Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • 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
• • 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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