesiveness and barrier properties.
  • the minimum with more preferable content of the said talc is 10 weight part, and a more preferable upper limit is 40 weight part.
  • the preferred lower limit of the silica content is 0.00 with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention. 1 part by weight, the preferred upper limit is 30 parts by weight.
  • the content of the silica is within this range, the resulting photocurable resin composition is more excellent in the effect of achieving both applicability and barrier properties.
  • a more preferable lower limit of the silica content is 1 part by weight, and a more preferable upper limit is 20 parts by weight.
  • the total content of the water-absorbing filler and the other filler is 100 parts by weight or less with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention. Preferably there is.
  • the total content of the water-absorbing filler and the other filler is within this range, the resulting photocurable resin composition is more excellent in the effect of achieving both adhesiveness and barrier properties.
  • a more preferable upper limit of the total content of the water-absorbing filler and the other filler is 80 parts by weight.
  • the photocurable resin composition of the present invention preferably contains a tackifier.
  • the tackifier include terpene resins, modified terpene resins, coumarone resins, indene resins, and petroleum resins.
  • the modified terpene resin include a hydrogenated terpene resin, a terpene phenol copolymer resin, and an aromatic modified terpene resin.
  • the petroleum resin include alicyclic petroleum resins, acyclic aliphatic petroleum resins, aromatic petroleum resins, and aliphatic aromatic copolymer petroleum resins.
  • the tackifier is preferably a petroleum resin, an alicyclic petroleum resin, Aromatic petroleum resins and aliphatic aromatic copolymer petroleum resins are more preferred, and alicyclic petroleum resins are particularly preferred. These tackifiers may be used alone or in combination of two or more.
  • Examples of commercially available alicyclic petroleum resins include alicyclic petroleum resins manufactured by Nippon Zeon, alicyclic petroleum resins manufactured by Arakawa Chemical Industries, and fats manufactured by Idemitsu Kosan Co., Ltd. Examples include cyclic petroleum resins and alicyclic petroleum resins manufactured by ExxonMobil. Examples of the alicyclic petroleum resin manufactured by Nippon Zeon Co., Ltd. include Quintone 1325, Quintone 1345, and the like. Examples of the alicyclic petroleum resin manufactured by Arakawa Chemical Industries include Alcon P-100, Alcon P-125, and Alcon P-140. Examples of the alicyclic petroleum resin manufactured by Idemitsu Kosan Co., Ltd.
  • Imabe S-100 examples include Imabe S-100, Imabe S-110, Imabe P-100, Imabe P-125, and Imabe P-140.
  • Examples of the alicyclic petroleum resin manufactured by ExxonMobil include Escorez 5300 series and 5600 series.
  • the content of the tackifier is preferably 1 part by weight with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention, and preferably 15 parts by weight with respect to the upper limit. It is. When the content of the tackifier is within this range, the resulting photocurable resin composition is more excellent in adhesiveness while maintaining excellent curability and barrier properties.
  • the minimum with more preferable content of the said tackifier is 5 weight part, and a more preferable upper limit is 10 weight part.
  • the photocurable resin composition of the present invention may contain a sensitizer.
  • the sensitizer has a role of further improving the polymerization initiation efficiency of the photoradical polymerization initiator and further promoting the curing reaction of the photocurable resin composition of the present invention.
  • Examples of the sensitizer include anthracene compounds, thioxanthone compounds, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, Examples include 4,4′-bis (dimethylamino) benzophenone and 4-benzoyl-4′methyldiphenyl sulfide.
  • Examples of the anthracene compound include 9,10-dibutoxyanthracene.
  • Examples of the thioxanthone compound include 2,4-diethylthioxanthone.
  • the content of the sensitizer is preferably 0.05 parts by weight with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention, and the preferable upper limit is 3 parts. Parts by weight.
  • the content of the sensitizer is 0.05 parts by weight or more, the sensitizing effect is more exhibited.
  • the content of the sensitizer is 3 parts by weight or less, light can be transmitted to a deep part without excessive absorption.
  • the minimum with more preferable content of the said sensitizer is 0.1 weight part, and a more preferable upper limit is 1 weight part.
  • the photocurable resin composition of the present invention may contain a silane coupling agent.
  • the said silane coupling agent has a role which improves the adhesiveness of the photocurable resin composition of this invention, a board
  • silane coupling agent the well-known silane coupling agent compatible with the polyolefin-type polymer concerning this invention can be used.
  • silane coupling agent for example, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxy Propyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-ethyl-((triethoxysilylpropoxy) methyl) oxetane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrime
  • the content of the silane coupling agent is preferably 0.1 parts by weight with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention, and preferably has an upper limit. 5 parts by weight.
  • the content of the silane coupling agent is within this range, the resulting photocurable resin composition is more excellent in adhesiveness while maintaining excellent barrier properties.
  • the minimum with more preferable content of the said silane coupling agent is 0.3 weight part, and a more preferable upper limit is 3 weight part.
  • the photocurable resin composition of the present invention does not contain a solvent. Since the photocurable resin composition of the present invention is excellent in coating properties even without containing the solvent, it does not require a drying step even when used in the production of organic EL display elements, quantum dot devices, etc., and is outgassed. It is possible to suppress damage to elements and devices due to the occurrence of the above.
  • “does not contain a solvent” means that the content of the solvent is less than 1000 ppm.
  • the photocurable resin composition of the present invention contains various known additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, and a colorant as necessary, as long as the object of the present invention is not impaired. You may contain.
  • the photocurable resin composition of the present invention for example, using a mixer, the polyisobutylene polymer according to the present invention, the (meth) acrylic monomer according to the present invention, and a radical photopolymerization initiator. And a method of mixing a water-absorbing filler and an additive such as a tackifier or a silane coupling agent.
  • the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll.
  • the lower limit of the viscosity of the photocurable resin composition of the present invention measured using an E-type viscometer at 25 ° C. and 2.5 rpm is 1 Pa ⁇ s, and the upper limit is 1000 Pa ⁇ s.
  • the preferable lower limit of the viscosity is 10 Pa ⁇ s
  • the preferable upper limit is 800 Pa ⁇ s
  • the more preferable lower limit is 50 Pa ⁇ s
  • the more preferable upper limit is 500 Pa ⁇ s.
  • the photocurable resin composition of this invention can be used suitably as a sealing agent for organic EL display elements.
  • the sealing agent for organic EL display elements which consists of the photocurable resin composition of this invention is also one of this invention.
  • the sealing of the organic EL display element with the sealing agent for organic EL display elements of the present invention is not like sticking the sealing agent in the form of a sheet, but is cured after applying the sealing agent in a desired shape. By doing so, a sealing portion is formed. Furthermore, the sealing agent for organic EL display elements of the present invention is suitably used for so-called dam fill sealing.
  • the shape of the sealing portion formed by the organic EL display element sealant of the present invention is not particularly limited as long as it is a shape that can protect the laminate having the organic light emitting material layer from the outside air, and the laminate is not limited. The shape may be completely covered, or a sealing wall may be formed around the laminate. Especially, since the sealing agent for organic EL display elements of this invention forms this sealing wall, it can be used suitably as a periphery sealing agent for organic EL display elements.
  • the organic EL display element using the sealing agent for organic EL display elements of the present invention is also one aspect of the present invention.
  • the photocurable resin composition of this invention can be used suitably as a sealing agent for quantum dot devices.
  • the encapsulant for quantum dot devices comprising the photocurable resin composition of the present invention is also one aspect of the present invention.
  • the sealing of the quantum dot device with the encapsulant for quantum dot devices of the present invention is not like sticking a sheet-like encapsulant, but is cured after applying the encapsulant in a desired shape. Thus, the sealing portion is formed. Furthermore, the encapsulant for quantum dot devices of the present invention is suitably used for so-called damfill encapsulation.
  • the shape of the sealing part formed by the encapsulant for quantum dot devices of the present invention is not particularly limited as long as it can protect the layer containing quantum dots from the outside air, and the layer containing the quantum dots is completely
  • the sealing wall may be formed around the layer containing the quantum dots.
  • a quantum dot device using the encapsulant for a quantum dot device of the present invention is also one aspect of the present invention.
  • a display element using quantum dots is preferable, and a liquid crystal display element using quantum dots is more preferable.
  • the encapsulant for quantum dot devices of the present invention is suitably used for sealing a wavelength conversion sheet using quantum dots.
  • paintability, adhesiveness, and barrier property can be provided.
  • the organic EL display element sealing agent which consists of this photocurable resin composition, the sealing agent for quantum dot devices, and the organic EL display which uses this sealing agent for organic EL display elements An element and a quantum dot device using the encapsulant for the quantum dot device can be provided.
  • Examples 1 to 17, Comparative Examples 1 to 11 According to the blending ratios described in Tables 1 to 3, each material was stirred and mixed at a stirring speed of 2000 rpm using a stirring mixer (“AR-250” manufactured by Sinky Co., Ltd.).
  • the photocurable resin compositions of Examples 1 to 17 and Comparative Examples 1 to 11 were prepared by kneading using “NR-42A” manufactured by Noritake Co., Ltd.
  • the viscosity measured on 25 degreeC and 2.5 rpm conditions using the E-type viscosity meter (the Toki Sangyo company make, "VISCOMETER TV-22") is Table 1- It was shown in 3.
  • the glass substrate A a glass surface having a length of 50 mm, a width of 25 mm, and a thickness of 0.7 mm washed with acetone and dried
  • the glass substrate B a glass having a length of 5 mm, a width of 5 mm, and a thickness of 0.7 mm was dipped and washed in acetone and dried
  • the glass substrate A and the glass substrate B were bonded together by curing the photocurable resin composition by irradiating an ultraviolet ray having a wavelength of 365 nm at 3000 mJ / cm 2 with a UV-LED irradiation device.
  • the shear adhesive strength between the glass substrate A and the glass substrate B was measured with a die shear tester (manufactured by Daisy Corporation, “Bond Tester 4000”) at a shear rate of 23 ° C. and 200 ⁇ m / second.
  • the adhesiveness was evaluated as “ ⁇ ” when the shear adhesive force was 200 N or more, “ ⁇ ” when the shear adhesive force was less than 200 N and 100 N or more, and “X” when it was less than 100 N.
  • the glass substrate having the surface coated with the photocurable resin composition is transferred to the Ca substrate via the photocurable resin composition.
  • the glass substrate was laminated on the vapor deposition pattern of Ca. At this time, the positions were aligned and bonded so that the deposited Ca existed at positions of 2 mm, 4 mm, and 6 mm from the end face of the glass substrate.
  • the photocurable resin composition was cured by irradiating with 3000 nm ultraviolet rays at 3000 mJ / cm 2 to prepare a Ca-TEST substrate.
  • the obtained Ca-TEST substrate is exposed to high-temperature and high-humidity conditions of 85 ° C.
  • paintability, adhesiveness, and barrier property can be provided.
  • the organic EL display element sealing agent which consists of this photocurable resin composition, the sealing agent for quantum dot devices, and the organic EL display which uses this sealing agent for organic EL display elements An element and a quantum dot device using the encapsulant for the quantum dot device can be provided.

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Abstract

One purpose of the present invention is to provide a photocurable resin composition which has excellent storage stability, coatability, adhesiveness and barrier properties. Another purpose of the present invention is to provide: a sealing agent for organic EL display elements and a sealing agent for quantum dot devices, which are formed from this photocurable resin composition; an organic EL display element which is obtained using this sealing agent for organic EL display elements; and a quantum dot device which is obtained using this sealing agent for quantum dot devices. The present invention is a photocurable resin composition which contains a polymer that has a repeating unit represented by formula (1) in the main chain, while having a weight average molecular weight of from 5,000 to 100,000 (inclusive), a monomer that has an alicyclic skeleton and a (meth)acryloyl group, a radical photopolymerization initiator and a water absorbent filler, while containing no solvent, and wherein: the content of the monomer that has an alicyclic skeleton and a (meth)acryloyl group is from 30 parts by weight to 90 parts by weight (inclusive) and the content of the water absorbent filler is from 5 parts by weight to 200 parts by weight (inclusive) relative to 100 parts by weight of the total of the polymer that has a repeating unit represented by formula (1) in the main chain, while having a weight average molecular weight of from 5,000 to 100,000 (inclusive) and the monomer that has an alicyclic skeleton and a (meth)acryloyl group; and the viscosity thereof as determined using an E-type viscometer at 25°C at 2.5 rpm is from 1 Pa·s to 1,000 Pa·s (inclusive).

Description

光硬化性樹脂組成物、有機ＥＬ表示素子用封止剤、有機ＥＬ表示素子、量子ドットデバイス用封止剤、及び、量子ドットデバイスPhotocurable resin composition, sealant for organic EL display element, organic EL display element, sealant for quantum dot device, and quantum dot device
本発明は、保存安定性、塗布性、接着性、及び、バリア性に優れる光硬化性樹脂組成物に関する。また、本発明は、該光硬化性樹脂組成物からなる有機ＥＬ表示素子用封止剤及び量子ドットデバイス用封止剤、該有機ＥＬ表示素子用封止剤を用いてなる有機ＥＬ表示素子、並びに、該量子ドットデバイス用封止剤を用いてなる量子ドットデバイスに関する。 The present invention relates to a photocurable resin composition having excellent storage stability, coating properties, adhesiveness, and barrier properties. The present invention also provides an organic EL display element sealant and a quantum dot device sealant comprising the photocurable resin composition, an organic EL display element using the organic EL display element sealant, In addition, the present invention relates to a quantum dot device using the encapsulant for quantum dot devices.
有機エレクトロルミネッセンス（以下、「有機ＥＬ」ともいう）表示素子は、互いに対向する一対の電極間に有機発光材料層が挟持された積層体構造を有し、この有機発光材料層に一方の電極から電子が注入されるとともに他方の電極から正孔が注入されることにより有機発光材料層内で電子と正孔とが結合して発光する。このように有機ＥＬ表示素子は自己発光を行うことから、バックライトを必要とする液晶表示素子等と比較して視認性がよく、薄型化が可能であり、しかも直流低電圧駆動が可能であるという利点を有している。 An organic electroluminescence (hereinafter, also referred to as “organic EL”) display element has a laminated structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other, and the organic light emitting material layer is formed from one electrode on the organic light emitting material layer. When electrons are injected and holes are injected from the other electrode, the electrons and holes are combined in the organic light emitting material layer to emit light. Thus, since the organic EL display element performs self-emission, it has better visibility than a liquid crystal display element that requires a backlight, can be reduced in thickness, and can be driven by a DC low voltage. Has the advantage.
有機ＥＬ表示素子を構成する有機発光材料層や電極は、水分や酸素等により特性が劣化しやすいという問題がある。従って、実用的な有機ＥＬ表示素子を得るためには、有機発光材料層や電極を大気と遮断して長寿命化を図る必要がある。有機発光材料層や電極を大気と遮断する方法として、例えば、特許文献１には、基板上に配列された有機発光材料層を有する積層体の上方を封止部材で覆い、その周囲をシール剤（周辺封止剤）により形成された封止壁で囲む方法が開示されている。このような周辺封止剤には、水分や酸素等を遮断する高度なバリア性、基板上にディスペンス等により塗布する際の塗布性、基板と封止部材とを貼り合せた後、光照射又は加熱により硬化させる際の硬化性、並びに、基板と封止部材とを接着固定し、剥がれやクラックによる欠陥を生じることなく封止を維持する接着性及び強靭性が要求される。 The organic light-emitting material layer and electrodes constituting the organic EL display element have a problem that the characteristics are easily deteriorated by moisture, oxygen, and the like. Therefore, in order to obtain a practical organic EL display element, it is necessary to extend the life by blocking the organic light emitting material layer and the electrode from the atmosphere. As a method for blocking the organic light emitting material layer and the electrode from the atmosphere, for example, in Patent Document 1, the upper part of the laminate having the organic light emitting material layer arranged on the substrate is covered with a sealing member, and the periphery thereof is a sealing agent. A method of surrounding with a sealing wall formed by (peripheral sealing agent) is disclosed. Such a peripheral sealing agent has a high barrier property to block moisture, oxygen, etc., applicability when applied on a substrate by dispensing, etc., after bonding a substrate and a sealing member, light irradiation or The curability at the time of curing by heating, and the adhesiveness and toughness for maintaining the sealing without causing defects due to peeling or cracking by bonding and fixing the substrate and the sealing member are required.
特許文献２には、周辺封止剤として用いることのできる硬化性樹脂組成物として、高分子量のポリイソブチレン樹脂と多官能性（メタ）アクリレートモノマーとを含有する組成物が開示されている。しかしながら、特許文献２に開示されているような従来の封止剤は、塗布時に溶剤希釈が必要であり、溶剤自体や塗布後に溶剤を除去するための乾燥工程における加熱によって有機ＥＬ表示素子にダメージを発生させ易いという問題があった。また、乾燥工程において封止剤の形状が不均一となり易く、有機発光材料層を有する積層体の周囲を封止する周辺封止剤として用いることが困難であった。 Patent Document 2 discloses a composition containing a high molecular weight polyisobutylene resin and a polyfunctional (meth) acrylate monomer as a curable resin composition that can be used as a peripheral sealing agent. However, the conventional sealant as disclosed in Patent Document 2 requires solvent dilution at the time of application, and the organic EL display element is damaged by heating in the drying process for removing the solvent itself or the solvent after application. There was a problem that it was easy to generate. Moreover, the shape of the sealing agent is likely to be non-uniform in the drying step, and it has been difficult to use the sealing agent as a peripheral sealing agent that seals the periphery of the laminate having the organic light emitting material layer.
また、近年、量子サイズ効果を利用した量子ドットデバイスが注目されている。量子サイズ効果とは、半導体結晶をナノメートルサイズの粒子となるまで小さくすると、電子がその微小領域内に閉じ込められて自由に運動できなくなることにより、電子がとり得るエネルギーが量子化される現象である。このように電子が微小領域内に閉じ込められた粒子は量子ドットと呼ばれ、量子ドットの粒子径を調整してバンドギャップを変化させることで光吸収波長等を制御することが可能となる。このような量子サイズ効果を利用した量子ドットデバイスとして、例えば、量子ドットを用いた波長変換シートをバックライト上に配置することで優れた色表示能力を実現した液晶表示素子等が開発されている。量子ドットは水分や酸素等により特性が劣化しやすいという問題があるため、このような波長変換シートにおいては、量子ドットを水分等と遮断することが必要となる。例えば、特許文献３には、量子ドットを用いた蛍光体層とバリアフィルムとを積層した波長変換シートが開示されている。しかしながら、従来のバリアフィルムを用いた封止では、充分に量子ドットを水分等と遮断することが困難であった。 In recent years, quantum dot devices utilizing the quantum size effect have attracted attention. The quantum size effect is a phenomenon in which when a semiconductor crystal is reduced to nanometer-sized particles, the electrons are confined in the minute region and cannot move freely, and the energy that the electrons can take is quantized. is there. Particles in which electrons are confined in a minute region are called quantum dots, and the light absorption wavelength and the like can be controlled by adjusting the particle diameter of the quantum dots and changing the band gap. As a quantum dot device using such a quantum size effect, for example, a liquid crystal display element that has realized excellent color display capability by arranging a wavelength conversion sheet using quantum dots on a backlight has been developed. . Since quantum dots have a problem that their characteristics are likely to deteriorate due to moisture, oxygen, and the like, in such a wavelength conversion sheet, it is necessary to block the quantum dots from moisture and the like. For example, Patent Document 3 discloses a wavelength conversion sheet in which a phosphor layer using quantum dots and a barrier film are laminated. However, it has been difficult to sufficiently block the quantum dots from moisture and the like by sealing using a conventional barrier film.
特開２００７－５９０９４号公報JP 2007-59094 A 特表２０１１－５２６６２９号公報Special table 2011-526629 国際公開第２０１５－０３７７３３号International Publication No. 2015-037733
本発明は、保存安定性、塗布性、接着性、及び、バリア性に優れる光硬化性樹脂組成物を提供することを目的とする。また、本発明は、該光硬化性樹脂組成物からなる有機ＥＬ表示素子用封止剤及び量子ドットデバイス用封止剤、該有機ＥＬ表示素子用封止剤を用いてなる有機ＥＬ表示素子、並びに、該量子ドットデバイス用封止剤を用いてなる量子ドットデバイスを提供することを目的とする。 An object of this invention is to provide the photocurable resin composition excellent in storage stability, applicability | paintability, adhesiveness, and barrier property. The present invention also provides an organic EL display element sealant and a quantum dot device sealant comprising the photocurable resin composition, an organic EL display element using the organic EL display element sealant, And it aims at providing the quantum dot device which uses this sealing agent for quantum dot devices.
本発明は、主鎖に下記式（１）で表される繰り返し単位を有し、重量平均分子量が５０００以上１０万以下であるポリマーと、脂環式骨格と（メタ）アクリロイル基とを有するモノマーと、光ラジカル重合開始剤と、吸水性フィラーとを含有し、溶剤を含有せず、上記主鎖に下記式（１）で表される繰り返し単位を有し、重量平均分子量が５０００以上１０万以下であるポリマーと上記脂環式骨格と（メタ）アクリロイル基とを有するモノマーとの合計１００重量部に対して、上記脂環式骨格と（メタ）アクリロイル基とを有するモノマーの含有量が３０重量部以上９０重量部以下であり、かつ、上記吸水性フィラーの含有量が５重量部以上２００重量部以下であり、Ｅ型粘度計を用いて２５℃、２．５ｒｐｍの条件で測定される粘度が１Ｐａ・ｓ以上１０００Ｐａ・ｓ以下である光硬化性樹脂組成物である。 The present invention provides a monomer having a repeating unit represented by the following formula (1) in the main chain, a polymer having a weight average molecular weight of 5,000 to 100,000, an alicyclic skeleton, and a (meth) acryloyl group. And a radical radical polymerization initiator, a water-absorbing filler, no solvent, a repeating unit represented by the following formula (1) in the main chain, and a weight average molecular weight of 5,000 to 100,000. The content of the monomer having the alicyclic skeleton and the (meth) acryloyl group is 30 with respect to a total of 100 parts by weight of the following polymer, the monomer having the alicyclic skeleton and the (meth) acryloyl group. It is not less than 90 parts by weight and the content of the water-absorbing filler is not less than 5 parts by weight and not more than 200 parts by weight, and is measured using an E-type viscometer at 25 ° C. and 2.5 rpm. 1P viscosity · S or more and 1000 Pa · s or less is a photocurable resin composition.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
以下に本発明を詳述する。
本発明者らは、樹脂成分として、（メタ）アクリルモノマー又はエポキシモノマーに低分子量のポリイソブチレン系ポリマーを加え、更に、吸水性フィラーを配合することにより、有機溶剤を用いずに塗布性に優れ、バリア性にも優れる封止剤を作製することを検討した。しかしながら、得られた封止剤は相分離し易く、保存安定性に劣るものであったり、硬化物の耐熱試験を行った際にポリイソブチレン系ポリマーがブリードアウトして接着性が低下したりするという問題があった。そこで本発明者らは、重量平均分子量が特定の範囲であるポリイソブチレン系ポリマーと、脂環式骨格と（メタ）アクリロイル基とを有するモノマーと、吸水性フィラーとを特定の含有割合となるように配合し、かつ、粘度が特定の範囲となるようにすることを検討した。その結果、保存安定性、塗布性、接着性、及び、バリア性の全てに優れる光硬化性樹脂組成物を得ることができることを見出し、本発明を完成させるに至った。
なお、本明細書において上記「（メタ）アクリロイル」は、アクリロイル又はメタクリロイルを意味する。 The present invention is described in detail below.
By adding a low molecular weight polyisobutylene polymer to a (meth) acrylic monomer or epoxy monomer as a resin component, and further blending a water-absorbing filler, the present inventors have excellent coating properties without using an organic solvent. Then, the production of a sealant having excellent barrier properties was studied. However, the obtained sealant is easy to phase-separate and is inferior in storage stability, or the polyisobutylene polymer bleeds out when the heat resistance test of the cured product is performed and the adhesiveness is lowered. There was a problem. Therefore, the inventors of the present invention have a specific content ratio of a polyisobutylene polymer having a weight average molecular weight in a specific range, a monomer having an alicyclic skeleton and a (meth) acryloyl group, and a water-absorbing filler. And the viscosity was considered to be within a specific range. As a result, it was found that a photocurable resin composition excellent in all of storage stability, applicability, adhesion, and barrier properties can be obtained, and the present invention has been completed.
In the present specification, the “(meth) acryloyl” means acryloyl or methacryloyl.
本発明の光硬化性樹脂組成物は、主鎖に上記式（１）で表される繰り返し単位を有し、重量平均分子量が５０００以上１０万以下であるポリマー（以下、「本発明にかかるポリイソブチレン系ポリマー」ともいう）を含有する。
本発明にかかるポリイソブチレン系ポリマーは、主鎖に上記式（１）で表される繰り返し単位からなる疎水性で嵩高い骨格を有することにより、非晶性でありながら排除体積が大きく、本発明の光硬化性樹脂組成物がバリア性に優れるものとなる。 The photocurable resin composition of the present invention comprises a polymer having a repeating unit represented by the above formula (1) in the main chain and a weight average molecular weight of from 5,000 to 100,000 (hereinafter referred to as “polyester according to the present invention”). It is also referred to as “isobutylene polymer”.
The polyisobutylene polymer according to the present invention has a hydrophobic and bulky skeleton composed of repeating units represented by the above formula (1) in the main chain, so that the excluded volume is large while being amorphous. This photocurable resin composition is excellent in barrier properties.
本発明にかかるポリイソブチレン系ポリマーは、上記式（１）で表される繰り返し単位以外の他の構成単位を有していてもよい。即ち、本発明にかかるポリイソブチレン系ポリマーは、上記式（１）で表される繰り返し単位を有していれば、末端に上記他の構成単位として（メタ）アクリロイル基等の反応性官能基を有していてもよいし、上記式（１）で表される繰り返し単位に加えて上記他の構成単位を繰り返し単位として有する共重合体であってもよい。 The polyisobutylene polymer according to the present invention may have a structural unit other than the repeating unit represented by the above formula (1). That is, if the polyisobutylene polymer according to the present invention has a repeating unit represented by the above formula (1), a reactive functional group such as a (meth) acryloyl group is added to the terminal as the above other structural unit. You may have, and the copolymer which has the said other structural unit as a repeating unit in addition to the repeating unit represented by the said Formula (1) may be sufficient.
上記他の構成単位を有する場合、バリア性の観点から、本発明にかかるポリイソブチレン系ポリマーは、上記式（１）で表される繰り返し単位を８０重量％以上含むことが好ましく、９０重量％以上含むことがより好ましい。 In the case of having the above other structural unit, from the viewpoint of barrier properties, the polyisobutylene polymer according to the present invention preferably contains 80% by weight or more of the repeating unit represented by the above formula (1), and is 90% by weight or more. More preferably.
本発明にかかるポリイソブチレン系ポリマーの重量平均分子量の下限は５０００、上限は１０万である。本発明にかかるポリイソブチレン系ポリマーの重量平均分子量がこの範囲であることにより、後述する脂環式骨格と（メタ）アクリロイル基とを有するモノマーとの相溶性に優れるものとなる。そのため、得られる光硬化性樹脂組成物が保存安定性に優れ、かつ、硬化物からの本発明にかかるポリイソブチレン系ポリマーのブリードアウトが抑制されて接着性にも優れるものとなる。本発明にかかるポリイソブチレン系ポリマーの重量平均分子量の好ましい下限は２万、好ましい上限は８万、より好ましい下限は３万、より好ましい上限は６万である。
なお、本明細書において上記重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定を行い、ポリスチレン換算により求められる値である。ＧＰＣによってポリスチレン換算による重量平均分子量を測定する際のカラムとしては、例えば、Ｓｈｏｄｅｘ　ＬＦ－８０４（昭和電工社製）等が挙げられる。また、ＧＰＣで用いる溶媒としては、テトラヒドロフラン等が挙げられる。 The lower limit of the weight average molecular weight of the polyisobutylene polymer according to the present invention is 5000, and the upper limit is 100,000. When the weight average molecular weight of the polyisobutylene polymer according to the present invention is within this range, the compatibility with the monomer having an alicyclic skeleton and a (meth) acryloyl group described later is excellent. Therefore, the photocurable resin composition obtained is excellent in storage stability, and the bleed-out of the polyisobutylene polymer according to the present invention from the cured product is suppressed, resulting in excellent adhesion. The preferable lower limit of the weight average molecular weight of the polyisobutylene polymer according to the present invention is 20,000, the preferable upper limit is 80,000, the more preferable lower limit is 30,000, and the more preferable upper limit is 60,000.
In addition, the said weight average molecular weight is a value calculated | required by polystyrene conversion by measuring with a gel permeation chromatography (GPC) in this specification. Examples of the column for measuring the weight average molecular weight in terms of polystyrene by GPC include Shodex LF-804 (manufactured by Showa Denko KK). Moreover, tetrahydrofuran etc. are mentioned as a solvent used by GPC.
本発明にかかるポリイソブチレン系ポリマーのうち市販されているものとしては、例えば、カネカ社製のポリイソブチレン系ポリマー、ＪＸ日鉱日石エネルギー社製のポリイソブチレン系ポリマー、ＢＡＳＦ社製のポリイソブチレン系ポリマー等が挙げられる。
上記カネカ社製のポリイソブチレン系ポリマーとしては、例えば、エピオン２００Ａ（重量平均分子量６９００）、エピオン４００Ａ（重量平均分子量１３０００）、エピオン６００Ａ（重量平均分子量１９０００）等が挙げられる。
上記ＪＸ日鉱日石エネルギー社製のポリイソブチレン系ポリマーとしては、例えば、テトラックス３Ｔ（重量平均分子量４９０００）、テトラックス４Ｔ（重量平均分子量５９０００）、テトラックス５Ｔ（重量平均分子量６９０００）、テトラックス６Ｔ（重量平均分子量８００００）、ハイモール４Ｈ（重量平均分子量５０００以上１０万以下）、ハイモール５Ｈ（重量平均分子量５０００以上１０万以下）、ハイモール５．５Ｈ（重量平均分子量５０００以上１０万以下）、ハイモール６Ｈ（重量平均分子量５０００以上１０万以下）等が挙げられる。
上記ＢＡＳＦ社製のポリイソブチレン系ポリマーとしては、例えば、Ｏｐｐａｎｏｌ　Ｂ１０（重量平均分子量３６０００）、Ｏｐｐａｎｏｌ　Ｂ１１（重量平均分子量４６０００）、Ｏｐｐａｎｏｌ　Ｂ１２（重量平均分子量５１０００）、Ｏｐｐａｎｏｌ　Ｂ１３（重量平均分子量６万）、Ｏｐｐａｎｏｌ　Ｂ１４（重量平均分子量６５０００）、Ｏｐｐａｎｏｌ　Ｂ１５（重量平均分子量７５０００）等が挙げられる。 Examples of commercially available polyisobutylene polymers according to the present invention include, for example, polyisobutylene polymers manufactured by Kaneka, polyisobutylene polymers manufactured by JX Nippon Oil & Energy, and polyisobutylene polymers manufactured by BASF. Etc.
Examples of the polyisobutylene polymer manufactured by Kaneka Corporation include Epion 200A (weight average molecular weight 6900), Epion 400A (weight average molecular weight 13000), Epion 600A (weight average molecular weight 19000), and the like.
Examples of the polyisobutylene polymer manufactured by JX Nippon Oil & Energy Corporation include Tetrax 3T (weight average molecular weight 49000), Tetrax 4T (weight average molecular weight 59000), Tetrax 5T (weight average molecular weight 69000), Tetrax. 6T (weight average molecular weight 80000), Hymor 4H (weight average molecular weight 5000 to 100,000), Hymor 5H (weight average molecular weight 5000 to 100,000), Hymor 5.5H (weight average molecular weight 5000 to 100,000) ), Hymol 6H (weight average molecular weight 5000 or more and 100,000 or less), and the like.
Examples of the polyisobutylene polymer manufactured by BASF include Oppanol B10 (weight average molecular weight 36000), Oppanol B11 (weight average molecular weight 46000), Oppanol B12 (weight average molecular weight 51000), Oppanol B13 (weight average molecular weight 60,000). , Opanol B14 (weight average molecular weight 65000), Oppanol B15 (weight average molecular weight 75000), and the like.
本発明にかかるポリイソブチレン系ポリマーは、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。 The polyisobutylene polymer according to the present invention may be used alone or in combination of two or more.
本発明の光硬化性樹脂組成物は、本発明の目的を阻害しない範囲で、本発明にかかるポリイソブチレン系ポリマー以外の他のポリマーを含有してもよい。 The photocurable resin composition of the present invention may contain a polymer other than the polyisobutylene polymer according to the present invention as long as the object of the present invention is not impaired.
上記他のポリマーとしては、例えば、ポリブテン系ポリマー、ポリイソプレン系ポリマー、水添ポリイソプレン系ポリマー、ポリブタジエン系ポリマー、水添ポリブタジエン系ポリマー、重量平均分子量が１０万を超えるポリイソブチレン系ポリマー、及び、これらの共重合体や変性体等が挙げられる。なかでも、バリア性の観点からは、重量平均分子量が１０万を超えるポリイソブチレン系ポリマーが好ましく、反応性の観点からは、末端に（メタ）アクリロイル基を有するポリブタジエン系ポリマー、及び、末端に（メタ）アクリロイル基を有するポリイソプレン系ポリマーが好ましい。
これらの他のポリマーは、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。 Examples of the other polymer include a polybutene polymer, a polyisoprene polymer, a hydrogenated polyisoprene polymer, a polybutadiene polymer, a hydrogenated polybutadiene polymer, a polyisobutylene polymer having a weight average molecular weight exceeding 100,000, and These copolymers, modified products and the like can be mentioned. Among them, a polyisobutylene polymer having a weight average molecular weight exceeding 100,000 is preferable from the viewpoint of barrier properties, and a polybutadiene polymer having a (meth) acryloyl group at the terminal and a terminal ( A polyisoprene-based polymer having a (meth) acryloyl group is preferred.
These other polymers may be used independently and 2 or more types may be used in combination.
上記重量平均分子量が１０万を超えるポリイソブチレン系ポリマーのうち市販されているものとしては、例えば、Ｏｐｐａｎｏｌ　Ｂ３０ＳＦ、Ｏｐｐａｎｏｌ　Ｂ５０、Ｏｐｐａｎｏｌ　Ｂ５０ＳＦ、Ｏｐｐａｎｏｌ　Ｂ８０、Ｏｐｐａｎｏｌ　Ｂ１００、Ｏｐｐａｎｏｌ　Ｂ１５０、Ｏｐｐａｎｏｌ　Ｂ２００（いずれもＢＡＳＦ社製）等が挙げられる。
上記末端に（メタ）アクリロイル基を有するポリブタジエン系ポリマーのうち市販されているものとしては、例えば、ＣＮ３０７、ＣＮ９０１４ＮＳ（いずれもアルケマ社製）、ＢＡＣ－４５（大阪有機化学工業社製）、ＴＥ－２０００、ＴＥＡＩ－１０００（いずれも日本曹達社製）等が挙げられる。
上記末端に（メタ）アクリロイル基を有するポリイソプレン系ポリマーのうち市販されているものとしては、例えば、クラプレン　ＵＣ－１０２Ｍ（クラレ社製）等が挙げられる。 Examples of commercially available polyisobutylene polymers having a weight average molecular weight exceeding 100,000 include, for example, Opanol B30SF, Opanol B50, Opanol B50SF, Opanol B80, Opanol B100, Opanol B150, Oppanol B200 (all BA Manufactured) and the like.
Examples of commercially available polybutadiene-based polymers having a (meth) acryloyl group at the terminal include CN307, CN9014NS (all manufactured by Arkema), BAC-45 (manufactured by Osaka Organic Chemical Industry), TE- 2000, TEAI-1000 (all manufactured by Nippon Soda Co., Ltd.) and the like.
Examples of commercially available polyisoprene polymers having a (meth) acryloyl group at the terminal include Claprene UC-102M (manufactured by Kuraray Co., Ltd.).
本発明の光硬化性樹脂組成物は、脂環式骨格と（メタ）アクリロイル基とを有するモノマー（以下、「本発明にかかる（メタ）アクリルモノマー」ともいう）を含有する。
本発明にかかる（メタ）アクリルモノマーは、本発明にかかるポリイソブチレン系ポリマーとの相溶性に優れる。そのため、本発明にかかる（メタ）アクリルモノマーを含有することにより、硬化物からの本発明にかかるポリイソブチレン系ポリマーのブリードアウトが抑制され、得られる光硬化性樹脂組成物が接着性に優れるものとなり、かつ、保存安定性にも優れるものとなる。
なお、本明細書において上記「（メタ）アクリル」は、アクリル又はメタクリルを意味する。 The photocurable resin composition of the present invention contains a monomer having an alicyclic skeleton and a (meth) acryloyl group (hereinafter also referred to as “(meth) acrylic monomer according to the present invention”).
The (meth) acrylic monomer according to the present invention is excellent in compatibility with the polyisobutylene polymer according to the present invention. Therefore, by containing the (meth) acrylic monomer according to the present invention, bleeding out of the polyisobutylene polymer according to the present invention from the cured product is suppressed, and the resulting photocurable resin composition has excellent adhesiveness. In addition, the storage stability is also excellent.
In the present specification, the “(meth) acryl” means acryl or methacryl.
本発明にかかる（メタ）アクリルモノマーの有する脂環式骨格は、バリア性等の観点から、有橋脂環式骨格であることが好ましい。 The alicyclic skeleton of the (meth) acrylic monomer according to the present invention is preferably a bridged alicyclic skeleton from the viewpoint of barrier properties and the like.
また、本発明にかかる（メタ）アクリルモノマーは、バリア性の観点から、（メタ）アクリロイル基としてメタクリル基を有することが好ましい。 Moreover, it is preferable that the (meth) acryl monomer concerning this invention has a methacryl group as a (meth) acryloyl group from a viewpoint of barrier property.
本発明にかかる（メタ）アクリルモノマーの分子量の好ましい上限は１０００である。本発明にかかる（メタ）アクリルモノマーの分子量が１０００以下であることにより、得られる光硬化性樹脂組成物が光硬化性により優れるものとなる。本発明にかかる（メタ）アクリルモノマーの分子量のより好ましい上限は５００である。
本発明にかかる（メタ）アクリルモノマーの分子量の好ましい下限は特にないが、実質的な下限は１５０である。 The upper limit with preferable molecular weight of the (meth) acryl monomer concerning this invention is 1000. When the molecular weight of the (meth) acrylic monomer according to the present invention is 1000 or less, the resulting photocurable resin composition is more excellent in photocurability. A more preferred upper limit of the molecular weight of the (meth) acrylic monomer according to the present invention is 500.
Although there is no particular lower limit of the molecular weight of the (meth) acrylic monomer according to the present invention, the substantial lower limit is 150.
本発明にかかる（メタ）アクリルモノマーとしては、具体的には例えば、ボルニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、トリメチルシクロヘキシル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、１－アダマンチル（メタ）アクリレート、２－アダマンチル（メタ）アクリレート、２－（メタ）アクリロイルオキシ－２－メチルアダマンタン、２－（メタ）アクリロイルオキシ－２－エチルアダマンタン、２－（メタ）アクリロイルオキシ－２－イソプロピルアダマンタン、１－（メタ）アクリロイルオキシ－３，５－ジメチルアダマンタン、１－アダマンタンメタノール（メタ）アクリレート、１－アダマンタンエタノール（メタ）アクリレート、３，５－ジメチル－１－メタノールアダマンタン（メタ）アクリレート、ジシクロペンタジエンジメタノールジ（メタ）アクリレート、シクロヘキサンジメタノールジ（メタ）アクリレート、１，３－アダマンタンジオールジ（メタ）アクリレート、１，３，５－アダマンタントリオールトリ（メタ）アクリレート等が挙げられる。なかでも、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、１－アダマンチル（メタ）アクリレート、ジシクロペンタジエンジメタノールジ（メタ）アクリレート、及び、トリメチルシクロヘキシル（メタ）アクリレートからなる群より選択される少なくとも１種が好ましく、イソボルニルメタクリレート、ジシクロペンタニルメタクリレート、１－アダマンチルメタクリレート、ジシクロペンタジエンジメタノールジメタクリレート、及び、トリメチルシクロヘキシルメタクリレートからなる群より選択される少なくとも１種がより好ましい。
これらの（メタ）アクリルモノマーは、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。 Specific examples of the (meth) acrylic monomer according to the present invention include bornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyl. Oxyethyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 2- (meth) acryloyloxy-2-methyladamantane, 2 -(Meth) acryloyloxy-2-ethyladamantane, 2- (meth) acryloyloxy-2-isopropyladamantane, 1- (meth) acryloyloxy-3,5-dimethyladamantane, 1-adaman Methanol (meth) acrylate, 1-adamantane ethanol (meth) acrylate, 3,5-dimethyl-1-methanol adamantane (meth) acrylate, dicyclopentadiene dimethanol di (meth) acrylate, cyclohexane dimethanol di (meth) acrylate 1,3-adamantanediol di (meth) acrylate, 1,3,5-adamantanetriol tri (meth) acrylate and the like. Among them, selected from the group consisting of isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 1-adamantyl (meth) acrylate, dicyclopentadiene dimethanol di (meth) acrylate, and trimethylcyclohexyl (meth) acrylate. And at least one selected from the group consisting of isobornyl methacrylate, dicyclopentanyl methacrylate, 1-adamantyl methacrylate, dicyclopentadiene dimethanol dimethacrylate, and trimethylcyclohexyl methacrylate is more preferable. .
These (meth) acrylic monomers may be used alone or in combination of two or more.
本発明にかかる（メタ）アクリルモノマーの含有量は、本発明にかかるポリイソブチレン系ポリマーと本発明にかかる（メタ）アクリルモノマーとの合計１００重量部のうち、下限が３０重量部、上限が９０重量部である。本発明にかかる（メタ）アクリルモノマーの含有量が３０重量部以上であることにより、得られる光硬化性樹脂組成物が塗布性、硬化性、及び、接着性に優れるものとなる。本発明にかかる（メタ）アクリルモノマーの含有量が９０重量部以下であることにより、得られる光硬化性樹脂組成物がバリア性に優れるものとなる。本発明にかかる（メタ）アクリルモノマーの含有量の好ましい下限は３５重量部、好ましい上限は８０重量部、より好ましい下限は４０重量部、より好ましい上限は７０重量部である。 The content of the (meth) acrylic monomer according to the present invention is such that the lower limit is 30 parts by weight and the upper limit is 90 parts out of a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention. Parts by weight. When the content of the (meth) acrylic monomer according to the present invention is 30 parts by weight or more, the resulting photocurable resin composition is excellent in applicability, curability, and adhesiveness. When the content of the (meth) acrylic monomer according to the present invention is 90 parts by weight or less, the resulting photocurable resin composition has excellent barrier properties. The minimum with preferable content of the (meth) acryl monomer concerning this invention is 35 weight part, a preferable upper limit is 80 weight part, a more preferable minimum is 40 weight part, and a more preferable upper limit is 70 weight part.
本発明の光硬化性樹脂組成物は、接着性をより向上させる等の目的で、本発明にかかる（メタ）アクリルモノマーに加えて、相溶性を損なわない範囲で他の重合性モノマーを含有してもよい。
上記他の重合性モノマーとしては、本発明にかかる（メタ）アクリルモノマー以外の他の（メタ）アクリルモノマーが好ましい。 In addition to the (meth) acrylic monomer according to the present invention, the photocurable resin composition of the present invention contains other polymerizable monomers as long as the compatibility is not impaired. May be.
As said other polymerizable monomer, other (meth) acryl monomers other than the (meth) acryl monomer concerning this invention are preferable.
上記他の（メタ）アクリルモノマーとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、イソノニル（メタ）アクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソミリスチル（メタ）アクリレート、ステアリル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、ベンジル（メタ）アクリレート、２－メトキシエチル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、２－ブトキシエチル（メタ）アクリレート、２－フェノキシエチル（メタ）アクリレート、メトキシエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、２，２，２－トリフルオロエチル（メタ）アクリレート、２，２，３，３－テトラフルオロプロピル（メタ）アクリレート、１Ｈ，１Ｈ，５Ｈ－オクタフルオロペンチル（メタ）アクリレート、イミド（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルホスフェート、グリシジル（メタ）アクリレート、１，３－ブタンジオールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、２－ｎ－ブチル－２－エチル－１，３－プロパンジオールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エチレンオキシド付加ビスフェノールＡジ（メタ）アクリレート、プロピレンオキシド付加ビスフェノールＡジ（メタ）アクリレート、エチレンオキシド付加ビスフェノールＦジ（メタ）アクリレート、２－ヒドロキシ－３－（メタ）アクリロイロキシプロピル（メタ）アクリレート、カーボネートジオールジ（メタ）アクリレート、ポリエーテルジオールジ（メタ）アクリレート、ポリエステルジオールジ（メタ）アクリレート、ポリカプロラクトンジオールジ（メタ）アクリレート、ポリブタジエンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、エチレンオキシド付加トリメチロールプロパントリ（メタ）アクリレート、プロピレンオキシド付加トリメチロールプロパントリ（メタ）アクリレート、カプロラクトン変性トリメチロールプロパントリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート、プロピレンオキシド付加グリセリントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリス（メタ）アクリロイルオキシエチルフォスフェート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられる。 Examples of the other (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isomyristyl (meth) acrylate, Stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , Benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxyethylene glycol (meth) Acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, ethyl carbitol (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2 , 3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, imide (meth) acrylate, dimethylaminoethyl (Meth) acrylate, diethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phosphate, glycidyl (meth) acrylate, 1,3-butanediol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanediol di ( Meta) Acu Relate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide added bisphenol A di (meth) acrylate, propylene oxide added Bisphenol A di (meth) acrylate, ethylene oxide-added bisphenol F di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonate diol di (meth) acrylate, polyether diol di (meth) ) Acrylate, polyester diol di (meth) acrylate, polycaprolactone diol di (meth) acrylate, polybutadiene diol di (meth) Acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, glycerin tri (meth) Acrylate, propylene oxide-added glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Examples include penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate. It is.
上記他の重合性モノマーは、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。 Said other polymerizable monomer may be used independently and 2 or more types may be used in combination.
本発明の光硬化性樹脂組成物は、光ラジカル重合開始剤を含有する。
上記光ラジカル重合開始剤としては、例えば、ベンゾフェノン系化合物、アセトフェノン系化合物、アシルフォスフィンオキサイド系化合物、チタノセン系化合物、オキシムエステル系化合物、ベンゾインエーテル系化合物、ベンジル、チオキサントン等が挙げられる。
これらの光ラジカル重合開始剤は、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。 The photocurable resin composition of the present invention contains a photoradical polymerization initiator.
Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, benzyl, thioxanthone, and the like.
These radical photopolymerization initiators may be used alone or in combination of two or more.
上記光ラジカル重合開始剤のうち市販されているものとしては、例えば、ＢＡＳＦ社製の光ラジカル重合開始剤、東京化成工業社製の光ラジカル重合開始剤等が挙げられる。
上記ＢＡＳＦ社製の光ラジカル重合開始剤としては、例えば、ＩＲＧＡＣＵＲＥ１８４、ＩＲＧＡＣＵＲＥ３６９、ＩＲＧＡＣＵＲＥ３７９、ＩＲＧＡＣＵＲＥ６５１、ＩＲＧＡＣＵＲＥ８１９、ＩＲＧＡＣＵＲＥ９０７、ＩＲＧＡＣＵＲＥ２９５９、ＩＲＧＡＣＵＲＥ　ＯＸＥ０１、ルシリンＴＰＯ等が挙げられる。
上記東京化成工業社製の光ラジカル重合開始剤としては、例えば、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等が挙げられる。 As what is marketed among the said radical photopolymerization initiators, the radical photopolymerization initiator by BASF, the radical photopolymerization initiator by Tokyo Chemical Industry, etc. are mentioned, for example.
Examples of the radical photopolymerization initiator manufactured by BASF include IRGACURE 184, IRGACURE 369, IRGACURE 379, IRGACURE 651, IRGACURE 819, IRGACURE 907, IRGACURE 2959, IRGACURE OXE01, and Lucyrin TPO.
Examples of the photo radical polymerization initiator manufactured by Tokyo Chemical Industry Co., Ltd. include benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether.
上記光ラジカル重合開始剤の含有量は、本発明にかかるポリイソブチレン系ポリマーと本発明にかかる（メタ）アクリルモノマーとの合計１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が１０重量部である。上記光ラジカル重合開始剤の含有量がこの範囲であることにより、得られる光硬化性樹脂組成物が、硬化性、保存安定性、及び、バリア性により優れるものとなる。上記光ラジカル重合開始剤の含有量のより好ましい下限は０．２重量部、より好ましい上限は５重量部、更に好ましい下限は０．５重量部、更に好ましい上限は３重量部である。 The content of the radical photopolymerization initiator is preferably 0.1 parts by weight, preferably the upper limit with respect to 100 parts by weight of the total of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention. Is 10 parts by weight. When the content of the radical photopolymerization initiator is within this range, the resulting photocurable resin composition is more excellent in curability, storage stability, and barrier properties. The more preferable lower limit of the content of the radical photopolymerization initiator is 0.2 parts by weight, the more preferable upper limit is 5 parts by weight, the still more preferable lower limit is 0.5 parts by weight, and the still more preferable upper limit is 3 parts by weight.
本発明の光硬化性樹脂組成物は、吸水性フィラーを含有する。
上記吸水性フィラーを含有することにより、本発明の光硬化性樹脂組成物は、バリア性に優れるものとなる。 The photocurable resin composition of the present invention contains a water-absorbing filler.
By containing the water-absorbing filler, the photocurable resin composition of the present invention has excellent barrier properties.
上記吸水性フィラーの平均一次粒子径の好ましい下限は０．５μｍ、好ましい上限は５μｍである。上記吸水性フィラーの平均一次粒子径がこの範囲であることにより、得られる光硬化性樹脂組成物が、有機ＥＬ表示素子用封止剤として用いた際にパネル剥がれを抑制しつつバリア性により優れるものとなる。上記吸水性フィラーの平均一次粒子径のより好ましい下限は０．８μｍ、より好ましい上限は３μｍである。
なお、本明細書において上記「平均一次粒子径」は、動的光散乱式粒子径測定装置（大塚電子社製、「ＥＬＳＺ－１０００Ｓ」）等により測定することができる。 The minimum with a preferable average primary particle diameter of the said water absorbing filler is 0.5 micrometer, and a preferable upper limit is 5 micrometers. When the average primary particle diameter of the water-absorbing filler is within this range, the resulting photocurable resin composition is more excellent in barrier properties while suppressing panel peeling when used as a sealing agent for organic EL display elements. It will be a thing. The minimum with a more preferable average primary particle diameter of the said water absorbing filler is 0.8 micrometer, and a more preferable upper limit is 3 micrometers.
In the present specification, the “average primary particle size” can be measured by a dynamic light scattering type particle size measuring device (“ELSZ-1000S” manufactured by Otsuka Electronics Co., Ltd.) or the like.
上記吸水性フィラーの比重の好ましい下限は１．５ｇ／ｃｍ３、好ましい上限は３．３ｇ／ｃｍ３である。上記吸水性フィラーの比重がこの範囲であることにより、得られる光硬化性樹脂組成物が、有機ＥＬ表示素子用封止剤として用いた際にパネル剥がれを抑制しつつバリア性により優れるものとなる。上記吸水性フィラーの比重のより好ましい下限は２．０ｇ／ｃｍ３、より好ましい上限は３．０ｇ／ｃｍ３である。
なお、上記「比重」は、ＪＩＳ　Ｚ８８０７に準じた方法により測定される値を意味する。 The preferable lower limit of the specific gravity of the water-absorbing filler is 1.5 g / cm 3 , and the preferable upper limit is 3.3 g / cm 3 . When the specific gravity of the water-absorbing filler is within this range, the resulting photocurable resin composition is superior in barrier properties while suppressing panel peeling when used as a sealing agent for organic EL display elements. . A more preferable lower limit of the specific gravity of the water-absorbing filler is 2.0 g / cm 3 , and a more preferable upper limit is 3.0 g / cm 3 .
The “specific gravity” means a value measured by a method according to JIS Z8807.
上記吸水性フィラーの平均比表面積の好ましい下限は５ｍ２／ｇ、好ましい上限は２０ｍ２／ｇである。上記吸水性フィラーの平均比表面積がこの範囲であることにより、得られる光硬化性樹脂組成物が、有機ＥＬ表示素子用封止剤として用いた際にパネル剥がれを抑制しつつバリア性により優れるものとなる。上記吸水性フィラーの平均比表面積のより好ましい下限は１０ｍ２／ｇ、より好ましい上限は１８ｍ２／ｇである。
なお、上記「吸水性フィラーの平均比表面積」は、比表面積測定装置（例えば、島津製作所社製、「ＡＳＡＰ－２０００」等）で窒素ガスを用いたＢＥＴ法により測定することができる。 The preferable lower limit of the average specific surface area of the water-absorbing filler is 5 m 2 / g, and the preferable upper limit is 20 m 2 / g. When the average specific surface area of the water-absorbing filler is within this range, the resulting photocurable resin composition has excellent barrier properties while suppressing panel peeling when used as a sealing agent for organic EL display elements. It becomes. The minimum with a more preferable average specific surface area of the said water absorbing filler is 10 m < 2 > / g, and a more preferable upper limit is 18 m < 2 > / g.
The “average specific surface area of the water-absorbing filler” can be measured by a BET method using nitrogen gas with a specific surface area measuring apparatus (for example, “ASAP-2000” manufactured by Shimadzu Corporation).
本発明の光硬化性樹脂組成物１００ｇ当たりの上記吸水性フィラーの総表面積の好ましい下限は１０ｍ２、好ましい上限は１００ｍ２である。上記吸水性フィラーの総表面積がこの範囲であることにより、得られる光硬化性樹脂組成物が、有機ＥＬ表示素子用封止剤として用いた際にパネル剥がれを抑制しつつバリア性により優れるものとなる。上記吸水性フィラーの総表面積のより好ましい下限は２０ｍ２、より好ましい上限は８０ｍ２である。
なお、上記「吸水性フィラーの総表面積」は、上記吸水性フィラーの含有量と上記吸水性フィラーの平均比表面積とから算出することができる。 A preferable lower limit of the total surface area of the water-absorbing filler per 100 g of the photocurable resin composition of the present invention is 10 m 2 , and a preferable upper limit is 100 m 2 . When the total surface area of the water-absorbing filler is within this range, the resulting photocurable resin composition has excellent barrier properties while suppressing panel peeling when used as a sealing agent for organic EL display elements. Become. A more preferable lower limit of the total surface area of the water-absorbing filler is 20 m 2 , and a more preferable upper limit is 80 m 2 .
The “total surface area of the water-absorbing filler” can be calculated from the content of the water-absorbing filler and the average specific surface area of the water-absorbing filler.
上記吸水性フィラーの吸水率の好ましい下限は１０重量％である。上記吸水性フィラーの吸水率が１０重量％以上であることにより、得られる光硬化性樹脂組成物がバリア性により優れるものとなる。上記吸水性フィラーの吸水率のより好ましい下限は２０重量％である。
また、上記吸水性フィラーの吸水率の好ましい上限は特にないが、実質的な上限は６５重量％である。
なお、上記「吸水率」は、温度８５℃、湿度８５％の雰囲気下で２４時間放置する高温高湿試験を行った場合における重量の変化率を意味する。具体的には、高温高湿試験（８５℃－８５％、２４時間）前の重量をＷ１、高温高湿試験後の重量をＷ２とした場合、下記式（Ｉ）により算出される。
　吸水率（重量％）＝（（Ｗ２－Ｗ１）／Ｗ１）×１００　　（Ｉ） The minimum with the preferable water absorption rate of the said water absorptive filler is 10 weight%. When the water absorption rate of the water-absorbing filler is 10% by weight or more, the resulting photocurable resin composition is more excellent in barrier properties. A more preferable lower limit of the water absorption rate of the water-absorbing filler is 20% by weight.
Moreover, there is no particular upper limit for the water absorption rate of the water-absorbing filler, but the substantial upper limit is 65% by weight.
The “water absorption rate” means the rate of change in weight when a high temperature and high humidity test is performed for 24 hours in an atmosphere at a temperature of 85 ° C. and a humidity of 85%. Specifically, when the weight before the high-temperature and high-humidity test (85 ° C.-85%, 24 hours) is W 1 and the weight after the high-temperature and high-humidity test is W 2 , it is calculated by the following formula (I).
Water absorption rate (% by weight) = ((W 2 −W 1 ) / W 1 ) × 100 (I)
上記吸水性フィラーを構成する材料としては、例えば、酸化カルシウム、酸化ストロンチウム、酸化バリウム等のアルカリ土類金属の酸化物、酸化マグネシウム、モレキュラーシーブ等が挙げられる。なかでも、吸水性の観点から、アルカリ土類金属の酸化物が好ましく、酸化カルシウムがより好ましい。
これらの吸水性フィラーは、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。 Examples of the material constituting the water-absorbing filler include alkaline earth metal oxides such as calcium oxide, strontium oxide, and barium oxide, magnesium oxide, and molecular sieve. Among these, from the viewpoint of water absorption, an alkaline earth metal oxide is preferable, and calcium oxide is more preferable.
These water-absorbing fillers may be used alone or in combination of two or more.
上記吸水性フィラーの含有量は、本発明にかかるポリイソブチレン系ポリマーと本発明にかかる（メタ）アクリルモノマーとの合計１００重量部に対して、下限が５重量部、上限が２００重量部である。上記吸水性フィラーの含有量がこの範囲であることにより、得られる光硬化性樹脂組成物がバリア性と接着性とを両立する効果に優れるものとなる。上記吸水性フィラーの含有量の好ましい下限は１０重量部、好ましい上限は１００重量部、より好ましい下限は１５重量部、より好ましい上限は６０重量部、更に好ましい上限は５０重量部である。 The content of the water-absorbing filler is such that the lower limit is 5 parts by weight and the upper limit is 200 parts by weight with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention. . When the content of the water-absorbing filler is within this range, the resulting photocurable resin composition has an excellent effect of achieving both barrier properties and adhesiveness. The preferable lower limit of the content of the water-absorbing filler is 10 parts by weight, the preferable upper limit is 100 parts by weight, the more preferable lower limit is 15 parts by weight, the more preferable upper limit is 60 parts by weight, and the further preferable upper limit is 50 parts by weight.
本発明の光硬化性樹脂組成物は、バリア性や塗布性を更に向上させること等を目的として、上記吸水性フィラー以外の他のフィラーを含有してもよい。
上記他のフィラーとしては、例えば、タルク、シリカ、アルミナ等の無機フィラーや、ポリエステル微粒子、ポリウレタン微粒子、ビニル重合体微粒子、アクリル重合体微粒子等の有機フィラー等が挙げられる。なかでも、タルク及び／又はシリカを含有することが好ましく、タルク及び／又はフュームドシリカを含有することがより好ましい。
これらの他のフィラーは、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。 The photocurable resin composition of the present invention may contain a filler other than the water-absorbing filler for the purpose of further improving the barrier property and coating property.
Examples of the other fillers include inorganic fillers such as talc, silica, and alumina, and organic fillers such as polyester fine particles, polyurethane fine particles, vinyl polymer fine particles, and acrylic polymer fine particles. Especially, it is preferable to contain a talc and / or silica, and it is more preferable to contain a talc and / or fumed silica.
These other fillers may be used independently and 2 or more types may be used in combination.
上記他のフィラーとしてタルクを用いる場合、バリア性及び塗布性の観点から、該タルクの平均一次粒子径の好ましい下限は５μｍ、好ましい上限は５０μｍ、より好ましい上限は１２μｍである。
上記他のフィラーとしてシリカを用いる場合、塗布性の観点から、該シリカの平均一次粒子径の好ましい下限は７ｎｍ、好ましい上限は１０μｍ、より好ましい下限は１０ｎｍ、より好ましい上限は１μｍである。 When talc is used as the other filler, the preferred lower limit of the average primary particle diameter of the talc is 5 μm, the preferred upper limit is 50 μm, and the more preferred upper limit is 12 μm from the viewpoint of barrier properties and coatability.
When silica is used as the other filler, from the viewpoint of coatability, the preferred lower limit of the average primary particle diameter of the silica is 7 nm, the preferred upper limit is 10 μm, the more preferred lower limit is 10 nm, and the more preferred upper limit is 1 μm.
上記タルクのうち市販されているものとしては、例えば、ＭＩＣＲＯ　ＡＣＥ　Ｐ－４、ＭＩＣＲＯ　ＡＣＥ　Ｐ－６、ＭＩＣＲＯ　ＡＣＥ　Ｐ－８（いずれも日本タルク社製）等が挙げられる。
上記シリカのうち市販されているものとしては、例えば、アエロジル２００、アエロジル３００、アエロジル３８０（いずれも日本アエロジル社製）等が挙げられる。 Examples of commercially available talc include MICRO ACE P-4, MICRO ACE P-6, and MICRO ACE P-8 (all manufactured by Nippon Talc Co., Ltd.).
Examples of commercially available silica include Aerosil 200, Aerosil 300, Aerosil 380 (all manufactured by Nippon Aerosil Co., Ltd.) and the like.
上記他のフィラーの含有量は、得られる光硬化性樹脂組成物の粘度等に応じて適宜調整すればよい。
上記他のフィラーとしてタルクを用いる場合、上記タルクの含有量は、本発明にかかるポリイソブチレン系ポリマーと本発明にかかる（メタ）アクリルモノマーとの合計１００重量部に対して、好ましい下限が５重量部、好ましい上限が５０重量部である。上記タルクの含有量がこの範囲であることにより、得られる光硬化性樹脂組成物が接着性及びバリア性を両立する効果により優れるものとなる。上記タルクの含有量のより好ましい下限は１０重量部、より好ましい上限は４０重量部である。
上記他のフィラーとしてシリカを用いる場合、上記シリカの含有量は、本発明にかかるポリイソブチレン系ポリマーと本発明にかかる（メタ）アクリルモノマーとの合計１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が３０重量部である。上記シリカの含有量がこの範囲であることにより、得られる光硬化性樹脂組成物が塗布性及びバリア性を両立する効果により優れるものとなる。上記シリカの含有量のより好ましい下限は１重量部、より好ましい上限は２０重量部である。 What is necessary is just to adjust content of said other filler suitably according to the viscosity etc. of the photocurable resin composition obtained.
When talc is used as the other filler, the content of the talc is preferably 5% by weight with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention. Parts, and the preferred upper limit is 50 parts by weight. When the content of the talc is within this range, the resulting photocurable resin composition is more excellent in the effect of achieving both adhesiveness and barrier properties. The minimum with more preferable content of the said talc is 10 weight part, and a more preferable upper limit is 40 weight part.
When silica is used as the other filler, the preferred lower limit of the silica content is 0.00 with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention. 1 part by weight, the preferred upper limit is 30 parts by weight. When the content of the silica is within this range, the resulting photocurable resin composition is more excellent in the effect of achieving both applicability and barrier properties. A more preferable lower limit of the silica content is 1 part by weight, and a more preferable upper limit is 20 parts by weight.
上記吸水性フィラーと上記他のフィラーとの合計の含有量は、本発明にかかるポリイソブチレン系ポリマーと本発明にかかる（メタ）アクリルモノマーとの合計１００重量部に対して、１００重量部以下であることが好ましい。上記吸水性フィラーと上記他のフィラーとの合計の含有量がこの範囲であることにより、得られる光硬化性樹脂組成物が接着性及びバリア性を両立する効果により優れるものとなる。上記吸水性フィラーと上記他のフィラーとの合計の含有量のより好ましい上限は８０重量部である。 The total content of the water-absorbing filler and the other filler is 100 parts by weight or less with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention. Preferably there is. When the total content of the water-absorbing filler and the other filler is within this range, the resulting photocurable resin composition is more excellent in the effect of achieving both adhesiveness and barrier properties. A more preferable upper limit of the total content of the water-absorbing filler and the other filler is 80 parts by weight.
本発明の光硬化性樹脂組成物は、粘着付与剤を含有することが好ましい。
上記粘着付与剤としては、例えば、テルペン樹脂、変性テルペン樹脂、クマロン樹脂、インデン樹脂、石油樹脂等が挙げられる。
上記変性テルペン樹脂としては、例えば、水素添加テルペン樹脂、テルペンフェノール共重合樹脂、芳香族変性テルペン樹脂等が挙げられる。
上記石油樹脂としては、例えば、脂環族系石油樹脂、非環式脂肪族系石油樹脂、芳香族系石油樹脂、脂肪族芳香族共重合系石油樹脂等が挙げられる。
なかでも、他の成分との相溶性や、得られる光硬化性樹脂組成物の接着性、バリア性等の観点から、上記粘着付与剤としては、石油樹脂が好ましく、脂環族系石油樹脂、芳香族系石油樹脂、脂肪族芳香族共重合系石油樹脂がより好ましく、脂環族系石油樹脂が特に好ましい。
これらの粘着付与剤は、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。 The photocurable resin composition of the present invention preferably contains a tackifier.
Examples of the tackifier include terpene resins, modified terpene resins, coumarone resins, indene resins, and petroleum resins.
Examples of the modified terpene resin include a hydrogenated terpene resin, a terpene phenol copolymer resin, and an aromatic modified terpene resin.
Examples of the petroleum resin include alicyclic petroleum resins, acyclic aliphatic petroleum resins, aromatic petroleum resins, and aliphatic aromatic copolymer petroleum resins.
Among these, from the viewpoints of compatibility with other components, adhesiveness of the resulting photocurable resin composition, barrier properties, etc., the tackifier is preferably a petroleum resin, an alicyclic petroleum resin, Aromatic petroleum resins and aliphatic aromatic copolymer petroleum resins are more preferred, and alicyclic petroleum resins are particularly preferred.
These tackifiers may be used alone or in combination of two or more.
上記脂環族系石油樹脂のうち市販されているものとしては、例えば、日本ゼオン社製の脂環族系石油樹脂、荒川化学工業社製の脂環族系石油樹脂、出光興産社製の脂環族系石油樹脂、エクソンモービル社製の脂環族系石油樹脂等が挙げられる。
上記日本ゼオン社製の脂環族系石油樹脂としては、例えば、Ｑｕｉｎｔｏｎｅ１３２５、Ｑｕｉｎｔｏｎｅ１３４５等が挙げられる。
上記荒川化学工業社製の脂環族系石油樹脂としては、例えば、アルコンＰ－１００、アルコンＰ－１２５、アルコンＰ－１４０等が挙げられる。
上記出光興産社製の脂環族系石油樹脂としては、例えば、アイマーブＳ－１００、アイマーブＳ－１１０、アイマーブＰ－１００、アイマーブＰ－１２５、アイマーブＰ－１４０等が挙げられる。
上記エクソンモービル社製の脂環族系石油樹脂としては、例えば、Ｅｓｃｏｒｅｚ５３００シリーズ、５６００シリーズ等が挙げられる。 Examples of commercially available alicyclic petroleum resins include alicyclic petroleum resins manufactured by Nippon Zeon, alicyclic petroleum resins manufactured by Arakawa Chemical Industries, and fats manufactured by Idemitsu Kosan Co., Ltd. Examples include cyclic petroleum resins and alicyclic petroleum resins manufactured by ExxonMobil.
Examples of the alicyclic petroleum resin manufactured by Nippon Zeon Co., Ltd. include Quintone 1325, Quintone 1345, and the like.
Examples of the alicyclic petroleum resin manufactured by Arakawa Chemical Industries include Alcon P-100, Alcon P-125, and Alcon P-140.
Examples of the alicyclic petroleum resin manufactured by Idemitsu Kosan Co., Ltd. include Imabe S-100, Imabe S-110, Imabe P-100, Imabe P-125, and Imabe P-140.
Examples of the alicyclic petroleum resin manufactured by ExxonMobil include Escorez 5300 series and 5600 series.
上記芳香族系石油樹脂のうち市販されているものとしては、例えば、ＥＮＤＥＸ１５５（イーストマン社製）等が挙げられる。 As what is marketed among the said aromatic petroleum resin, ENDEX155 (made by Eastman) etc. are mentioned, for example.
上記脂肪族芳香族共重合系石油樹脂のうち市販されているものとしては、例えば、ＱｕｉｎｔｏｎｅＤ１００（日本ゼオン社製）等が挙げられる。 As what is marketed among the said aliphatic aromatic copolymerization petroleum resin, QuintoneD100 (made by Nippon Zeon) etc. are mentioned, for example.
上記粘着付与剤の含有量は、本発明にかかるポリイソブチレン系ポリマーと本発明にかかる（メタ）アクリルモノマーとの合計１００重量部に対して、好ましい下限が１重量部、好ましい上限が１５重量部である。上記粘着付与剤の含有量がこの範囲であることにより、得られる光硬化性樹脂組成物が優れた硬化性及びバリア性を維持しつつ、接着性により優れるものとなる。上記粘着付与剤の含有量のより好ましい下限は５重量部、より好ましい上限は１０重量部である。 The content of the tackifier is preferably 1 part by weight with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention, and preferably 15 parts by weight with respect to the upper limit. It is. When the content of the tackifier is within this range, the resulting photocurable resin composition is more excellent in adhesiveness while maintaining excellent curability and barrier properties. The minimum with more preferable content of the said tackifier is 5 weight part, and a more preferable upper limit is 10 weight part.
本発明の光硬化性樹脂組成物は、増感剤を含有してもよい。上記増感剤は、上記光ラジカル重合開始剤の重合開始効率をより向上させて、本発明の光硬化性樹脂組成物の硬化反応をより促進させる役割を有する。 The photocurable resin composition of the present invention may contain a sensitizer. The sensitizer has a role of further improving the polymerization initiation efficiency of the photoradical polymerization initiator and further promoting the curing reaction of the photocurable resin composition of the present invention.
上記増感剤としては、例えば、アントラセン系化合物、チオキサントン系化合物、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、ベンゾフェノン、２，４－ジクロロベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、４，４’－ビス（ジメチルアミノ）ベンゾフェノン、４－ベンゾイル－４’メチルジフェニルサルファイド等が挙げられる。
上記アントラセン系化合物としては、例えば、９，１０－ジブトキシアントラセン等が挙げられる。
上記チオキサントン系化合物としては、例えば、２，４－ジエチルチオキサントン等が挙げられる。
これらの増感剤は、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。 Examples of the sensitizer include anthracene compounds, thioxanthone compounds, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, Examples include 4,4′-bis (dimethylamino) benzophenone and 4-benzoyl-4′methyldiphenyl sulfide.
Examples of the anthracene compound include 9,10-dibutoxyanthracene.
Examples of the thioxanthone compound include 2,4-diethylthioxanthone.
These sensitizers may be used independently and 2 or more types may be used in combination.
上記増感剤の含有量は、本発明にかかるポリイソブチレン系ポリマーと本発明にかかる（メタ）アクリルモノマーとの合計１００重量部に対して、好ましい下限は０．０５重量部、好ましい上限は３重量部である。上記増感剤の含有量が０．０５重量部以上であることにより、増感効果がより発揮される。上記増感剤の含有量が３重量部以下であることにより、吸収が大きくなり過ぎずに深部まで光を伝えることができる。上記増感剤の含有量のより好ましい下限は０．１重量部、より好ましい上限は１重量部である。 The content of the sensitizer is preferably 0.05 parts by weight with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention, and the preferable upper limit is 3 parts. Parts by weight. When the content of the sensitizer is 0.05 parts by weight or more, the sensitizing effect is more exhibited. When the content of the sensitizer is 3 parts by weight or less, light can be transmitted to a deep part without excessive absorption. The minimum with more preferable content of the said sensitizer is 0.1 weight part, and a more preferable upper limit is 1 weight part.
本発明の光硬化性樹脂組成物は、シランカップリング剤を含有してもよい。上記シランカップリング剤は、本発明の光硬化性樹脂組成物と基板等との接着性を向上させる役割を有する。 The photocurable resin composition of the present invention may contain a silane coupling agent. The said silane coupling agent has a role which improves the adhesiveness of the photocurable resin composition of this invention, a board | substrate, etc.
上記シランカップリング剤としては、本発明にかかるポリオレフィン系ポリマーと相溶可能な公知のシランカップリング剤を用いることができる。具体的には例えば、３－（メタ）アクリロキシプロピルメチルジメトキシシラン、３－（メタ）アクリロキシプロピルトリメトキシシラン、３－（メタ）アクリロキシプロピルメチルジエトキシシラン、３－（メタ）アクリロキシプロピルトリエトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－エチル－（（トリエトキシシリルプロポキシ）メチル）オキセタン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン等が挙げられる。
これらのシランカップリング剤は、単独で用いられてもよいし、２種以上が組み合わせて用いられてもよい。 As said silane coupling agent, the well-known silane coupling agent compatible with the polyolefin-type polymer concerning this invention can be used. Specifically, for example, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxy Propyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-ethyl-((triethoxysilylpropoxy) methyl) oxetane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-aminopropyltri Tokishishiran, 3-aminopropyltriethoxysilane, and the like.
These silane coupling agents may be used alone or in combination of two or more.
上記シランカップリング剤の含有量は、本発明にかかるポリイソブチレン系ポリマーと本発明にかかる（メタ）アクリルモノマーとの合計１００重量部に対して、好ましい下限が０．１重量部、好ましい上限が５重量部である。上記シランカップリング剤の含有量がこの範囲であることにより、得られる光硬化性樹脂組成物が優れたバリア性を維持しつつ、の接着性により優れるものとなる。上記シランカップリング剤の含有量のより好ましい下限は０．３重量部、より好ましい上限は３重量部である。 The content of the silane coupling agent is preferably 0.1 parts by weight with respect to a total of 100 parts by weight of the polyisobutylene polymer according to the present invention and the (meth) acrylic monomer according to the present invention, and preferably has an upper limit. 5 parts by weight. When the content of the silane coupling agent is within this range, the resulting photocurable resin composition is more excellent in adhesiveness while maintaining excellent barrier properties. The minimum with more preferable content of the said silane coupling agent is 0.3 weight part, and a more preferable upper limit is 3 weight part.
本発明の光硬化性樹脂組成物は、溶剤を含有しない。
本発明の光硬化性樹脂組成物は、該溶剤を含有しなくても塗布性に優れるため、有機ＥＬ表示素子や量子ドットデバイス等の製造に用いた場合でも、乾燥工程を必要とせず、アウトガスの発生等による素子や装置へのダメージを抑制することができる。
なお、本明細書において「溶剤を含有しない」とは、溶剤の含有量が１０００ｐｐｍ未満であることを意味する。 The photocurable resin composition of the present invention does not contain a solvent.
Since the photocurable resin composition of the present invention is excellent in coating properties even without containing the solvent, it does not require a drying step even when used in the production of organic EL display elements, quantum dot devices, etc., and is outgassed. It is possible to suppress damage to elements and devices due to the occurrence of the above.
In the present specification, “does not contain a solvent” means that the content of the solvent is less than 1000 ppm.
また、本発明の光硬化性樹脂組成物は、本発明の目的を阻害しない範囲で、必要に応じて、紫外線吸収剤、光安定剤、酸化防止剤、着色剤等の公知の各種添加剤を含有してもよい。 In addition, the photocurable resin composition of the present invention contains various known additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, and a colorant as necessary, as long as the object of the present invention is not impaired. You may contain.
本発明の光硬化性樹脂組成物を製造する方法としては、例えば、混合機を用いて、本発明にかかるポリイソブチレン系ポリマーと、本発明にかかる（メタ）アクリルモノマーと、光ラジカル重合開始剤と、吸水性フィラーと、粘着付与剤やシランカップリング剤等の添加剤とを混合する方法等が挙げられる。
上記混合機としては、例えば、ホモディスパー、ホモミキサー、万能ミキサー、プラネタリーミキサー、ニーダー、３本ロール等が挙げられる。 As a method for producing the photocurable resin composition of the present invention, for example, using a mixer, the polyisobutylene polymer according to the present invention, the (meth) acrylic monomer according to the present invention, and a radical photopolymerization initiator. And a method of mixing a water-absorbing filler and an additive such as a tackifier or a silane coupling agent.
Examples of the mixer include a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three roll.
本発明の光硬化性樹脂組成物は、Ｅ型粘度計を用いて２５℃、２．５ｒｐｍの条件で測定される粘度の下限が１Ｐａ・ｓ、上限が１０００Ｐａ・ｓである。上記粘度がこの範囲であることにより、本発明の光硬化性樹脂組成物が塗布性及び形状保持性に優れるものとなる。上記粘度の好ましい下限は１０Ｐａ・ｓ、好ましい上限は８００Ｐａ・ｓ、より好ましい下限は５０Ｐａ・ｓ、より好ましい上限は５００Ｐａ・ｓである。 The lower limit of the viscosity of the photocurable resin composition of the present invention measured using an E-type viscometer at 25 ° C. and 2.5 rpm is 1 Pa · s, and the upper limit is 1000 Pa · s. When the viscosity is within this range, the photocurable resin composition of the present invention is excellent in applicability and shape retention. The preferable lower limit of the viscosity is 10 Pa · s, the preferable upper limit is 800 Pa · s, the more preferable lower limit is 50 Pa · s, and the more preferable upper limit is 500 Pa · s.
本発明の光硬化性樹脂組成物は、有機ＥＬ表示素子用封止剤として好適に用いることができる。本発明の光硬化性樹脂組成物からなる有機ＥＬ表示素子用封止剤もまた、本発明の１つである。 The photocurable resin composition of this invention can be used suitably as a sealing agent for organic EL display elements. The sealing agent for organic EL display elements which consists of the photocurable resin composition of this invention is also one of this invention.
本発明の有機ＥＬ表示素子用封止剤による有機ＥＬ表示素子の封止は、シート状とした封止剤を貼り付けるようなものではなく、封止剤を所望の形状に塗布した後、硬化させることにより封止部を形成するものである。更に言えば、本発明の有機ＥＬ表示素子用封止剤は、いわゆるダムフィル封止に好適に用いられる。
本発明の有機ＥＬ表示素子用封止剤により形成される封止部の形状としては、有機発光材料層を有する積層体を外気から保護しうる形状であれば特に限定されず、該積層体を完全に被覆する形状であってもよいし、該積層体の周囲に封止壁を形成してもよい。なかでも、本発明の有機ＥＬ表示素子用封止剤は、該封止壁を形成するため有機ＥＬ表示素子用周辺封止剤として好適に用いることができる。 The sealing of the organic EL display element with the sealing agent for organic EL display elements of the present invention is not like sticking the sealing agent in the form of a sheet, but is cured after applying the sealing agent in a desired shape. By doing so, a sealing portion is formed. Furthermore, the sealing agent for organic EL display elements of the present invention is suitably used for so-called dam fill sealing.
The shape of the sealing portion formed by the organic EL display element sealant of the present invention is not particularly limited as long as it is a shape that can protect the laminate having the organic light emitting material layer from the outside air, and the laminate is not limited. The shape may be completely covered, or a sealing wall may be formed around the laminate. Especially, since the sealing agent for organic EL display elements of this invention forms this sealing wall, it can be used suitably as a periphery sealing agent for organic EL display elements.
本発明の有機ＥＬ表示素子用封止剤を用いてなる有機ＥＬ表示素子もまた、本発明の１つである。 The organic EL display element using the sealing agent for organic EL display elements of the present invention is also one aspect of the present invention.
また、本発明の光硬化性樹脂組成物は、量子ドットデバイス用封止剤として好適に用いることができる。本発明の光硬化性樹脂組成物からなる量子ドットデバイス用封止剤もまた、本発明の１つである。 Moreover, the photocurable resin composition of this invention can be used suitably as a sealing agent for quantum dot devices. The encapsulant for quantum dot devices comprising the photocurable resin composition of the present invention is also one aspect of the present invention.
本発明の量子ドットデバイス用封止剤による量子ドットデバイスの封止は、シート状とした封止剤を貼り付けるようなものではなく、封止剤を所望の形状に塗布した後、硬化させることにより封止部を形成するものである。更に言えば、本発明の量子ドットデバイス用封止剤は、いわゆるダムフィル封止に好適に用いられる。
本発明の量子ドットデバイス用封止剤により形成される封止部の形状としては、量子ドットを含む層を外気から保護しうる形状であれば特に限定されず、該量子ドットを含む層を完全に被覆する形状であってもよいし、該量子ドットを含む層の周囲に封止壁を形成してもよい。 The sealing of the quantum dot device with the encapsulant for quantum dot devices of the present invention is not like sticking a sheet-like encapsulant, but is cured after applying the encapsulant in a desired shape. Thus, the sealing portion is formed. Furthermore, the encapsulant for quantum dot devices of the present invention is suitably used for so-called damfill encapsulation.
The shape of the sealing part formed by the encapsulant for quantum dot devices of the present invention is not particularly limited as long as it can protect the layer containing quantum dots from the outside air, and the layer containing the quantum dots is completely The sealing wall may be formed around the layer containing the quantum dots.
本発明の量子ドットデバイス用封止剤を用いてなる量子ドットデバイスもまた、本発明の１つである。本発明の量子ドットデバイスとしては、量子ドットを使用した表示素子が好ましく、量子ドットを使用した液晶表示素子がより好ましい。本発明の量子ドットデバイスが量子ドットを使用した表示素子である場合、本発明の量子ドットデバイス用封止剤は、量子ドットを用いた波長変換シートの封止に好適に用いられる。 A quantum dot device using the encapsulant for a quantum dot device of the present invention is also one aspect of the present invention. As the quantum dot device of the present invention, a display element using quantum dots is preferable, and a liquid crystal display element using quantum dots is more preferable. When the quantum dot device of the present invention is a display element using quantum dots, the encapsulant for quantum dot devices of the present invention is suitably used for sealing a wavelength conversion sheet using quantum dots.
本発明によれば、保存安定性、塗布性、接着性、及び、バリア性に優れる光硬化性樹脂組成物を提供することができる。また、本発明によれば、該光硬化性樹脂組成物からなる有機ＥＬ表示素子用封止剤及び量子ドットデバイス用封止剤、該有機ＥＬ表示素子用封止剤を用いてなる有機ＥＬ表示素子、並びに、該量子ドットデバイス用封止剤を用いてなる量子ドットデバイスを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the photocurable resin composition excellent in storage stability, applicability | paintability, adhesiveness, and barrier property can be provided. Moreover, according to this invention, the organic EL display element sealing agent which consists of this photocurable resin composition, the sealing agent for quantum dot devices, and the organic EL display which uses this sealing agent for organic EL display elements An element and a quantum dot device using the encapsulant for the quantum dot device can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（実施例１～１７、比較例１～１１）
表１～３に記載された配合比に従い、各材料を、各材料を撹拌混合機（シンキー社製、「ＡＲ－２５０」）を用い、撹拌速度２０００ｒｐｍで撹拌混合した後、更に３本ロール（ノリタケ社製、「ＮＲ－４２Ａ」）を用いて混練することにより、実施例１～１７、比較例１～１１の光硬化性樹脂組成物を作製した。
得られた各光硬化性樹脂組成物について、Ｅ型粘度計（東機産業社製、「ＶＩＳＣＯＭＥＴＥＲ　ＴＶ－２２」）を用いて、２５℃、２．５ｒｐｍの条件において測定した粘度を表１～３に示した。 (Examples 1 to 17, Comparative Examples 1 to 11)
According to the blending ratios described in Tables 1 to 3, each material was stirred and mixed at a stirring speed of 2000 rpm using a stirring mixer (“AR-250” manufactured by Sinky Co., Ltd.). The photocurable resin compositions of Examples 1 to 17 and Comparative Examples 1 to 11 were prepared by kneading using “NR-42A” manufactured by Noritake Co., Ltd.
About each obtained photocurable resin composition, the viscosity measured on 25 degreeC and 2.5 rpm conditions using the E-type viscosity meter (the Toki Sangyo company make, "VISCOMETER TV-22") is Table 1- It was shown in 3.
＜評価＞
実施例及び比較例で得られた各光硬化性樹脂組成物について、以下の評価を行った。結果を表１～３に示した。 <Evaluation>
The following evaluation was performed about each photocurable resin composition obtained by the Example and the comparative example. The results are shown in Tables 1-3.
（保存安定性（相分離））
実施例及び比較例で得られた各光硬化性樹脂組成物を、ドクターブレードを用いてガラス板上に１００μｍの厚さに塗布した。２５℃で１０分間放置した後、光学顕微鏡（倍率２０倍）で塗膜を観察し、相分離が見られなかった場合を「○」、相分離が見られた場合を「△」、光学顕微鏡を使用せずに目視で相分離が観察された場合を「×」として保存安定性を評価した。 (Storage stability (phase separation))
Each photocurable resin composition obtained in Examples and Comparative Examples was applied to a thickness of 100 μm on a glass plate using a doctor blade. After standing at 25 ° C. for 10 minutes, the coating film was observed with an optical microscope (magnification 20 times), “◯” when phase separation was not observed, “Δ” when phase separation was observed, optical microscope The storage stability was evaluated as “x” when the phase separation was observed visually without using.
（接着性）
実施例及び比較例で得られた各光硬化性樹脂組成物１０ｇに対して、直径１０μｍのスペーサー粒子（積水化学工業社製、「ミクロパールＳＰ－２１０」）０．０３ｇを加え、撹拌混合機（シンキー社製、「ＡＲ－２５０」）を用いて均一に分散させた。ガラス基板Ａ（長さ５０ｍｍ、幅２５ｍｍ、厚さ０．７ｍｍのガラス表面をアセトンで洗浄後乾燥したもの）上に該スペーサー粒子を分散させた光硬化性樹脂組成物を塗布した後、ガラス基板Ｂ（長さ５ｍｍ、幅５ｍｍ、厚さ０．７ｍｍのガラスをアセトンに浸漬洗浄し、乾燥したもの）を貼り付け、加圧して厚みを均一にした。次いで、ＵＶ－ＬＥＤ照射装置にて波長３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２照射して光硬化性樹脂組成物を硬化させることにより、ガラス基板Ａとガラス基板Ｂとを接着した。ガラス基板Ａとガラス基板Ｂとの剪断接着力をダイシェアテスター（デイジ社製、「ボンドテスター４０００」）にて２３℃、２００μｍ／秒の剪断速度条件で測定した。
剪断接着力が２００Ｎ以上であった場合を「○」、２００Ｎ未満１００Ｎ以上であった場合を「△」、１００Ｎ未満であった場合を「×」として接着性を評価した。 (Adhesiveness)
To 10 g of each photocurable resin composition obtained in Examples and Comparative Examples, 0.03 g of spacer particles having a diameter of 10 μm (manufactured by Sekisui Chemical Co., Ltd., “Micropearl SP-210”) was added, and the mixture was stirred. (“AR-250”, manufactured by Shinky Corp.) was used to uniformly disperse. After applying the photocurable resin composition in which the spacer particles are dispersed on a glass substrate A (a glass surface having a length of 50 mm, a width of 25 mm, and a thickness of 0.7 mm washed with acetone and dried), the glass substrate B (a glass having a length of 5 mm, a width of 5 mm, and a thickness of 0.7 mm was dipped and washed in acetone and dried) was applied and pressed to make the thickness uniform. Next, the glass substrate A and the glass substrate B were bonded together by curing the photocurable resin composition by irradiating an ultraviolet ray having a wavelength of 365 nm at 3000 mJ / cm 2 with a UV-LED irradiation device. The shear adhesive strength between the glass substrate A and the glass substrate B was measured with a die shear tester (manufactured by Daisy Corporation, “Bond Tester 4000”) at a shear rate of 23 ° C. and 200 μm / second.
The adhesiveness was evaluated as “◯” when the shear adhesive force was 200 N or more, “Δ” when the shear adhesive force was less than 200 N and 100 N or more, and “X” when it was less than 100 N.
（バリア性）
実施例及び比較例で得られた各光硬化性樹脂組成物について、以下のＣａ－ＴＥＳＴを行った。
まず、実施例及び比較例で得られた各光硬化性樹脂組成物１０ｇに対して、直径１０μｍのスペーサー粒子（積水化学工業社製、「ミクロパールＳＰ－２１０」）０．０３ｇを加え、撹拌混合機（シンキー社製、「ＡＲ－２５０」）を用いて均一に分散させた。次いで、スペーサー粒子を分散させた光硬化性樹脂組成物をガラス基板の表面に塗布した。
次に、３０ｍｍ×３０ｍｍの大きさの別のガラス基板に２ｍｍ×２ｍｍの開口部を複数有するマスクを被せ、Ｃａを真空蒸着機により蒸着させた。蒸着の条件は、真空蒸着装置の蒸着器内を２×１０－３Ｐａまで減圧してＣａを５．０Å／ｓの蒸着速度で２０００Å成膜するものとした。Ｃａを蒸着したガラス基板を露点（－６０℃以上）に管理されたグローボックス内に移動させ、表面に光硬化性樹脂組成物を塗布したガラス基板を、光硬化性樹脂組成物を介してＣａを蒸着したガラス基板のＣａの蒸着パターン上に貼り合わせた。この時、ガラス基板端面から２ｍｍ、４ｍｍ、６ｍｍの位置に蒸着したＣａが存在するように位置を合わせて貼り合わせた。加圧して光硬化性樹脂組成物層の厚みを均一にした後、３６５ｎｍの紫外線を３０００ｍＪ／ｃｍ２照射することにより光硬化性樹脂組成物を硬化させ、Ｃａ－ＴＥＳＴ基板を作製した。
得られたＣａ－ＴＥＳＴ基板を、８５℃、８５％ＲＨの高温高湿条件に暴露し、２枚のガラス基板に挟まれた光硬化性樹脂組成物の硬化物からなる層へのガラス基板端面からの時間毎の水分の浸入距離をＣａの消失から観測した。その結果、水分の浸入距離が６ｍｍに達するまでの時間が１０００時間以上であった場合を「○」、５００時間以上１０００時間未満であった場合を「△」、５００時間未満であった場合を「×」としてバリア性を評価した。
なお、比較例１１で得られた光硬化性樹脂組成物は、Ｃａ－ＴＥＳＴ中にガラス基板が剥離したため、バリア性を評価することができなかった。 (Barrier properties)
The following Ca-TEST was performed on each photocurable resin composition obtained in Examples and Comparative Examples.
First, 0.03 g of spacer particles having a diameter of 10 μm (manufactured by Sekisui Chemical Co., Ltd., “Micropearl SP-210”) was added to 10 g of each photocurable resin composition obtained in Examples and Comparative Examples, followed by stirring. The mixture was uniformly dispersed using a mixer (“AR-250”, manufactured by Shinky Corporation). Next, a photocurable resin composition in which spacer particles were dispersed was applied to the surface of the glass substrate.
Next, another glass substrate having a size of 30 mm × 30 mm was covered with a mask having a plurality of openings of 2 mm × 2 mm, and Ca was vapor-deposited by a vacuum vapor deposition machine. The conditions for the vapor deposition were that the inside of the vapor deposition unit of the vacuum vapor deposition apparatus was depressurized to 2 × 10 −3 Pa and a film of 2000 mm of Ca was formed at a vapor deposition rate of 5.0 kg / s. The glass substrate on which Ca is vapor-deposited is moved into a glow box controlled at a dew point (−60 ° C. or more), and the glass substrate having the surface coated with the photocurable resin composition is transferred to the Ca substrate via the photocurable resin composition. The glass substrate was laminated on the vapor deposition pattern of Ca. At this time, the positions were aligned and bonded so that the deposited Ca existed at positions of 2 mm, 4 mm, and 6 mm from the end face of the glass substrate. After pressurizing to uniformize the thickness of the photocurable resin composition layer, the photocurable resin composition was cured by irradiating with 3000 nm ultraviolet rays at 3000 mJ / cm 2 to prepare a Ca-TEST substrate.
The obtained Ca-TEST substrate is exposed to high-temperature and high-humidity conditions of 85 ° C. and 85% RH, and an end surface of the glass substrate on a layer made of a cured product of a photocurable resin composition sandwiched between two glass substrates. From the disappearance of Ca, the intrusion distance of water every hour from was observed. As a result, the case where the time until the water penetration distance reaches 6 mm is 1000 hours or more, “◯”, the case where it is 500 hours or more and less than 1000 hours is “△”, the case where it is less than 500 hours Barrier property was evaluated as “×”.
Note that the photocurable resin composition obtained in Comparative Example 11 could not be evaluated for barrier properties because the glass substrate was peeled off during Ca-TEST.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
本発明によれば、保存安定性、塗布性、接着性、及び、バリア性に優れる光硬化性樹脂組成物を提供することができる。また、本発明によれば、該光硬化性樹脂組成物からなる有機ＥＬ表示素子用封止剤及び量子ドットデバイス用封止剤、該有機ＥＬ表示素子用封止剤を用いてなる有機ＥＬ表示素子、並びに、該量子ドットデバイス用封止剤を用いてなる量子ドットデバイスを提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the photocurable resin composition excellent in storage stability, applicability | paintability, adhesiveness, and barrier property can be provided. Moreover, according to this invention, the organic EL display element sealing agent which consists of this photocurable resin composition, the sealing agent for quantum dot devices, and the organic EL display which uses this sealing agent for organic EL display elements An element and a quantum dot device using the encapsulant for the quantum dot device can be provided.

Claims (12)

  1. 主鎖に下記式（１）で表される繰り返し単位を有し、重量平均分子量が５０００以上１０万以下であるポリマーと、脂環式骨格と（メタ）アクリロイル基とを有するモノマーと、光ラジカル重合開始剤と、吸水性フィラーとを含有し、溶剤を含有せず、
    前記主鎖に下記式（１）で表される繰り返し単位を有し、重量平均分子量が５０００以上１０万以下であるポリマーと前記脂環式骨格と（メタ）アクリロイル基とを有するモノマーとの合計１００重量部に対して、前記脂環式骨格と（メタ）アクリロイル基とを有するモノマーの含有量が３０重量部以上９０重量部以下であり、かつ、前記吸水性フィラーの含有量が５重量部以上２００重量部以下であり、
    Ｅ型粘度計を用いて２５℃、２．５ｒｐｍの条件で測定される粘度が１Ｐａ・ｓ以上１０００Ｐａ・ｓ以下である
    ことを特徴とする光硬化性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
         A polymer having a repeating unit represented by the following formula (1) in the main chain and having a weight average molecular weight of from 5,000 to 100,000, a monomer having an alicyclic skeleton and a (meth) acryloyl group, a photo radical Contains a polymerization initiator and a water-absorbing filler, does not contain a solvent,
    The total of the polymer which has a repeating unit represented by following formula (1) in the said principal chain, and whose weight average molecular weight is 5000 or more and 100,000 or less, the said alicyclic skeleton, and a (meth) acryloyl group The content of the monomer having the alicyclic skeleton and the (meth) acryloyl group is from 30 parts by weight to 90 parts by weight with respect to 100 parts by weight, and the water-absorbing filler content is 5 parts by weight. More than 200 parts by weight,
    A photocurable resin composition having a viscosity of 1 Pa · s or more and 1000 Pa · s or less measured at 25 ° C. and 2.5 rpm using an E-type viscometer.
    Figure JPOXMLDOC01-appb-C000001
  2. 前記脂環式骨格と（メタ）アクリロイル基とを有するモノマーは、イソボルニル（メタ）アクリレート及び／又はジシクロペンタジエンジメタノールジ（メタ）アクリレートである請求項１記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 1, wherein the monomer having an alicyclic skeleton and a (meth) acryloyl group is isobornyl (meth) acrylate and / or dicyclopentadiene dimethanol di (meth) acrylate.
  3. 前記脂環式骨格と（メタ）アクリロイル基とを有するモノマーは、イソボルニルメタクリレート及び／又はジシクロペンタジエンジメタノールジメタクリレートである請求項２記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 2, wherein the monomer having an alicyclic skeleton and a (meth) acryloyl group is isobornyl methacrylate and / or dicyclopentadiene dimethanol dimethacrylate.
  4. 前記吸水性フィラーは、平均一次粒子径が０．５μｍ以上５μｍ以下であり、比重が１．５ｇ／ｃｍ３以上３．３ｇ／ｃｍ３以下である請求項１、２又は３記載の光硬化性樹脂組成物。 4. The photocurable composition according to claim 1, wherein the water-absorbing filler has an average primary particle size of 0.5 μm to 5 μm and a specific gravity of 1.5 g / cm 3 to 3.3 g / cm 3 . Resin composition.
  5. 前記吸水性フィラーは、酸化カルシウムである請求項１、２、３又は４記載の光硬化性樹脂組成物。 The photocurable resin composition according to claim 1, wherein the water-absorbing filler is calcium oxide.
  6. 前記吸水性フィラー以外の他のフィラーを含有する請求項１、２、３、４又は５記載の光硬化性樹脂組成物。 The photocurable resin composition of Claim 1, 2, 3, 4 or 5 containing fillers other than the said water absorbing filler.
  7. 前記他のフィラーとして、タルク及び／又はシリカを含有する請求項６記載の光硬化性樹脂組成物。 The photocurable resin composition of Claim 6 which contains a talc and / or a silica as said other filler.
  8. 前記主鎖に式（１）で表される繰り返し単位を有し、重量平均分子量が５０００以上１０万以下であるポリマーと前記脂環式骨格と（メタ）アクリロイル基とを有するモノマーとの合計１００重量部に対して、粘着付与剤を１重量部以上１５重量部以下含有する請求項１、２、３、４、５、６又は７記載の光硬化性樹脂組成物。 A total of 100 of the polymer having a repeating unit represented by the formula (1) in the main chain and having a weight average molecular weight of 5,000 or more and 100,000 or less, the alicyclic skeleton, and a monomer having a (meth) acryloyl group. The photocurable resin composition according to claim 1, 2, 3, 4, 5, 6 or 7, comprising 1 to 15 parts by weight of a tackifier with respect to parts by weight.
  9. 請求項１、２、３、４、５、６、７又は８記載の光硬化性樹脂組成物からなる有機ＥＬ表示素子用封止剤。 The sealing agent for organic EL display elements which consists of a photocurable resin composition of Claim 1, 2, 3, 4, 5, 6, 7 or 8.
  10. 請求項９記載の有機ＥＬ表示素子用封止剤を用いてなる有機ＥＬ表示素子。 The organic electroluminescent display element which uses the sealing agent for organic electroluminescent display elements of Claim 9.
  11. 請求項１、２、３、４、５、６、７又は８記載の光硬化性樹脂組成物からなる量子ドットデバイス用封止剤。 A sealant for a quantum dot device comprising the photocurable resin composition according to claim 1, 2, 3, 4, 5, 6, 7 or 8.
  12. 請求項１１記載の量子ドットデバイス用封止剤を用いてなる量子ドットデバイス。 The quantum dot device formed using the sealing agent for quantum dot devices of Claim 11.
PCT/JP2018/004353 2017-02-14 2018-02-08 Photocurable resin composition, sealing agent for organic el display elements, organic el display element, sealing agent for quantum dot devices, and quantum dot device WO2018151002A1 (en)

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