CN112912407A - Curable resin composition, cured product, and organic EL display element - Google Patents

Curable resin composition, cured product, and organic EL display element Download PDF

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Publication number
CN112912407A
CN112912407A CN201980068585.1A CN201980068585A CN112912407A CN 112912407 A CN112912407 A CN 112912407A CN 201980068585 A CN201980068585 A CN 201980068585A CN 112912407 A CN112912407 A CN 112912407A
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curable resin
resin composition
organic
cured product
present
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金千鹤
山本拓也
增井良平
西海由季
笹野美香
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants
    • 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
    • C08F20/00—Homopolymers and 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
    • 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
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • 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
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    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • 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
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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Abstract

The purpose of the present invention is to provide a curable resin composition which has excellent curability and low outgassing properties with respect to light having a long wavelength, and which can suppress display defects in an organic EL display device. Further, the present invention aims to provide a cured product of the curable resin composition and an organic EL display element having the cured product. The curable resin composition of the present invention is used as a sealing agent for an organic EL display element, and comprises a curable resin, a photopolymerization initiator, and a sensitizer, wherein the sensitizer contains an anthracene compound having no ester bond, and the amount of anthraquinone, which is determined by thermal desorption GC-MS measurement of a cured product of the curable resin composition under thermal desorption conditions of 110 ℃ for 30 minutes, is 3000ppm or less in terms of toluene.

Description

Curable resin composition, cured product, and organic EL display element
Technical Field
The present invention relates to a curable resin composition which is excellent in curability and low outgassing property with respect to light having a long wavelength and can suppress display defects of an organic EL display device. The present invention also relates to a cured product of the curable resin composition and an organic EL display device having the cured product.
Background
An organic electroluminescence (hereinafter, also referred to as "organic EL") display element has a laminate structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other, and electrons are injected from one electrode into the organic light emitting material layer, and holes are injected from the other electrode into the organic light emitting material layer, whereby the electrons and the holes are combined in the organic light emitting material layer to emit light. Since the organic EL display element emits light in this manner, the organic EL display element has advantages of being excellent in visibility, being thin, and being capable of dc low-voltage driving, as compared with a liquid crystal display element or the like that requires a backlight.
The organic light-emitting material layer and the electrode constituting the organic EL display device have a problem that their characteristics are easily deteriorated by moisture, oxygen, or the like. Therefore, in order to obtain a practical organic EL display element, it is necessary to prolong the life by isolating the organic light-emitting material layer and the electrode from the atmosphere. As a method of isolating the organic light emitting material layer and the electrode from the atmosphere, a method of sealing the organic EL display element with a sealant has been performed (for example, patent document 1). In sealing an organic EL display element with a sealant, in general, in order to sufficiently suppress permeation of moisture, oxygen, or the like, a method is used in which an inorganic film called a passivation film is provided on a laminate having organic light emitting material layers, and the inorganic film is sealed with a sealant.
In recent years, instead of a bottom emission type organic EL display element in which light emitted from an organic light emitting material layer is extracted from the substrate surface side on which a light emitting element is formed, a top emission type organic EL display element in which light is extracted from the upper surface side of an organic light emitting layer has attracted attention. This system has an advantage that the open ratio (Japanese: open ratio) is high, and the system is driven at a low voltage, which is advantageous for a long service life. In such a top emission type organic EL display element, since the upper surface side of the light-emitting layer needs to be transparent, a transparent moisture-proof substrate such as glass is laminated on the upper surface side of the light-emitting element with a transparent sealing layer interposed therebetween, and sealing is performed (for example, patent document 2).
As a method of forming the sealing layer, there is a method of applying a sealing agent on a substrate by an ink jet method and then curing the sealing agent. If such a coating method by an inkjet method is used, the sealing layer can be uniformly formed at high speed. However, when a sealant suitable for application by an ink jet method is used for a top emission type organic EL display element, there is a problem that display defects such as dark spots (japanese: ダ - クスポツト) may occur in the obtained organic EL display element. In particular, even in the case of a bottom emission type, a sealant in which no display failure occurs may be used, and in the case of a top emission type organic EL display element, a display failure may occur.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2007-115692
Patent document 2: japanese laid-open patent publication No. 2009-051980
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a curable resin composition which has excellent curability and low outgassing properties with respect to light having a long wavelength, and which can suppress display defects in an organic EL display device. Further, the present invention aims to provide a cured product of the curable resin composition and an organic EL display element having the cured product.
Means for solving the problems
The present invention is a curable resin composition used as a sealing agent for an organic EL display element, the curable resin composition containing a curable resin, a photopolymerization initiator, and a sensitizer, the sensitizer containing an anthracene compound having no ester bond, wherein the amount of anthraquinone, as quantified in terms of toluene, is 3000ppm or less when a cured product of the curable resin composition is measured by thermal desorption GC-MS under thermal desorption conditions of 110 ℃ and 30 minutes.
The present invention is described in detail below.
The present inventors have studied, from the viewpoint of reducing damage to an organic EL display element, and the like: a sensitizer is added to a curable resin composition used as a sealing agent for an organic EL display element, and the curable resin composition is cured by light having a wavelength of 395nm or the like. In addition, in order to make the curable resin composition excellent in curability, the use of an anthracene compound as the sensitizer has been studied. However, the resultant organic EL display element sometimes generates dark spots. The inventors believe that: the reason why the dark spot is generated when the anthracene compound is used as a sensitizer is that, in the case where the anthracene compound having an ester bond is used as the anthracene compound, an acid derived from the ester bond is generated upon decomposition of the anthracene compound. Therefore, the present inventors have studied to use an anthracene compound having no ester bond as the anthracene compound. However, when an organic EL display device is produced using the obtained curable resin composition, display defects such as peeling of a cured product of the curable resin composition and non-emission of light over the entire surface may occur. The inventors believe that: the reason why the cured product of the curable resin composition is peeled off when the anthracene compound is used is that outgas from the anthracene compound is generated because the anthracene compound is exposed to a high-temperature environment in a specific step (for example, a step of forming a passivation film by a CVD method or the like) in the production of an organic EL display device. Therefore, the present inventors studied: the anthraquinone produced when this anthracene compound is decomposed is determined to have a quantitative value equal to or less than a specific value when a cured product is measured by thermal desorption GC-MS under specific conditions. As a result, they have found that a curable resin composition which is excellent in curability and low outgassing property with respect to light having a long wavelength and can suppress display defects of an organic EL display element can be obtained, and have completed the present invention.
The curable resin composition of the present invention has an anthraquinone content of 3000ppm or less as quantified in terms of toluene when a cured product is measured by thermal desorption GC-MS under thermal desorption conditions of 110 ℃ for 30 minutes. When the amount of anthraquinone is 3000ppm or less, the curable resin composition of the present invention can provide an organic EL display device having excellent display performance.
The upper limit of the amount of the above-mentioned anthraquinones is preferably 2500ppm, more preferably 2000 ppm. The above anthraquinone amount is most preferably 0 ppm.
The measurement of the amount of anthraquinone and the total amount of outgas described below can be performed as follows: for 1mg of the cured product, using a thermal desorption apparatus and a GC-MS apparatus, the amount of gas component generated when heating was performed under thermal desorption conditions of 110 ℃ for 30 minutes was measured.
In addition, the thermal desorption GC-MS was measured using a cured product obtained by irradiating 2000mJ/cm of the curable resin composition with an LED lamp2Ultraviolet rays having a wavelength of 395 nm.
In the curable resin composition of the present invention, it is preferable that the total amount of outgas determined in terms of toluene is 6000ppm or less when the cured product is measured by thermal desorption GC-MS under thermal desorption conditions of 110 ℃ for 30 minutes. When the total amount of outgas is 6000ppm or less, the curable resin composition of the present invention has an excellent effect of suppressing the occurrence of dark spots and the like in the obtained organic EL display device. The above-mentioned total amount of outgas is most preferably 0 ppm.
The amount of anthraquinone and the total amount of outgas can be set to the above ranges by: selection of the kind, combination, and adjustment of the content ratio of each constituent component such as a sensitizer containing an anthracene compound having no ester bond, a curable resin, a photopolymerization initiator, and a stabilizer, which will be described later, are performed.
The curable resin composition of the present invention contains a curable resin.
As the curable resin, a cationically polymerizable compound or a radically polymerizable compound can be used. Among them, a cationically polymerizable compound is preferably contained.
Examples of the cationically polymerizable compound include an oxetane compound, an epoxy compound, and a vinyl ether compound. Among them, the curable resin preferably contains at least 1 selected from an oxetane compound and an epoxy compound.
Examples of the oxetane compound include 3-ethyl-3- (((3-ethyloxetan-3-yl) methoxy) methyl) oxetane, 3-ethyl-3- ((2-ethylhexyloxy) methyl) oxetane, 3-ethyl-3- ((3- (triethoxysilyl) propoxy) methyl) oxetane, phenol novolac oxetane, and 1, 4-bis (((3-ethyl-3-oxetanyl) methoxy) methyl) benzene. Among them, 3-ethyl-3- (((3-ethyloxetan-3-yl) methoxy) methyl) oxetane is preferable.
These oxetane compounds may be used alone, or 2 or more kinds thereof may be used in combination.
Examples of the epoxy compound include 1, 7-octadiene diepoxide, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, phenyl glycidyl ether, and phenylene diglycidyl ether. Among them, 1, 6-hexanediol diglycidyl ether is preferable.
These epoxy compounds may be used alone, or 2 or more kinds may be used in combination.
Examples of the vinyl ether compound include benzyl vinyl ether, cyclohexanedimethanol monovinyl ether, dicyclopentadiene vinyl ether, 1, 4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, and the like.
These vinyl ether compounds may be used alone, or 2 or more kinds may be used in combination.
The radical polymerizable compound is preferably a (meth) acrylic compound.
In the present specification, the "(meth) acrylic" means an acrylic or methacrylic, the "(meth) acrylic compound" means a compound having a (meth) acryloyl group, and the "(meth) acryloyl group" means an acryloyl group or a methacryloyl group.
Examples of the (meth) acrylic compound include isobornyl (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1, 12-dodecanediol di (meth) acrylate, lauryl (meth) acrylate, and the like. Among them, isobornyl (meth) acrylate and 1, 6-hexanediol di (meth) acrylate are preferable.
These (meth) acrylic compounds may be used alone or in combination of 2 or more.
In the present specification, the "(meth) acrylate" refers to an acrylate or a methacrylate.
The curable resin composition of the present invention contains a photopolymerization initiator.
As the photopolymerization initiator, a photo cation polymerization initiator or a photo radical polymerization initiator is suitably used depending on the kind of the curable resin used, and the like.
The photo cation polymerization initiator is not particularly limited as long as it generates a protonic acid or a lewis acid by light irradiation, and may be an ionic photo acid generation type or a nonionic photo acid generation type.
Examples of the anionic moiety of the above ionic photoacid generator type photocationic polymerization initiator include BF4 -、PF6 -、SbF6 -、(BX4)-(wherein X represents a phenyl group substituted with at least 2 or more fluorine or trifluoromethyl groups), and the like. Further, as the above-mentioned anion moiety, there may be mentioned PFm(CnF2n+1)6-m -(wherein m is an integer of 0 to 5 inclusive, and n is an integer of 1 to 6 inclusive), and the like.
Examples of the ionic photoacid generator type photo-cationic polymerization initiator include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts, and (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salts having the above-mentioned anionic portion.
Examples of the aromatic sulfonium salt include bis (4- (diphenylsulfonium) phenyl) sulfide bishexafluoroantimonate, bis (4- (diphenylsulfonium) phenyl) sulfide bistetrafluoroborate, bis (4- (diphenylsulfonium) phenyl) sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetrafluoroborate, and triphenylsulfonium tetrakis (pentafluorophenyl) borate, Bis (4- (2-hydroxyethoxy)) phenylsulfone) phenyl) sulfide bishexafluorophosphate, bis (4- (2-hydroxyethoxy)) phenylsulfone) phenyl) sulfide bishexafluoroantimonate, bis (4- (2-hydroxyethoxy)) phenylsulfone) phenyl) sulfide bistetrafluoroborate, bis (4- (2-hydroxyethoxy)) phenylsulfone) phenyl) sulfide tetrakis (pentafluorophenyl) borate, tris (4- (4-acetylphenyl) thiophenyl) sulfonium tetrakis (pentafluorophenyl) borate, and the like. Among them, triarylsulfonium tetrakis (pentafluorophenyl) borate such as triphenylsulfonium tetrakis (pentafluorophenyl) borate is preferable.
Examples of the aromatic iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate, etc.
Examples of the aromatic diazonium salt include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate.
Examples of the aromatic ammonium salt include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.
Examples of the (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe salt include (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (ii) hexafluorophosphate, (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (ii) hexafluoroantimonate, (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (ii) tetrafluoroborate, and (2, 4-cyclopentadien-1-yl) ((1-methylethyl) benzene) -Fe (ii) tetrakis (pentafluorophenyl) borate.
Examples of the nonionic photoacid-generating type photocationic polymerization initiator include nitrobenzyl esters, sulfonic acid derivatives, phosphate esters, phenolsulfonic acid esters, diazonaphthoquinones, and N-hydroxyimide sulfonic acid esters.
Examples of commercially available products of the photo cation polymerization initiator include a photo cation polymerization initiator manufactured by Midori chemical company, a photo cation polymerization initiator manufactured by Union Carbide company, a photo cation polymerization initiator manufactured by ADEKA company, a photo cation polymerization initiator manufactured by 3M company, a photo cation polymerization initiator manufactured by BASF company, a photo cation polymerization initiator manufactured by Rhodia company, and a photo cation polymerization initiator manufactured by San-Apro company.
Examples of the photo-cationic polymerization initiator manufactured by Midori chemical company include DTS-200.
Examples of the photo-cationic polymerization initiator manufactured by Union Carbide include UVI6990 and UVI 6974.
Examples of the photo cation polymerization initiator manufactured by ADEKA include SP-150 and SP-170.
Examples of the photo cation polymerization initiator manufactured by 3M include FC-508 and FC-512.
Examples of the photo-cationic polymerization initiator manufactured by BASF include IRGACURE261 and IRGACURE 290.
Examples of the photo cation polymerization initiator manufactured by Rhodia include PI 2074.
Examples of the photo-cationic polymerization initiator manufactured by San-Apro include CPI-100P, CPI-200K, CPI-210S and the like.
Examples of the photo radical polymerization initiator include benzophenone compounds, acetophenone compounds, acylphosphine oxide compounds, titanocene compounds, oxime ester compounds, benzoin ether compounds, thioxanthone compounds, and the like.
Specific examples of the photo radical polymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 1, 2- (dimethylamino) -2- ((4-methylphenyl) methyl) -1- (4- (4-morpholinophenyl) -1-butanone, 2-dimethoxy-1, 2-diphenylethan-1-one, bis (2, 4, 6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2-methyl-propan-1-one 1-propan-1-one, 1- (4- (phenylthio) phenyl) -1, 2-octanedione 2- (O-benzoyloxime), 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like.
The preferable lower limit of the content of the photopolymerization initiator is 0.01 part by weight and the preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the curable resin. By setting the content of the photopolymerization initiator to 0.01 parts by weight or more, the obtained curable resin composition is more excellent in photocurability. By setting the content of the photopolymerization initiator to 10 parts by weight or less, the curing reaction of the obtained curable resin composition does not become excessively fast, the workability becomes more excellent, and the cured product can be made more uniform. The lower limit of the content of the polymerization initiator is more preferably 0.05 part by weight, and the upper limit is more preferably 5 parts by weight.
The curable resin composition of the present invention may contain a thermal polymerization initiator in an amount not to impair the object of the present invention.
As the thermal polymerization initiator, a thermal cationic polymerization initiator or a thermal radical polymerization initiator is suitably used depending on the kind of the curable resin to be used, and the like.
Examples of the thermal cationic polymerization initiator include: the anion being partly substituted by BF4 -、PF6 -、SbF6 -Or (BX)4)-(wherein X represents a phenyl group substituted with at least 2 or more fluorine groups or trifluoromethyl groups), sulfonium salts, phosphonium salts, ammonium salts, and the like. Among them, sulfonium salts and ammonium salts are preferable.
Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate and triphenylsulfonium hexafluoroantimonate.
Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.
Examples of the above ammonium salts include dimethylphenyl (4-methoxybenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methoxybenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methoxybenzyl) ammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorophosphate, dimethylphenyl (4-methylbenzyl) ammonium hexafluoroantimonate, dimethylphenyl (4-methylbenzyl) ammonium hexafluorotetrakis (pentafluorophenyl) borate, methylphenyldibenzylammonium hexafluorophosphate, methylphenyldibenzylammonium hexafluoroantimonate, methylphenyldibenzylammonium tetrakis (pentafluorophenyl) borate, phenyltribenzylammonium tetrakis (pentafluorophenyl) borate, dimethylphenyl (3, 4-dimethylbenzyl) ammonium tetrakis (pentafluorophenyl) borate, N-dimethyl-N-benzylanilinium hexafluoroantimonate, N-dimethyl-N-benzylammonium hexafluoroantimonate, N-methylbenzyl-ammonium hexafluoroantimonate, N-methyl-phenyl, N, N-diethyl-N-benzylanilinium tetrafluoroborate, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N-diethyl-N-benzylpyridinium trifluoromethanesulfonate and the like.
Examples of commercially available products of the above thermal cationic polymerization initiator include thermal cationic polymerization initiators manufactured by shin chemical Industries, and thermal cationic polymerization initiators manufactured by King Industries.
Examples of the thermal cationic polymerization initiator manufactured by Sanxin chemical industries include San-Aid SI-60, San-Aid SI-80, San-Aid SI-B3, San-Aid SI-B3A, and San-Aid SI-B4.
Examples of the thermal cationic polymerization initiator manufactured by King Industries include CXC-1612 and CXC-1821.
Examples of the thermal radical polymerization initiator include thermal radical polymerization initiators containing azo compounds, organic peroxides, and the like.
Examples of the azo compound include 2, 2' -azobis (2, 4-dimethylvaleronitrile), azobisisobutyronitrile, and the like.
Examples of the organic peroxide include benzoyl peroxide, ketone peroxide, peroxyketal, hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxydicarbonate, and the like.
Examples of commercially available products of the thermal radical polymerization initiator include VPE-0201, VPE-0401, VPE-0601, VPS-0501, VPS-1001, and V-501 (all manufactured by Fuji film & Wako pure chemical industries, Ltd.).
The lower limit of the content of the thermal polymerization initiator is preferably 0.01 part by weight and the upper limit is preferably 10 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the thermal polymerization initiator is in this range, the obtained curable resin composition is more excellent in storage stability and thermosetting property. A more preferable lower limit and a more preferable upper limit of the content of the thermal polymerization initiator are 0.05 parts by weight and 5 parts by weight, respectively.
The curable resin composition of the present invention contains a sensitizer.
The above sensitizer contains an anthracene compound having no ester bond.
The curable resin composition of the present invention has excellent curability against light of a long wavelength by containing the anthracene compound having no ester bond as the sensitizer.
In the case where an anthracene compound having an ester bond is used as the sensitizer, there is a problem that acids generated by decomposition easily cause dark spots in the obtained organic EL display device, and therefore, the curable resin composition of the present invention preferably does not contain the anthracene compound having an ester bond.
Examples of the anthracene compound having no ester bond include 9, 10-anthracene derivatives and the like.
Examples of the 9, 10-anthracene derivative include 9, 10-dialkoxyanthracene. Among them, 9, 10-dibutoxyanthracene is preferable. In addition, a substituted anthracene derivative such as 9- (n-propoxy) anthracene can also be used.
The lower limit of the content of the anthracene compound having no ester bond is preferably 0.1 part by weight, and the upper limit is preferably 5 parts by weight, based on 100 parts by weight of the curable resin. The sensitizing effect is further exhibited by setting the content of the anthracene compound having no ester bond to 0.1 part by weight or more. By setting the content of the anthracene compound having no ester bond to 5 parts by weight or less, the obtained liquid crystal display element is more excellent in display performance. A more preferable lower limit of the content of the anthracene compound having no ester bond is 0.3 parts by weight, and a more preferable upper limit is 3 parts by weight.
The curable resin composition of the present invention may contain a thermosetting agent in an amount not to impair the object of the present invention.
Examples of the heat-curing agent include hydrazide compounds, imidazole derivatives, acid anhydrides, dicyandiamide, guanidine derivatives, modified aliphatic polyamines, and addition products of various amines and epoxy resins.
Examples of the hydrazide compound include 1, 3-bis (hydrazinocarbonylethyl (Japanese: ヒドラジノカルボノエチル)) -5-isopropylhydantoin, sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide, malonic dihydrazide, and the like.
Examples of the imidazole derivative include 1-cyanoethyl-2-phenylimidazole, N- (2- (2-methyl-1-imidazolyl) ethyl) urea, 2, 4-diamino-6- (2 '-methylimidazolyl- (1')) -ethyl s-triazine, N '-bis (2-methyl-1-imidazolylethyl) urea, N' - (2-methyl-1-imidazolylethyl) -adipamide, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2-phenyl-4, 5-dihydroxymethylimidazole.
Examples of the acid anhydride include tetrahydrophthalic anhydride and ethylene glycol bis (anhydrotrimellitate).
These heat-curing agents may be used alone, or 2 or more of them may be used in combination.
Examples of commercially available products of the above heat-curing agents include a heat-curing agent manufactured by Otsuka chemical Co., Ltd and a heat-curing agent manufactured by Ajinomoto Fine-Technio Co., Ltd.
Examples of the heat-curing agent manufactured by Otsuka chemical company include SDH and ADH.
Examples of the heat-curing agent manufactured by Ajinomoto Fine-Technio include AMICURE VDH, AMICURE VDH-J, and AMICURE UDH.
The lower limit of the content of the heat-curing agent is preferably 0.5 parts by weight and the upper limit is preferably 30 parts by weight with respect to 100 parts by weight of the curable resin. When the content of the thermosetting agent is in this range, the obtained curable resin composition has excellent thermosetting properties while maintaining excellent storage stability. The lower limit of the content of the thermosetting agent is more preferably 1 part by weight, and the upper limit is more preferably 15 parts by weight.
The curable resin composition of the present invention preferably contains a stabilizer. By containing the stabilizer, the curable resin composition of the present invention is more excellent in storage stability.
As the stabilizer, an aromatic amine compound is preferably used.
Examples of the aromatic amine compound include benzylamine and aminophenol type epoxy resins.
Examples of the aminophenol type epoxy resin include triglycidyl-p-aminophenol.
Among them, benzylamine is preferable.
These stabilizers may be used alone or in combination of 2 or more.
The lower limit of the content of the stabilizer is preferably 0.001 parts by weight, and the upper limit is preferably 2 parts by weight, based on 100 parts by weight of the curable resin. When the content of the stabilizer is in this range, the obtained curable resin composition has more excellent storage stability while maintaining excellent curability. A more preferable lower limit of the content of the stabilizer is 0.005 parts by weight, and a more preferable upper limit is 1 part by weight.
The curable resin composition of the present invention may contain a silane coupling agent. The silane coupling agent has an effect of improving the adhesion of the curable resin composition of the present invention to a substrate or the like.
Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-isocyanatopropyltrimethoxysilane. These silane coupling agents may be used alone, or 2 or more of them may be used in combination.
The preferable lower limit of the content of the silane coupling agent is 0.1 part by weight, and the preferable upper limit is 10 parts by weight, based on 100 parts by weight of the curable resin. When the content of the silane coupling agent is in this range, bleeding of the excess silane coupling agent is suppressed, and the effect of improving the adhesion is further enhanced. A more preferable lower limit of the content of the silane coupling agent is 0.5 parts by weight, and a more preferable upper limit is 5 parts by weight.
The curable resin composition of the present invention may further contain a surface modifier within a range not to impair the object of the present invention. The surface modifier can improve the flatness of the coating film of the curable resin composition of the present invention.
Examples of the surface modifier include a surfactant and a leveling agent.
Examples of the surface modifier include silicone-based surface modifiers and fluorine-based surface modifiers.
Examples of commercially available surface modifiers include surface modifiers manufactured by BYK-Chemie Japan and surface modifiers manufactured by AGC SEIMI CHEMICAL.
Examples of the surface modifier manufactured by BYK-Chemie Japan include BYK-330, BYK-340 and BYK-345.
Examples of the surface modifier manufactured by AGC SEIMI CHEMICAL include Surflon S-611.
The curable resin composition of the present invention may contain a solvent for the purpose of adjusting viscosity or the like, but since there is a possibility that the organic light-emitting material layer deteriorates or outgas occurs due to the residual solvent, it is preferable that the solvent is not contained or the content of the solvent is 0.05 wt% or less.
The curable resin composition of the present invention may contain, as necessary, various known additives such as reinforcing agents, softening agents, plasticizers, viscosity modifiers, ultraviolet absorbers, and antioxidants.
Examples of the method for producing the curable resin composition of the present invention include a method in which a curable resin, a photopolymerization initiator, a sensitizer, and additives such as a stabilizer and a surface modifier are mixed by using a mixer.
Examples of the mixer include a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roll mixer.
The curable resin composition of the present invention can be suitably applied by an ink jet method.
In the ink jet method, the curable resin composition of the present invention can be used for coating by a non-heating type ink jet method, and can also be used for coating by a heating type ink jet method.
In the present specification, the "non-heating type ink jet method" is a method of performing ink jet coating at a coating head temperature of less than 28 ℃, and the "heating type ink jet method" is a method of performing ink jet coating at a coating head temperature of 28 ℃ or higher.
In the above-described heating type ink jet method, an ink jet coating head equipped with a heating mechanism is used. By mounting the heating mechanism on the ink jet coating head, viscosity and surface tension can be reduced when the curable resin composition is discharged.
Examples of the ink-jet coating head equipped with the heating mechanism include KM1024 series manufactured by Konica Minolta, and SG1024 series manufactured by FUJIFILM Dimatix.
When the curable resin composition of the present invention is used for coating by the above-described heating inkjet method, the heating temperature of the coating head is preferably in the range of 28 to 80 ℃. By setting the heating temperature of the coating head in this range, the viscosity increase of the curable resin composition with time is further suppressed, and the ejection stability is further improved.
The viscosity of the curable resin composition of the present invention at 25 ℃ is preferably 5 mPas at the lower limit and 50 mPas at the upper limit. When the viscosity at 25 ℃ is in this range, the coating can be appropriately performed by an ink jet method.
In the present specification, the "viscosity" refers to a value measured by using an E-type viscometer at 25 ℃ and 100 rpm. The E-type VISCOMETER includes, for example, a viscoester TV-22 (manufactured by eastern industries), and a CP1 type cone plate can be used.
The viscosity of the curable resin composition of the present invention at 25 ℃ when applied by the non-heating inkjet method has a preferred lower limit of 5mPa · s and a preferred upper limit of 20mPa · s. When the viscosity at 25 ℃ is in this range, the coating can be appropriately performed by a non-heating type inkjet method. A more preferable lower limit of the viscosity at 25 ℃ of the curable resin composition of the present invention when applied by the non-heating inkjet method is 8mPa · s, a more preferable upper limit is 16mPa · s, a further more preferable lower limit is 10mPa · s, and a further more preferable upper limit is 13mPa · s.
On the other hand, the viscosity of the curable resin composition of the present invention used for coating by the above-mentioned heating inkjet method at 25 ℃ preferably has a lower limit of 10mPa · s and an upper limit of 50mPa · s. When the viscosity is in this range, the coating can be appropriately performed by a heating inkjet method. A more preferable lower limit of the viscosity at 25 ℃ of the curable resin composition of the present invention used for coating by the above-described heating inkjet method is 20mPa · s, and a more preferable upper limit is 40mPa · s.
The lower limit of the surface tension of the curable resin composition of the present invention at 25 ℃ is preferably 15mN/m, and the upper limit is preferably 35 mN/m. By setting the surface tension at 25 ℃ to this range, the coating can be appropriately performed by an ink jet method. A more preferable lower limit to the surface tension at 25 ℃ is 20mN/m, a more preferable upper limit is 30mN/m, a further preferable lower limit is 22mN/m, and a further preferable upper limit is 28 mN/m.
The surface tension is a value measured by the Wilhelmy method using a dynamic wettability tester. Examples of the dynamic wettability tester include WET-6100 (manufactured by RHESCA).
The lower limit of the total light transmittance of a cured product of the curable resin composition of the present invention for light having a wavelength of 380nm to 800nm is preferably 80%. By setting the total light transmittance to 80% or more, the optical characteristics of the obtained organic EL display device are more excellent. A more preferable lower limit of the total light transmittance is 85%.
The total light transmittance can be measured, for example, by a spectrometer.
Examples of the spectrometer include AUTOMATIC HAZE METER MODEL TC-III DPK (manufactured by Tokyo electrochrome Co., Ltd.).
The cured product used for the measurement of the total light transmittance may be obtained by irradiating the curable resin composition with 2000mJ/cm using an LED lamp, for example2Ultraviolet rays having a wavelength of 395 nm.
The curable resin composition of the present invention preferably has a transmittance at 400nm of 85% or more in an optical path length of 20 μm after the cured product is irradiated with ultraviolet light for 100 hours. When the transmittance after 100 hours of irradiation with the ultraviolet ray is 85% or more, the transparency is high, the loss of light emission is small, and the color reproducibility is further excellent. A more preferable lower limit of the transmittance after the irradiation with the ultraviolet ray for 100 hours is 90%, and a further preferable lower limit is 95%.
As the light source for irradiating the ultraviolet ray, a conventionally known light source such as a xenon lamp or a carbon arc lamp can be used.
The cured product used for the measurement of the transmittance after the irradiation with ultraviolet light for 100 hours may be obtained by, for example, irradiating a curable resin composition with an LED lamp at 2000mJ/cm2Ultraviolet rays having a wavelength of 395 nm.
The curable resin composition of the present invention preferably has a moisture permeability of 100 μm at a thickness of 100 μm measured by exposing a cured product to an atmosphere of 85 ℃ and 85% RH for 24 hours in accordance with JIS Z02082The following. By setting the above moisture permeability to 100g/m2As described above, the effect of preventing the occurrence of dark spots due to the moisture from reaching the organic light-emitting material layer is more excellent, and the reliability of the obtained organic EL display element is more excellent.
The cured product used for the measurement of the moisture permeability may be, for example, a cured product ofIrradiating the curable resin composition with an LED lamp at 2000mJ/cm2Ultraviolet rays having a wavelength of 395 nm.
In the curable resin composition of the present invention, when the cured product is exposed to an environment of 85 ℃ and 85% RH for 24 hours, the water content of the cured product is preferably less than 0.5%. When the water content of the cured product is less than 0.5%, the effect of preventing the organic light-emitting material layer from being deteriorated by the water content in the cured product is more excellent, and the reliability of the obtained organic EL display device is more excellent. A more preferable upper limit of the water content of the cured product is 0.3%.
Examples of the method for measuring the water content include a method of obtaining the water content by the karl fischer method according to JIS K7251, and a method of obtaining the weight gain after water absorption according to JIS K7209-2.
The cured product used for the measurement of the water content can be obtained by irradiating the curable resin composition with 2000mJ/cm using an LED lamp, for example2Ultraviolet rays having a wavelength of 395 nm.
A cured product of the curable resin composition of the present invention, that is, a cured product of a sealing agent for an organic EL display element, wherein the sealing agent for an organic EL display element contains a curable resin, a photopolymerization initiator, and a sensitizer, the sensitizer contains an anthracene compound having no ester bond, and the amount of anthraquinone, which is quantified in terms of toluene, is 3000ppm or less when the cured product is measured by thermal desorption GC-MS under thermal desorption conditions of 110 ℃ and 30 minutes, is also one aspect of the present invention.
The cured product of the present invention can be obtained by irradiating the curable resin composition of the present invention with light.
Specifically, the curable resin composition of the present invention can be produced by irradiating 300mJ/cm2Above 3000mJ/cm2The following light of the accumulated light amount is appropriately cured. The curable resin composition of the present invention can be cured by irradiation with light having a long wavelength such as 395 nm.
Examples of the light source used for the light irradiation include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, an excimer laser, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, a metal halide lamp, a sodium lamp, a halogen lamp, a xenon lamp, an LED lamp, a fluorescent lamp, sunlight, and an electron beam irradiation device. These light sources may be used alone, or 2 or more kinds may be used in combination.
These light sources may be appropriately selected according to the kinds of the photopolymerization initiator and the sensitizer.
Examples of the means for irradiating light to the curable resin composition of the present invention include simultaneous irradiation with various light sources, sequential irradiation with a time difference, and combined irradiation of simultaneous irradiation and sequential irradiation.
Examples of the method for producing an organic EL display element using the curable resin composition of the present invention include: a method comprising a step of applying the curable resin composition of the present invention to a substrate, and a step of curing the applied curable resin composition.
In the step of applying the curable resin composition of the present invention to a substrate, the curable resin composition of the present invention may be applied to the entire surface of the substrate or may be applied to a part of the substrate. The shape of the sealing portion of the curable resin composition of the present invention formed by coating is not particularly limited as long as it is a shape capable of protecting the laminate having the organic light-emitting material layer from the external gas, and may be a shape completely covering the laminate, a closed pattern may be formed in the peripheral portion of the laminate, or a pattern having a shape in which an opening is partially formed in the peripheral portion of the laminate.
The cured product of the present invention obtained by the step of curing the curable resin composition can be coated with an inorganic material film.
As the inorganic material constituting the inorganic material film, conventionally known inorganic materials can be used, and examples thereof include silicon nitride (SiN)x) Silicon oxide (SiO)x) And the like. The inorganic material film may be formed of 1 layer, or may be formed by laminating a plurality of layers. Further, the inorganic material film may be formed by combining the inorganic material film with the bodyThe cured product of the invention is alternately and repeatedly laminated to cover the laminate.
The method of manufacturing the organic EL display element may have: a step of bonding a substrate (hereinafter, also referred to as "one substrate") coated with the curable resin composition of the present invention to another substrate.
The substrate (hereinafter, also referred to as "one substrate") to which the curable resin composition of the present invention is applied may be a substrate on which a laminate having an organic light-emitting material layer is formed, or may be a substrate on which the laminate is not formed.
In the case where the one substrate is a substrate on which the laminate is not formed, the curable resin composition of the present invention may be applied to the one substrate so that the laminate can be protected from external air when the other substrate is bonded. That is, the entire surface of the portion to be the position of the laminate when the other substrate is bonded may be coated, or the sealant portion having the closed pattern may be formed in a shape in which the portion to be the position of the laminate when the other substrate is bonded is completely received.
The step of curing the curable resin composition may be performed before the step of bonding the one substrate to the other substrate, or may be performed after the step of bonding the one substrate to the other substrate.
In the case of the step of curing the curable resin composition before the step of bonding the one substrate to the other substrate, the curable resin composition of the present invention preferably has a pot life of 1 minute or more from the time of light irradiation until the curing reaction proceeds and bonding is impossible. By setting the usable time to 1 minute or more, curing does not excessively proceed before the one base material and the other base material are bonded to each other, and a higher adhesive strength can be obtained.
In the step of bonding the one substrate to the other substrate, it is preferable that the one substrate and the other substrate are bonded to each other in a reduced-pressure atmosphere.
The lower limit of the degree of vacuum in the reduced pressure atmosphere is preferably 0.01kPa, and the upper limit is preferably 10 kPa. By setting the degree of vacuum in the reduced-pressure atmosphere to this range, bubbles in the curable resin composition of the present invention at the time of bonding the one substrate to the other substrate can be removed more efficiently without taking a long time to achieve a vacuum state from the viewpoint of airtightness of a vacuum apparatus and the capability of a vacuum pump.
The curable resin composition of the present invention can be used as a sealant for an organic EL display element.
An organic EL display device having the cured product of the present invention is also one aspect of the present invention. The curable resin composition of the present invention is particularly suitable for sealing a top emission type organic EL display element.
The curable resin composition of the present invention is also suitable as an adhesive for lithium ion batteries.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a curable resin composition which is excellent in curability against light of a long wavelength and low outgassing property and can suppress display defects of an organic EL display element can be provided. Further, the present invention can provide a cured product of the curable resin composition and an organic EL display element having the cured product.
Detailed Description
The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
Examples 1 to 4 and comparative examples 1 to 3
The curable resin compositions of examples 1 to 4 and comparative examples 1 to 3 were prepared by uniformly stirring and mixing the respective materials at a stirring speed of 300rpm using a homogeneously dispersed stirring mixer in accordance with the mixing ratios shown in table 1. As the homo-dispersion type stirring mixer, homo-disperser L type (manufactured by PRIMIX Co., Ltd.) was used.
The obtained curable resin composition was irradiated with an LED lamp at 2000mJ/cm in a dry chamber having a dew point of-50 ℃ or lower2Ultraviolet rays having a wavelength of 395nm, thereby obtaining a cured product. 1mg of each cured product obtained was subjected to pyrolysisAn adsorption apparatus and a GC-MS apparatus were used to measure the amount of anthraquinone and the total amount of outgas in terms of toluene when heated under thermal desorption conditions of 110 ℃ for 30 minutes. Specific measurement conditions are shown below.
A thermal desorption device: turbo Matrix650(Perkin Elmer Co., Ltd.)
Thermal desorption conditions: 110 ℃ for 30 minutes
Shunting: 15 mL/min at the inlet, 15 mL/min at the outlet and 5.2% of the injection amount
GC-MS apparatus: JMS Q1000 (Japanese electronic official system)
Separating the column: EQUITY-1 (nonpolarity)
0.32mm×60m×0.25μm
GC temperature rise rate: 4 minutes at 40 deg.C → 10 deg.C/min → 10 minutes at 300 deg.C
Carrier gas (flow rate): he (1.5 mL/min)
MS measurement range: 29 to 600amu (scanning 500ms)
Ionization voltage: 70eV
MS temperature: the ion source is 230 ℃, and the interface is 250 DEG C
The results are shown in Table 1.
< evaluation >
The following evaluations were made for each of the curable resin compositions obtained in examples and comparative examples. The results are shown in Table 1.
(1) Viscosity of the oil
The viscosity of each of the curable resin compositions obtained in examples and comparative examples was measured at 25 ℃ and 100rpm using a CP1 type conical plate with an E-type VISCOMETER ("VISCOMETER TV-22" manufactured by Toyobo industries Co., Ltd.).
(2) Surface tension
The surface tension of each of the curable resin compositions obtained in examples and comparative examples was measured at 25 ℃ by a dynamic wettability tester ("WET-6100" manufactured by RHESCA).
(3) Display performance of organic EL display element
The organic EL display devices were obtained by the methods shown in (3-1) to (3-4) below. The obtained organic EL display devices were evaluated for display performance by the following methods (3-5) to (3-7).
(3-1) production of substrate having laminate comprising organic light-emitting Material layer
On glass with the length of 25mm, the width of 25mm and the thickness of 0.7mm to form
Figure BDA0003024519710000201
The ITO electrode was formed into a film to form a substrate. The substrate was ultrasonically cleaned with acetone, an aqueous alkali solution, ion-exchange water, and isopropyl alcohol for 15 minutes, then cleaned with boiling isopropyl alcohol for 10 minutes, and further pretreated with a UV-ozone cleaner. As the UV-ozone cleaner, NL-UV253 (manufactured by Nippon Laser electronics Co., Ltd.) was used.
Next, the pretreated substrate was fixed to a substrate holder of a vacuum deposition apparatus, 200mg of N, N '-di (1-naphthyl) -N, N' -diphenylbenzidine (. alpha. -NPD) was charged into a bisque-fired crucible, and 200mg of tris (8-hydroxyquinoline) aluminum (Alq) was charged into another bisque-fired crucible3) The pressure in the vacuum chamber is reduced to 1 × 10-4Pa. Then, the crucible containing the alpha-NPD is heated to evaporate the alpha-NPD at a vapor deposition rate
Figure BDA0003024519710000211
Deposited on a substrate to form a film having a thickness
Figure BDA0003024519710000212
The hole transport layer of (1). Next, adding Alq3Is heated to
Figure BDA0003024519710000213
The deposition rate of (2) is set to a film thickness
Figure BDA0003024519710000214
The organic light emitting material layer of (1). Then, the substrate on which the hole transport layer and the organic light emitting material layer were formed was transferred to another vacuum deposition apparatus having a tungsten resistance heating boat, and one tungsten resistance was placed in the vacuum deposition apparatus200mg of lithium fluoride was added to the heated boat, and 1.0g of an aluminum wire was placed in another tungsten resistance-heated boat. Then, the pressure in the evaporator of the vacuum evaporation apparatus was reduced to 2 × 10-4Pa, adding lithium fluoride to
Figure BDA0003024519710000215
The deposition rate of (2) is
Figure BDA0003024519710000216
Then, aluminum is added
Figure BDA0003024519710000217
At a rate of film formation of
Figure BDA0003024519710000218
The inside of the evaporator was returned to normal pressure by nitrogen, and the substrate provided with the laminate having the organic light-emitting material layers of 10mm × 10mm was taken out.
(3-2) coating with an inorganic Material film
A mask having an opening of 13mm × 13mm was provided on the obtained substrate on which the laminate was disposed, and an inorganic material film was formed by a plasma CVD method so as to cover the entire laminate.
The plasma CVD method was performed under the following conditions: using SiH4Gas and nitrogen gas were used as raw material gases, and the respective flow rates were SiH4The gas was changed to 10sccm and the nitrogen gas was changed to 200sccm, the RF power was changed to 10W (frequency: 2.45GHz), the temperature in the chamber was changed to 100 ℃, and the pressure in the chamber was changed to 0.9 Torr.
The thickness of the inorganic material film formed was about 1 μm.
(3-3) formation of cured product
The curable resin compositions obtained in examples and comparative examples were applied to the entire surface of a concave portion of a glass lid separately prepared and having a concave portion of 15mm × 15mm so as to have a thickness of 10 μm using an inkjet ejection apparatus. As the inkjet ejection device, NanoPrinter300 (manufactured by Microjet) was used, and as the inkjet application head, IJH-30 (manufactured by IJT) was used, and inkjet application was performed without heating (application head temperature 25 ℃).
Then, 2000mJ/cm was irradiated with an LED lamp2And 395nm, curing the curable resin composition to form a cured product.
(3-4) glass Cap seal
The peripheral edge of the glass cover obtained in the step of "(3-3) formation of the cured product" was coated with a low moisture-permeable epoxy adhesive, and the glass cover was sealed so as to cover the substrate obtained in the step of "(3-2) coating with an inorganic material film", thereby obtaining an organic EL display device for evaluation.
(3-5) Lighting State
With respect to the obtained organic EL display element, the display performance (lighting state) of the organic EL display element was evaluated by marking the case where lighting was confirmed when a voltage of 3V was applied as "o" and the case where the entire surface was not lit as "x".
(3-6) measurement of initial dark Point diameter
The organic EL display device obtained was observed by an optical microscope for the light emission state when a voltage of 3V was applied, and the initial dark spot diameter was measured. When there are a plurality of dark spots, the dark spots having a diameter of about 20 μm are observed preferentially.
(3-7) dark spot diameter enlargement Rate
The obtained organic EL display device was heated at 110 ℃ under an atmosphere having a humidity of less than 1% for 30 minutes, and then a voltage of 3V was applied, and the light emission state of the organic EL display device was observed with an optical microscope, and the diameter of the dark spot after 110 ℃ and 30 minutes was measured in the same manner as the above "(3-6) measurement of the initial diameter of the dark spot".
The display performance (dark spot diameter enlargement ratio) of the organic EL display element was evaluated by designating the dark spot diameter enlargement ratio as "very good" when it was 2.5 times or less, designating the case of more than 2.5 times and 3.0 times or less as "good", designating the case of more than 3.0 times and 3.5 times or less as "Δ", and designating the case of more than 3.5 times as "x". In the above "(3-5) evaluation of lighting state", the case where the lighting state is not lit over the entire surface (x) is represented as "-".
The dark spot diameter enlargement ratio was calculated by the following equation.
Dark spot diameter enlargement rate (110 ℃, dark spot diameter after 30 minutes)/(initial dark spot diameter)
[ Table 1]
Figure BDA0003024519710000241
Industrial applicability
The present invention can provide a curable resin composition which has excellent curability with respect to light of a long wavelength and low outgassing property, and can suppress display defects of an organic EL display device. Further, the present invention can provide a cured product of the curable resin composition and an organic EL display element having the cured product.

Claims (6)

1. A curable resin composition which is used as a sealing agent for an organic EL display element,
the curable resin composition contains a curable resin, a photopolymerization initiator and a sensitizer,
the sensitizer contains an anthracene compound having no ester bond,
when a cured product of the curable resin composition is measured by thermal desorption GC-MS under thermal desorption conditions of 110 ℃ for 30 minutes, the amount of anthraquinone, which is quantified in terms of toluene, is 3000ppm or less.
2. The curable resin composition according to claim 1, wherein the total amount of outgas determined in terms of toluene is 6000ppm or less when the cured product is measured by thermal desorption GC-MS under thermal desorption conditions of 110 ℃ for 30 minutes.
3. The curable resin composition according to claim 1 or 2, having a viscosity of 5 mPas or more and 50 mPas or less at 25 ℃.
4. The curable resin composition according to claim 1, 2 or 3, having a surface tension at 25 ℃ of 15mN/m or more and 35mN/m or less.
5. A cured product of a sealing agent for an organic EL display element,
the sealant for organic EL display elements contains a curable resin, a photopolymerization initiator and a sensitizer,
the sensitizer contains an anthracene compound having no ester bond,
when the cured product was measured by thermal desorption GC-MS under thermal desorption conditions of 110 ℃ for 30 minutes, the amount of anthraquinone was 3000ppm or less as calculated in terms of toluene.
6. An organic EL display device, which has the claim 5 of the cured product.
CN201980068585.1A 2018-12-18 2019-12-12 Curable resin composition, cured product, and organic EL display element Pending CN112912407A (en)

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