WO2014083844A1

WO2014083844A1 - Resin composition, and cured product (2) thereof

Info

Publication number: WO2014083844A1
Application number: PCT/JP2013/006963
Authority: WO
Inventors: 伸彦内藤; 潤木戸場; 雄一朗松尾
Original assignee: 日本化薬株式会社
Priority date: 2012-11-28
Filing date: 2013-11-27
Publication date: 2014-06-05
Also published as: KR102031575B1; CN107556457A; TW201428026A; JP5967654B2; KR20150090059A; JP2014105286A; TWI591093B; CN104822729A

Abstract

The present invention relates to a resin composition for sealing a surface of an organic electroluminescent (EL) element, said resin composition including: an alicyclic compound (A) having an oxetanyl group or an epoxy group; and a cyclic compound (B) which has an oxetanyl group or an epoxy group, and which satisfies the following condition (condition for cyclic compound (B): that the ring in cyclic compound (B) be either an aliphatic ring or a heterocycle, and in cases when the ring is an aliphatic ring, that the cyclic compound have a structure different to that of the compound used as alicyclic compound (A)). This resin composition for sealing a surface of an organic EL element exhibits an excellent liquid refractive index, and is cured by heat or energy rays such as light to obtain a cured product exhibiting excellent visible light transmission, excellent light resistance, a high Tg, low cure shrinkage, and a low water vapour transmission rate, and thus is particularly suitable as a surface sealant for an organic EL element.

Description

Resin composition and cured product thereof (2)

Nowadays, low moisture permeability materials are important materials in various industries. Particularly in the vicinity of electric and electronic displays, it is an indispensable material for maintaining quality, and a higher performance low moisture permeability material is desired.
In recent years, thin displays called flat panel displays (FPD), in particular, plasma displays (PDP) and liquid crystal displays (LCD) have been put on the market and are widely used. In addition, organic EL displays (OLEDs) are expected as next-generation self-luminous thin film displays, and some commercial products have already been put into practical use. An organic EL element of an organic EL display has a structure in which an element body composed of a thin film laminate including a light emitting layer sandwiched between a cathode and an anode is formed on a glass substrate on which a driving circuit such as a TFT is formed. Have. A layer such as a light emitting layer or an electrode of the element portion is easily deteriorated by moisture or oxygen, and the deterioration of brightness, life, and discoloration occurs due to the deterioration. Therefore, the organic EL element is sealed so as to block moisture or impurities from entering from the outside. In order to realize a high-quality and high-reliability organic EL element, a higher-performance sealing material is desired, and various sealing techniques have been studied.

As a typical sealing method of an organic EL element, a method of fixing a metal or glass sealing cap in which a desiccant is inserted in advance to a substrate of an organic EL element using a sealing adhesive has been studied. (Patent Document 1). In this method, an adhesive is applied to the outer peripheral portion of the substrate of the organic EL element, a sealing cap is placed thereon, and then the adhesive is solidified to fix the substrate and the sealing cap. It is sealed. In such a method, sealing with a glass sealing cap is the mainstream. However, a glass sealing cap is produced by processing a digging for inserting a desiccant into a flat glass substrate, and thus tends to be expensive. Moreover, since the desiccant is inserted inside the sealing cap, the sealing with the sealing cap cannot extract light from the sealing cap side. In other words, the light emitted from the light source is extracted from the substrate side of the element, and is limited to the bottom emission type element. In the case of a bottom emission type element, there are problems of a decrease in aperture ratio due to the drive circuit portion formed on the substrate and a decrease in extraction efficiency due to light being partially blocked by the drive circuit portion. Therefore, development of a sealing method applicable to a top emission type element that extracts light from the opposite side of the substrate of the organic EL element is desired.

As a typical sealing method applicable to a top emission type element, there are a thin film sealing method and a solid sealing method. The thin film sealing method is a method in which a thin film made of an inorganic or organic material is laminated on an organic EL element to form a passivation film (Patent Document 2). In order to impart sufficient moisture resistance to the device by this method, it is necessary to sequentially stack a number of thin films on the device. Therefore, in the thin film sealing method, the film forming process is long and expensive, and the initial investment tends to be high due to the introduction of a large vacuum system required for film formation.

On the other hand, the solid sealing method is a method in which a passivation film is provided so as to cover the entire element portion of the organic EL element, and a sealing transparent substrate is provided thereon via a sealing material. In general, a passivation film is formed by vapor deposition or sputtering of an inorganic material, and it is often an incomplete film having pinholes or a film having low mechanical strength. Therefore, in the solid sealing method, after providing a passivation film on the element, a sealing transparent substrate such as a glass substrate is provided through a sealing adhesive to improve sealing reliability. In addition, a technique for enhancing the reliability of sealing by filling the air gap with heat or photo-curing resin has been studied. Such a solid sealing method is attracting attention as a method capable of sealing a top emission type element simply and at low cost.

In sealing an organic EL element by a solid sealing method, it is possible to use a heat or photo-curing resin as a sealing adhesive or a surface sealing adhesive. This is very important because it can significantly affect the productivity of the sealing operation. For example, if the water vapor transmission rate of the sealing adhesive is not sufficient, it may enter the element portion from the pinhole of the passivation film and cause deterioration of the element. Further, if the curing reaction of the sealing material is slow, the curing process takes time, and the productivity of the sealing work may be reduced.

The sealing adhesive used for these has high transmittance in the visible light region, light resistance that can withstand light emission, stable moldability, low curing shrinkage for suppressing residual stress, and light emitting elements in moisture. For example, a low water vapor transmission rate for protecting from water is required. Although it is possible to perform sealing by a solid sealing method using a known adhesive as an organic EL element sealing adhesive, it is possible to obtain satisfactory results in both reliability and productivity. The current situation is difficult, and development of a sealing adhesive that can be suitably used in the solid sealing method is desired.

Patent No. 4876609 JP2012-059553A Patent No. 4655172 JP 2001-81182 A JP 2011-225773 A Japanese Patent No. 4850231

An object of the present invention is to provide a sealing material for an organic EL device, particularly a resin composition suitable for surface sealing, and excellent in visible light transmittance, light resistance and curability, high Tg, curing shrinkage rate, water vapor transmission rate. It provides a cured product having a low viscosity.

As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition having a specific composition and a cured product thereof can solve the above problems, and have completed the present invention.

That is, the present invention relates to the inventions described in the following (1) to (19).
(1) Resin composition for surface sealing of an organic EL device containing an alicyclic compound (A) having an oxetanyl group or an epoxy group, a cyclic compound (B) having an oxetanyl group or an epoxy group and satisfying the following conditions object,
Conditions for the cyclic compound (B):
The ring in the cyclic compound (B) is an aliphatic ring or a heterocycle, and when the ring is an aliphatic ring, the cyclic compound is a compound used as the alicyclic compound (A). It is a compound having a different structure.
(2) The resin composition according to (1), wherein the alicyclic compound (A) has a skeleton selected from the group described in (A-1) below,

A-1: Tricyclodecane, isobornyl, adamantane, cyclopentane, cyclohexane, hydrogenated bisphenol A, hydrogenated bisphenol F, and hydrogenated bisphenol S.

(3) The above alicyclic compound (A) is an oxetane compound or an epoxy compound having a skeleton selected from the group consisting of tricyclodecane, adamantane, cyclohexane and hydrogenated bisphenol A as an aliphatic ring (1 ) Or (2).

(4) The resin composition according to any one of (1) to (3), wherein the cyclic compound (B) has a skeleton selected from the group described in (B-1) below,

B-1: Tricyclodecane, isobornyl, adamantane, cyclopentane, cyclohexane, hydrogenated bisphenol A, hydrogenated bisphenol F, and hydrogenated bisphenol S.

(5) In the above (4), the cyclic compound (B) is an oxetane compound or an epoxy compound having a skeleton selected from the group consisting of tricyclodecane, adamantane, cyclohexane and hydrogenated bisphenol A as an aliphatic ring. The resin composition as described.

(6) The resin composition according to any one of (1) to (3), wherein the cyclic compound (B) has a skeleton selected from the group described in (B-3) below,

B-3: Morpholine, tetrahydrofuran, oxane, dioxane, triazine, carbazole, pyrrolidine and piperidine.

(7) The resin composition according to (6), wherein the cyclic compound (B) is an oxetane compound or an epoxy compound having a skeleton selected from the group consisting of oxane, dioxane, and triazine as a heterocyclic ring.
(8) The resin composition according to any one of (1) to (7), further including a curing agent (C).
(9) The resin composition according to (8), wherein the curing agent (C) is a photocationic polymerization initiator and the resin composition is an energy ray curable resin composition.
(10) The energy ray curable resin composition according to (9), wherein the photocationic polymerization initiator is a compound selected from the group described in (C-1) below,

C-1: sulfonium salt, iodonium salt, phosphonium salt, ammonium salt and antimonate.

(11) The thermosetting resin composition according to (8), wherein the curing agent (C) is a thermosetting agent and the resin composition is a thermosetting resin composition.
(12) The thermosetting resin composition according to (11), wherein the thermosetting agent is a compound selected from the group described in (C-2) below,

C-2: Amine compound, acid anhydride compound, amide compound, phenol compound, carboxylic acid compound, imidazole compound, isocyanuric acid adduct, metal compound, sulfonium salt, ammonium salt, antimonate, phosphonium Salt and microcapsule type curing agents.

(13) The above (1) to (12) containing 20 to 80 parts by mass of the alicyclic compound (A) with respect to 100 parts by mass of the total amount of the alicyclic compound (A) and the cyclic compound (B). The resin composition as described in any one of).
(14) The above-mentioned (1) to (13) containing 20 to 80 parts by mass of the cyclic compound (B) with respect to 100 parts by mass of the total amount of the alicyclic compound (A) and the cyclic compound (B). The resin composition as described in any one.
(15) Said (1) thru | or (14) which contains 0.1-5 mass parts of hardening | curing agents (C) with respect to 100 mass parts of total amounts of the said alicyclic compound (A) and the said cyclic compound (B). The resin composition according to any one of the above.
(16) The resin composition according to any one of (1) to (15), wherein the viscosity measured at 25 ° C. is 15 Pa · s or less.
(17) An organic EL display whose surface is sealed with a cured product obtained by curing the resin composition according to any one of (1) to (16).
(18) A surface sealing film for an organic EL display having a barrier performance obtained by applying and curing the resin composition according to any one of (1) to (16) on a substrate.
(19) Use of the resin composition according to any one of (1) to (16) for surface sealing of an organic EL element.

The resin composition for surface sealing of the organic EL device of the present invention (hereinafter simply referred to as “surface sealing resin composition” or “resin composition” in the present specification) has a low viscosity, and The cured product is excellent in visible light transmittance and light resistance, has a high Tg, and has a low curing shrinkage rate and low water vapor transmission rate. Therefore, the cured product is particularly suitable for a surface sealing material for an organic EL element.

As an alicyclic compound (A) having an oxetanyl group or an epoxy group contained in the resin composition of the present invention (also referred to as “alicyclic compound (A)” or “component (A)” in this specification). Any compound can be used as long as it has at least one aliphatic ring and at least one oxetanyl group or epoxy group in the molecule. Examples of the alicyclic compound (A) include an oxetane compound having an aliphatic ring exemplified below or an epoxy compound having an aliphatic ring.

Examples of the alicyclic compound (A) contained in the resin composition of the present invention include an alicyclic hydrocarbon skeleton or a cycloalkylene skeleton having a bridge structure (without a bridge structure), an oxetanyl group, and an epoxy. A cyclic compound having a group; or an alicyclic epoxy compound having at least one alicyclic epoxy skeleton in the molecule can be used. Examples of these specific structures will be described in detail below.
The alicyclic hydrocarbon skeleton or cycloalkylene skeleton having the above bridge structure may or may not have a substituent. In the case where the alicyclic hydrocarbon skeleton or the cycloalkylene skeleton has a substituent, examples of the substituent include an alkyl group, an alkoxy group, and an alkenyl group. It is preferably 1 to 4.
By combining such a compound with the above-mentioned cyclic compound (B) having an oxetanyl group or an epoxy group (also referred to as “cyclic compound (B)” or “component (B)” in this specification), the compound is extremely excellent. A cured product having an effect of moisture resistance can be obtained. This is because the skeleton serves as a sufficient barrier against moisture and prevents moisture permeation.

The alicyclic hydrocarbon group having a bridge structure refers to an aliphatic ring in which a polycyclic skeleton is formed by a bridge structure. Specifically, an adamantane skeleton, a tricyclodecane skeleton ( Preferred examples include a dicyclopentadiene skeleton) and an isobornyl skeleton. As described above, these groups may have a substituent selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkenyl group having 1 to 4 carbon atoms. As the alicyclic hydrocarbon group having the bridge structure, a tricyclodecane skeleton is particularly preferable.

Examples of the cycloalkylene skeleton include cycloalkylene skeletons preferably having 4 to 7 carbon atoms, more preferably 5 or 6 carbon atoms, and specific examples include cyclopentane skeleton, cyclohexane skeleton and cycloheptane skeleton. Etc. As the cycloalkylene skeleton, a cyclohexane skeleton is particularly preferable.
In the cycloalkylene skeleton, two cyclohexane skeletons are bonded via a direct bond or a coupler, and the following formula (AA)

(In the above formula, Y represents a direct bond, a sulfur atom or an alkylene group having 1 to 10 carbon atoms, an alkylene group having an ether bond or an alkylene group having an ester bond, and each R ₃ independently represents a hydrogen atom or 1 carbon atom. Or a skeleton represented by t represents an integer of 1 to 4.
In the skeleton represented by the formula (AA), Y is preferably a direct bond or an alkylene group having 1 to 10 carbon atoms, and Y is a direct bond, a methylene group or propane-2,2- Those that are diyl groups are more preferred, and those in which Y is a direct bond are particularly preferred.

The alicyclic hydrocarbon skeleton having the bridge structure, the cycloalkylene skeleton (including the formula (AA) skeleton), and the oxetanyl group or the epoxy group may be directly or by a linking group containing a hydrocarbon group. It is preferable that it is connected.
Examples of the linking group in the case where the skeleton and the oxetanyl group or the epoxy group are linked by a linking group containing the hydrocarbon group include a hydrocarbon group that may include an ether bond or an ester bond, Examples thereof include an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 10 carbon atoms having an ether bond, and an alkylene group having 1 to 10 carbon atoms having an ester bond.
Among the linking groups, specific examples of the hydrocarbon group containing an ether bond include a C1-C4 alkylene-oxy-C1-C4 alkylene group, more preferably a C1-C3 alkylene-oxy-C1-C3 alkylene group, An alkylene group having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms containing an ether bond between carbon atoms; and a C1-C4 alkylene group having an ether bond such as an -oxymethyl group at the terminal of the alkylene group (- An oxy-C1-C4 alkylene group), more preferably an -oxy-C1-C3 alkylene group. When the alkylene group has an ether bond at the terminal, the oxy group is usually bonded to the aliphatic ring and the alkyl group is bonded to the oxetane ring or the epoxy ring.
Among the above linking groups, specific examples of the hydrocarbon group containing an ester bond include a C1-C6 alkylene group having an ester bond at one end (ester bond-C1-C6 alkylene group), more preferably an ester bond-C1. -C3 alkylene group; ester bond-C1-C6 alkylene (more preferably C2-C5 alkylene) -C1-C6 alkylene group having an ester bond at both ends, such as an ester bond; and C1-C4 alkylene-ester bond- A C1-C4 alkylene group, a C1-C3 alkylene-ester bond, a C1-C6 alkylene-ester bond, a C1-C3 alkylene group and the like, containing 2 to 10 carbon atoms (more preferably Examples thereof include alkylene groups having 2 to 8 carbon atoms. When the hydrocarbon group containing an ester bond has an ester bond at the end, usually, in the ester bond, a carbonyl group is bonded to an aliphatic ring and an ether group is bonded to an alkylene group.
More preferable examples of the linking group include a C1-C3 alkylene-oxy-C1-C3 alkylene group, an oxy-C1-C3 alkylene group, and an ester bond-C1-C3 alkylene group.

The alicyclic epoxy compound is a compound having an aliphatic ring in which an alicyclic epoxy group is formed, and can be used as the alicyclic compound (A) in the present invention. An alicyclic epoxy group refers to an epoxy group formed directly on an aliphatic ring by bonding one oxygen atom to two carbon atoms constituting the aliphatic ring. Examples of the aliphatic ring in which the alicyclic epoxy group in the alicyclic epoxy compound is formed include the cycloalkylene skeleton or the alicyclic hydrocarbon skeleton having a bridge structure, and more specifically, cyclopentane. Examples thereof include a cycloalkylene skeleton having 5 to 7 carbon atoms such as a skeleton and a cyclohexane skeleton, an adamantane skeleton, a tricyclodecane skeleton, and an isobornyl skeleton.
The alicyclic epoxy compound may have two or more alicyclic epoxy groups, and is preferably a compound having two or more aliphatic rings formed with one alicyclic epoxy group. In this case, an aliphatic ring in which two or more alicyclic epoxy groups are formed is preferably linked directly or by a linking group containing the hydrocarbon group.
The alicyclic epoxy compound may have an oxetanyl group or an epoxy group in addition to the alicyclic epoxy group, and the aliphatic ring formed with the alicyclic epoxy group and the oxetanyl group or the epoxy group, It may be a compound formed by being linked directly or by a linking group containing the above-mentioned hydrocarbon group.
Suitable examples of the alicyclic epoxy compound include compounds having a skeleton selected from a cyclopentane skeleton, a cyclohexane skeleton, and a tricyclodecane skeleton, and an alicyclic epoxy group formed on the skeleton. A compound having a cyclohexane skeleton in which an alicyclic epoxy group is formed is more preferable, and a compound in which two 1,2-epoxycyclohexane skeletons are linked directly or via an alkylene group having 1 to 3 carbon atoms having an ester bond is Further preferred.

Examples of the aliphatic ring (including those formed with an alicyclic epoxy group) included in the alicyclic compound (A) of the present invention include the groups described in the following (A-1):
A-1: Tricyclodecane skeleton, isobornyl skeleton, adamantane skeleton, cyclopentane skeleton, cyclohexane skeleton, hydrogenated bisphenol A skeleton, hydrogenated bisphenol F skeleton and hydrogenated bisphenol S skeleton.
Preferred is a skeleton selected from the group described in the following (A-2):
A-2: a tricyclodecane skeleton, an adamantane skeleton, a cyclohexane skeleton, and a hydrogenated bisphenol A skeleton.
A skeleton selected from is more preferable.
Among the alicyclic compounds (A), preferred examples of the oxetane compounds having an aliphatic ring include 3 (4), 8 (9) -bis [(1-ethyl-3-oxetanyl) methoxymethyl]- And tricyclo [5.2.2.1.6] decane.

Of the alicyclic compound (A), preferred specific examples of the epoxy compound having an aliphatic ring are shown in the groups described in (a-1a), (a-1b) and (a-1c) described later. Alicyclic epoxy compounds; bisphenol A type epoxy compounds such as hydrogenated bisphenol A diglycidyl ether, brominated hydrogenated bisphenol A diglycidyl ether; hydrogenated bisphenol F diglycidyl ether, brominated hydrogenated bisphenol F diglycidyl ether, etc. Bisphenol F type epoxy compounds; hydrogenated bisphenol S type diglycidyl ethers, hydrogenated bisphenol S type epoxy compounds such as brominated hydrogenated bisphenol S diglycidyl ethers; diepoxy tricyclodecane, tricyclodecane dimethanol diglycidyl ether, etc. Has tricyclodecane skeleton That an epoxy compound, epoxy compound having an adamantane skeleton such as an adamantane glycidyl ether.

Formula (a-1a):

Formula (a-1b):

Formula (a-1c):

(N is an average value and represents a positive number from 1 to 5.)

As the alicyclic compound (A) contained in the resin composition of the present invention, among the compounds, a skeleton selected from the group consisting of an alicyclic epoxy compound, or a hydrogenated bisphenol A skeleton and a tricyclodecane skeleton. Oxetane compounds or epoxy compounds having the following are preferred:
As the alicyclic compound (A) of the present invention, a compound having two or more oxetanyl groups or epoxy groups is more preferable, and a compound having two functions is more preferable.
The content of the component (A) of the present invention is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts per 100 parts by mass of the total amount of the component (A) and the component (B) which are reactive compounds. Part by mass. In order to achieve low moisture permeability of the cured product obtained from the resin composition of the present invention, the functional group equivalent of component (A) is preferably 10 to 500 g / eq, and preferably 50 to 250 g / eq. Is more preferable.

The cyclic compound (B) having an oxetanyl group or an epoxy group (also referred to as “cyclic compound (B)” or “component (B)” in the present specification) contained in the resin composition of the present invention has the following conditions. Meet.
Conditions of the cyclic compound (B): “As the ring contained in the cyclic compound (B), there is an aliphatic ring or a heterocycle. When the ring is an aliphatic ring, the cyclic compound (B) A compound having a structure different from the compound used as the alicyclic compound (A) is used. "
That is, when using the cyclic compound (B) whose ring is an aliphatic ring, the resin composition of the present invention contains an oxetane compound having two different types of aliphatic rings or an epoxy compound having an aliphatic ring. Will be.
Among the cyclic compounds (B), as the compound whose ring is an aliphatic ring, the compounds listed as the alicyclic compound (A) can be used. Preferred examples of the compound in which the ring is an aliphatic ring among the cyclic compounds (B) include compounds that are preferred in the description of the alicyclic compound (A). The same applies to more preferable compounds. In the resin composition of the present invention, when a compound whose ring is an aliphatic ring is used as the cyclic compound (B), it is more preferable to use a compound having a skeleton different from the compound used as the alicyclic compound (A). .

In the cyclic compound (B), when the ring is an aliphatic ring, the aliphatic ring (including those formed with an alicyclic epoxy group) is the group described in the following (B-1):
B-1: Tricyclodecane skeleton, isobornyl skeleton, adamantane skeleton, cyclopentane skeleton, cyclohexane skeleton, hydrogenated bisphenol A skeleton, hydrogenated bisphenol F skeleton and hydrogenated bisphenol S skeleton.
A skeleton selected from is preferable, and the group described in (B-2) below:
B-2: Tricyclodecane skeleton, adamantane skeleton, cyclohexane skeleton and hydrogenated bisphenol A skeleton.
A skeleton selected from is more preferable.
Hereinafter, the specific example of the compound whose ring is an aliphatic ring among cyclic compounds (B) is demonstrated.

Among the cyclic compounds (B), preferred specific examples of the oxetane compound having an aliphatic ring include 3 (4), 8 (9) -bis [(1-ethyl-3-oxetanyl) methoxymethyl] -tricyclo [5 2.1.2.6] decane and the like.

Among the cyclic compounds (B), preferred specific examples of the epoxy compound having an aliphatic ring include alicyclic rings shown in the group described in (b-1a), (b-1b) and (b-1c) described later. Formula epoxy compounds; Hydrogenated bisphenol A type epoxy compounds such as hydrogenated bisphenol A diglycidyl ether and brominated hydrogenated bisphenol A diglycidyl ether; Hydrogenated bisphenol F diglycidyl ether, Brominated hydrogenated bisphenol F diglycidyl ether and the like Hydrogenated bisphenol F type epoxy compounds; hydrogenated bisphenol S type epoxy compounds such as hydrogenated bisphenol S diglycidyl ether and brominated hydrogenated bisphenol S diglycidyl ether; diepoxy tricyclodecane, tricyclodecane dimethanol diglycidyl ether, etc. The tricyclodecane skeleton Epoxy compounds having an adamantane skeleton such as an adamantane glycidyl ether; epoxy compounds.

Formula (b-1a):

Formula (b-1b):

Formula (b-1c):

(N is an average value and represents a positive number from 1 to 5.)

Among the cyclic compounds (B) of the present invention, the oxetane compound or epoxy compound in which the ring is an aliphatic ring is a compound different from the alicyclic compound (A) among the compounds, and among them, the alicyclic An epoxy compound or an epoxy compound having a skeleton selected from the group consisting of the tricyclodecane skeleton, the adamantane skeleton, and the hydrogenated bisphenol A skeleton is preferable.
Among the cyclic compounds (B), the oxetane compound and epoxy compound whose ring is an aliphatic ring are low in viscosity and moisture permeability and excellent in light transmittance, and thus the alicyclic epoxy compound and the tricyclo compound. Epoxy compounds having a decane skeleton or the adamantane skeleton are particularly preferred.
Moreover, as a cyclic compound (B) whose ring is an aliphatic ring, the compound which has an oxetanyl group or an epoxy group bifunctional or more is preferable, and the compound which is bifunctional is more preferable.
Of the cyclic compound (B) of the present invention, the preferable content of the cyclic compound (B) when the ring is an aliphatic ring is 100 parts by mass in total of the component (A) and the component (B) which are reactive compounds. The amount is 20 to 80 parts by mass, and more preferably 30 to 70 parts by mass. In order to achieve low moisture permeability for the cured product obtained from the resin composition of the present invention, the functional group equivalent of the cyclic compound (B) when the ring is an aliphatic ring is 10 to 1000 g / eq. Is more preferable, and 50 to 500 g / eq is more preferable.

Among the cyclic compounds (B), as a compound having a ring as a heterocycle, at least one heterocycle composed of a carbon atom and a hetero atom other than a carbon atom, and at least an oxetanyl group or an epoxy group in the molecule. Any compound that has one compound can be used. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.
Examples of the heterocyclic ring contained in the cyclic compound (B) in which the ring is a heterocyclic ring include the skeleton described in the following (B-3).
B-3: morpholine skeleton, tetrahydrofuran skeleton, oxane skeleton, dioxane skeleton, triazine skeleton (including isocyanurate ring), carbazole skeleton, pyrrolidine skeleton and piperidine skeleton.
The heterocycle may have a substituent or may not have a substituent. Examples of the substituent in the case where the heterocycle has a substituent include an alkyl group, an alkoxy group, and an alkenyl group, and these groups all preferably have 1 to 4 carbon atoms. Further, the substituent present in the heterocyclic skeleton is more preferably an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 1 to 3 carbon atoms.
As the cyclic compound (B) in which the ring is a heterocycle, among the above heterocycles, the group described in the following (B-4):
B-4: Oxane skeleton, dioxane skeleton and triazine skeleton (including isocyanurate ring)
And a compound having a skeleton selected from: and an oxetanyl group or an epoxy group.
Moreover, as a cyclic compound (B) whose ring is a heterocyclic ring, the compound which has 2 or more oxetanyl group or an epoxy group is preferable, and the compound which is bifunctional is more preferable.

The heterocyclic skeleton and the oxetanyl group or epoxy group are usually linked directly or by a linking group containing a hydrocarbon group, and are preferably linked by the linking group.
Examples of the linking group in the case where the skeleton and the oxetanyl group or the epoxy group are linked by a linking group containing the hydrocarbon group include a hydrocarbon group that may include an ether bond. Or an alkylene group having 1 to 10 carbon atoms having an ether bond. More preferable examples of the linking group include a C1-C4 alkylene group and a C1-C4 alkylene group having an ether bond at the terminal of the alkylene group (-oxy-C1-C4 alkylene group).

Among the cyclic compound (B) in which the ring is a heterocycle, preferred specific examples of the oxetane compound having a heterocycle include a reaction product of isocyanuric acid (CIC acid) and oxetane alcohol.

Among the cyclic compounds (B) in which the ring is a heterocycle, preferred specific examples of the epoxy compound having a heterocycle include 1,3,5-triglycidyl isocyanurate and 1-allyl-3,5-diglycidyl isocyanurate. And an epoxy compound such as a compound having an isocyanurate skeleton, and a compound having a dioxane glycol skeleton such as dioxane glycol diglycidyl ether.

When using the oxetane compound or epoxy compound which has a heterocyclic ring as the cyclic compound (B) of this invention, the epoxy compound which has an isocyanurate frame | skeleton is preferable among the said compounds. Among these, a compound having 2 or 3 epoxy groups together with the isocyanurate skeleton is particularly preferable.
Of the cyclic compound (B) of the present invention, the preferable content of the cyclic compound (B) when the ring is a heterocycle is 100 parts by mass in total of the component (A) and the component (B) which are reactive compounds. On the other hand, it is 20 to 80 parts by mass, more preferably 30 to 70 parts by mass. In order to achieve low moisture permeability for the cured product obtained from the resin composition of the present invention, the functional group equivalent of the cyclic compound (B) in which the ring is a heterocycle is preferably 10 to 1000 g / eq, More preferably, it is 50 to 500 g / eq.

The present invention is a curable resin composition containing the component (A) and the component (B). Hereinafter, suitable combinations of these components will be described.
As a preferable combination, the component (A) or the component (B) has a weight average molecular weight of 2000 or less, more preferably 1000 or less, and particularly preferably 500 or less to obtain a curable resin composition. It is preferable. By using such a low molecular weight component for either component (A) or component (B), the resin composition has a low viscosity while ensuring low hygroscopicity of the cured product, and tends to spread after coating. Therefore, a composition excellent in the production of OLED can be obtained. It is more preferable when both the component (A) and the component (B) are the low molecular weight compounds.
In particular, when the resin composition of the present invention is cured by thermosetting, it is also preferable that either one of the component (A) and the component (B) is an oxetane compound. It is because the resin composition excellent in sclerosis | hardenability in a short time can be obtained, ensuring low hygroscopicity by making either one into an oxetane compound.
The preferred use ratio of component (A) to component (B) in the resin composition of the present invention is such that (A) / (B) is 8/2 to 2/8 in terms of mass ratio, and 7/3 to 3 / 7 is more preferable.
When it is desired to improve the Tg (glass transition point) of the cured product obtained from the resin composition of the present invention, a compound having a dicyclopentadiene skeleton, an isobornyl skeleton or an adamantane skeleton is used as the component (A) or the component (B). It is good to introduce.

Further, when the alicyclic epoxy compound is used as the component (A) or the component (B), since the alicyclic epoxy compound has a low viscosity, a resin composition having good processability and excellent curing speed is obtained. It is done. In this respect, it is preferable to use the alicyclic epoxy compound in the resin composition of the present invention. Among the alicyclic epoxy compounds, bifunctional alicyclic epoxy compounds are more preferable, and 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate is particularly preferable.
In the present invention, the viscosity of the resin composition (viscosity measured at 25 ° C. with an E-type viscometer, the same shall apply hereinafter) is 15 Pa · s or less, more preferably 3500 mPa · s or less, still more preferably 1000 mPa · s or less, particularly preferably It is preferable to prepare the resin composition of the present invention by selecting the component (A) and the component (B) so as to be 500 mPa · s or less, most preferably 300 mPa · s or less.

The curing agent (C) contained in the resin composition of the present invention has reactivity with the epoxy compound and the oxetane compound. As the curing agent, a compound that initiates a curing reaction with energy rays such as heat or light can be used. In the present invention, any curing agent can be used, but a curing agent (C) that initiates a curing reaction with energy rays is usually preferred.

The curing agent (C) that initiates the curing reaction with energy rays such as light can be used without limitation as long as it is a compound that generates cations upon receiving ultraviolet rays (wavelength of about 200 to 400 nm). Examples of the curing agent (C) that initiates a curing reaction with an energy beam such as light include a cationic polymerization initiator that generates a cation upon receiving an energy beam such as light (hereinafter also referred to as a photocation polymerization initiator). Examples thereof include sulfonium salts, iodonium salts, phosphonium salts, ammonium salts, and antimonates.

Examples of the sulfonium salt used as the photocationic polymerization initiator include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis [diphenylsulfonio Diphenyl sulfide-bishexafluorophosphate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide-bishexafluoroantimonate, 7- [di (p-toluyl) sulfonio] -2- Isopropylthioxanthone hexafluorophosphate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate, 7- [di (p-toluyl) Sulfonio] -2-isopropyltetrakis (pentafluorophenyl) borate, phenylcarbonyl-4'-diphenylsulfonio-diphenyl sulfide-hexafluorophosphate, phenylcarbonyl-4'-diphenylsulfonio-diphenyl sulfide-hexafluoroantimonate, 4 -Tert-butylphenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-hexafluorophosphate, 4-tert-butylphenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-hexafluoroantimonate, 4-tert-butylphenyl Carbonyl-4'-diphenylsulfonio-diphenyl sulfide-tetrakis (pentafluorophenyl) borate, thiophenyl diphe Nylsulfonium hexafluoroantimonate, thiophenyldiphenylsulfonium hexafluorophosphate, 4- {4- (2-chlorobenzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, thiophenyldiphenylsulfonium hexafluoroantimonate 4,4 ′, 4 ″ -tri (β-hydroxyethoxyphenyl) sulfonium hexafluoroantimonate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide-bishexafluoroantimonate, diphenyl [4 -(Phenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate and tris [4- (4-acetylphenylsulfanyl) phenyl Sulfonyl] sulfonium tris [(trifluoromethyl) sulfonyl] methanide and the like.

Examples of the iodonium salt used as the photocationic polymerization initiator include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and , (Tricumyl) iodonium tetrakis (pentafluorophenyl) borate and the like.

Examples of the phosphonium salt used as the photocationic polymerization initiator include tri-n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride.

Examples of ammonium salts used as the photocationic polymerization initiator include benzyltrimethylammonium chloride, phenyltributylammonium chloride, and benzyltrimethylammonium bromide.

Antimonates used as photocationic polymerization initiators include triphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, and bis Examples include [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate and diallyliodonium hexafluoroantimonate.

As the curing agent (C) that initiates the curing reaction with an energy beam such as light used in the present invention, the iodonium salt and the sulfonium salt are preferable, and among them, it is highly sensitive and easily available from the market (Tricumyl). Iodonium tetrakis (pentafluorophenyl) borate, thiophenyldiphenylsulfonium hexafluoroantimonate, 4- {4- (2-chlorobenzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, diphenyl [4- ( Phenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate and tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tris [(trifluoromethyl) sulfonyl] methanide It is more preferable.
Furthermore, in view of the harmfulness to the environment and the human body and the regulations of each country, the antimony element-free (tricumyl) iodonium tetrakis (pentafluorophenyl) borate as the curing agent (C) that initiates the curing reaction with the energy rays. , Diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate, or tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tris [(trifluoromethyl) sulfonyl] methanide Is most preferred.
In the resin composition of the present invention, the preferred content when using the cationic photopolymerization initiator is 0.05 to 5 parts by mass with respect to 100 parts by mass as the total of component (A) and component (B). The amount is preferably 0.1 to 3 parts by mass. In addition, in the resin composition of this invention, a photocationic polymerization initiator may be used independently and may be used in mixture of multiple types.

In the resin composition of the present invention, a thermosetting agent that initiates a curing reaction with the epoxy compound and the oxetane compound by heat can be used as the curing agent (C). Examples of the thermosetting agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, carboxylic acid compounds, and the like.
Specific examples of thermosetting agents that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a polyamide resin synthesized from linolenic acid and ethylenediamine, imidazole, trifluoroborane- Amines and amide compounds such as amine complexes and guanidine derivatives; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride , Nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methyl Acid anhydride compounds such as cyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1,1′-biphenyl] -4, 4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, Alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde , Acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, Polycondensates with 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1,4′-bis (chloromethyl) benzene or 1,4′-bis (methoxymethyl) benzene, and the like Modified compounds, halogenated bisphenols such as tetrabromobisphenol A, and phenolic compounds such as condensates of terpenes and phenols are included, but are not limited thereto. These may be used alone or in combination of two or more.

In addition, it is often preferable to use an acid anhydride having excellent transparency after curing for surface sealing in a sealing material, particularly an organic EL element, and among them, methyltetrahydrophthalic anhydride, methyl nadic anhydride, Nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1 ] An acid anhydride having an alicyclic skeleton such as heptane-2,3-dicarboxylic acid anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is preferred. As these acid anhydrides having an alicyclic skeleton, commercially available products can be used. For example, H-TMA series, such as Mitsubishi Gas Chemical Co., Ltd. Products or liquid products (however, they are described as liquid products but are semi-solid at room temperature and workability is very inferior).
In addition, when cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is used as a thermosetting agent, workability becomes extremely poor due to the solid or semi-solid state with high viscosity when used alone. There is a case. Therefore, it is desirable to use in combination with another curing agent, preferably an acid anhydride having an alicyclic skeleton. The curing agent that can be used in this case is not particularly limited as long as it is liquid and has a low viscosity. For example, commercially available curing agents include methyl nadic acid anhydride and Ricacid HNA-100 containing Nadic anhydride (manufactured by Shin Nippon Rika Co., Ltd.), and Ricacid containing hexahydrophthalic anhydride and methylhexahydrophthalic anhydride. Examples of the curing agent include MH700 (manufactured by Shin Nippon Rika Co., Ltd.). When a cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and another curing agent are used in combination as a thermosetting agent, a solid or semi-solid cyclohexane-1,3,4-tricarboxylic acid is used in advance. By mixing the acid-3,4-anhydride and a curing agent having a low viscosity until it becomes uniform at room temperature or under heating conditions, it is possible to obtain a good workability state. The heating condition at this time is preferably 150 ° C. or less, more preferably 120 ° C., in order to prevent volatilization of the curing agent. Further, from the viewpoint of handling workability and the depression of the sealing material after curing, the use ratio of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride in the total curing agent is 20 to 90 mass. %, More preferably in the range of 30 to 80% by mass or less. When the mixing ratio exceeds 90% by weight, workability as a curing agent is extremely inferior. On the other hand, when the amount is less than 20% by mass, the improvement effect may be reduced in terms of the depression of the sealing material.

In this invention, when using a thermosetting agent as a hardening | curing agent (C), the compounding ratio of the thermosetting agent is the functional group equivalent contained in the said epoxy compound or the said oxetane compound, and the functional group which this thermosetting agent has. It is determined by the equivalent of (for example, a carboxyl group of a carboxylic acid curing agent). Preferably, the functional group of the thermosetting agent such as a carboxyl group is 0.2 to 5 equivalents, more preferably 0 to 1 equivalent of the epoxy group and oxetanyl group which are the functional groups of the component (A) and the component (B). .5 to 2 equivalents. When exceeding this range, the curing reaction does not proceed sufficiently, and excess functional groups remain, so that the toughness and heat resistance of the cured product cannot be fully exhibited.

In the resin composition of the present invention, a curing catalyst (also referred to as a curing accelerator) can be used in combination with the thermosetting agent, and the curing catalyst can be used alone without using the thermosetting agent. it can.
Specific examples of the curing accelerator that can be used in the resin composition of the present invention include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino -6 (2′-methylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino- 6 (2′-ethyl, 4-methylimidazole (1 ′)) ethyl-s-triazine, 2,4 Diamino-6 (2′-methylimidazole (1 ′)) ethyl-s-triazine / isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl -3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole imidazoles; these imidazoles and phthalic acid , Isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, salts with polyvalent carboxylic acids such as oxalic acid; amides such as dicyandiamide; 1,8-diaza-bicyclo (5.4) 0.0) Diaza compounds such as undecene-7 and the like Salts such as tetraphenylborate and phenol novolak, salts with the above polycarboxylic acids, or phosphinic acids; ammonium salt-based thermal cation initiators such as tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide; Phosphine-based or phosphonium compound-based thermal cation initiators such as triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate; 1-naphthylmethylmethyl-p-hydroxyphenylsulfonium hexafluoroantimonate Benzylmethyl-p-hydroxyphenylsulfonium hexafluoroantimonate, dimethyl-p-acetoxyphenylsulfate Antimonate-based thermal cation initiators such as nium hexafluoroantimonate; 1-naphthylmethylmethyl-p-hydroxyphenylsulfonium hexafluorophosphate, benzylmethyl-p-hydroxyphenylsulfonium hexafluorophosphate, dimethyl-p-acetoxyphenylsulfonium Phosphonium salt thermal cation initiators such as hexafluorophosphate; phenols such as 2,4,6-trisaminomethylphenol; metal compounds such as amine adducts and tin octylate; and these curing accelerators in microcapsules And a microcapsule type curing accelerator.
Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions. The curing accelerator is preferably a thermal cation initiator, and particularly preferably a phosphonium salt-based thermal cation initiator. A preferable content of the curing accelerator such as a thermal cation initiator is usually in the range of 0.001 to 15 parts by mass, more preferably 0.01 to 100 parts by mass of the total amount of the component (A) and the component (B). Is 5 parts by mass.

The resin composition of the present invention is also effective in combination with a cleavage type photopolymerization initiator used in a radical polymerization system and cured by a redox reaction. When the cleavage type photopolymerization initiator is used in combination, the ease of the one-electron transfer reaction determines the reactivity. In this case, the iodonium salt having a low level of LUMO (lowest orbital: a measure of the ease with which an electron transfer reaction occurs) has good reactivity, so that an iodonium salt may be used as the curing agent (C). preferable. When a cleavage photopolymerization initiator is used in combination, any cleavage photopolymerization initiator can be used, and examples thereof include 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl-phenylketone. .

The thermosetting agent used in the resin composition of the present invention is preferably a thermosetting agent that initiates thermosetting at 100 ° C. or less in consideration of the reaction rate and the thermal history of the constituent members. More preferably used. In the present invention, it is preferable to use a photocationic polymerization initiator that does not require heat energy in terms of the heat history of the constituent members.

The resin composition of this invention can contain other components other than the said component (A), the said component (B), and the said component (C) as needed. The other components include fine particles, a dispersant, reactive compounds other than the components (A) and (B) (for example, oxetane compounds or epoxy compounds having an aromatic ring, (meth) acrylates, etc.), photocationic polymerization. Examples include photopolymerization initiators other than the initiator, other additives, and the like.
Fine particles can be used in combination with the resin composition of the present invention as necessary. Examples of the fine particles include organic fine particles and inorganic fine particles. Further, the fine particles can be used alone or in admixture of plural kinds in consideration of light transmittance, hardness, scratch resistance, curing shrinkage rate and refractive index required for the cured product.

Examples of organic fine particles that can be used in the present invention include polystyrene resin beads, acrylic resin beads, urethane resin beads, polycarbonate resin beads, and other organic polymer beads; porous polystyrene resin beads, porous acrylic resin beads, porous Porous organic polymer beads such as urethane resin beads and porous polycarbonate resin beads; resin powder of benzoguanamine-formalin condensate, resin powder of benzoguanamine-melamine-formalin condensate, resin powder of urea-formalin condensate, aspartic acid ester derivative Powder, zinc stearate powder, stearamide powder, epoxy resin powder, polyethylene powder and the like. Among these, crosslinked polymethyl methacrylate resin beads, crosslinked polymethyl methacrylate / styrene resin beads, and the like are preferable. These organic fine particles can be easily obtained as a commercial product, and can also be prepared with reference to known literature.

Examples of inorganic fine particles that can be used in the present invention include conductive metal oxides, transparent metal oxides, and other inorganic fillers.

Examples of the conductive metal oxide that can be used in the present invention include zinc antimonate, tin oxide-doped indium oxide (ITO), antimony-doped tin oxide (ATO), antimony pentoxide, tin oxide, aluminum-doped zinc oxide, and gallium. Examples thereof include doped zinc oxide and fluorine-doped tin oxide.

Examples of the transparent metal oxide that can be used in the present invention include silica, titanium oxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, titanium oxide / zirconium oxide / tin oxide / antimony pentoxide composite, and zirconium oxide. / Tin oxide / antimony pentoxide composite and titanium oxide / zirconium oxide / tin oxide composite.

Other inorganic fillers that can be used in the present invention include calcium oxide, calcium chloride, zeolite and silica gel.

The fine particles that can be used in the present invention are preferably fine particles having excellent hardness and scratch resistance and a high refractive index, such as titanium oxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, titanium oxide / zirconium oxide / oxidation. A tin / antimony pentoxide composite, a zirconium oxide / tin oxide / antimony pentoxide composite, and a titanium oxide / zirconium oxide / tin oxide composite are preferably used. Moreover, since the optical sheet used for the display is required to have a high light transmittance, the primary particle diameter of the fine particles is preferably 100 nm or less.
When the fine particles are blended in the resin composition of the present invention, the preferred blending ratio is 1 to 30 parts by weight, more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the total amount of component (A) and component (B). Part.

When fine particles are used together in the present invention, as a fine particle dispersant, a polycarboxylic acid-based dispersant; a silicone-based dispersant such as a silane coupling agent, a titanate-based coupling agent, or a modified silicone oil; or an organic copolymer system It is also possible to use a dispersant or the like in combination.
A preferable blending ratio when the above dispersant is blended with the resin composition of the present invention is about 0.001 to 30% by mass, more preferably 0.05 to 5% by mass with respect to the total mass of the resin composition of the present invention. %.

The primary particle size means the smallest particle size of the particles when the aggregation is broken. That is, in the case of elliptical fine particles, the minor axis is the primary particle diameter. The primary particle size can be measured by a dynamic light scattering method, observation with an electron microscope, or the like. Specifically, the primary particle size of the fine particles can be measured using a JSM-7700F field emission scanning electron microscope manufactured by JEOL Ltd. under the condition of an acceleration voltage of 30 kV.

These fine particles can be used by being dispersed in a solvent. In particular, the inorganic fine particles are readily available as commercial products in a form dispersed in water or an organic solvent. Examples of the organic solvent used include hydrocarbon solvents, ester solvents, ether solvents, and ketone solvents.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane and decane; and petroleum ether, white which is a mixture thereof. Examples include gasoline and solvent naphtha.
Examples of ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, and cyclic esters such as γ-butyrolactone; ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene (Mono or poly) alkylene glycol monoalkyl ether monoacetates such as glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate and butylene glycol monomethyl ether monoacetate; dialkyl glutarate, dialkyl succinate and Alkyl polycarboxylates such as dialkyl adipates Ester, and the like can be mentioned.
Examples of ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether; glycols such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether. Ethers: cyclic ethers such as tetrahydrofuran and the like.
Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

In the present invention, an oxetane compound or an epoxy compound having an aromatic ring can be used as an optional component.

Examples of oxetane compounds having an aromatic ring that can be used as optional components include 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3-phenoxymethyloxetane, 1,4 -Bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,2-bis [(3-ethyloxetane-3 -Yl) methoxy] benzene, 4,4′-bis [(3-ethyloxetane-3-yl) methoxy] biphenyl, 2,2′-bis [(3-ethyl-3-oxetanyl) methoxy] biphenyl, 3, 3 ′, 5,5′-tetramethyl [4,4′-bis (3-ethyloxetane-3-yl) methoxy] biphenyl, 2,7-bis [(3-ethyloxy 3-yl) methoxy] naphthalene and 4,4'-bis [(1-ethyl-3-oxetanyl) methyl] such thiodiglycol benzene thioether acid.

Examples of the epoxy compound having an aromatic ring that can be used as an optional component include epoxy compounds having a phenyl skeleton such as styrene oxide, phenyl glycidyl ether, and p-tert-butylphenyl glycidyl ether; biphenyl glycidyl ether, biphenyl diglycidyl ether, 3, Epoxy compounds having a biphenyl skeleton such as 3 ′, 5,5′-tetramethyl-4,4′-bis (glycidyloxy) -1,1′-biphenyl and biphenyl aralkyl type epoxy compounds; phenol novolac type epoxy compounds and cresols Novolak type epoxy compounds such as novolak type epoxy compounds; Bisphenol A type epoxy compounds such as bisphenol A diglycidyl ether and brominated bisphenol A diglycidyl ether; Bisphenol F type epoxy compounds such as phenol F diglycidyl ether and brominated bisphenol F diglycidyl ether; Bisphenol S type epoxy compounds such as bisphenol S diglycidyl ether and brominated bisphenol S diglycidyl ether; 1,3-bis (4 ′ -Epoxy compounds having an adamantane skeleton substituted with an aromatic ring such as glycidyloxyphenyl) adamantane and 2,2-bis (4'-glycidyloxyphenyl) adamantane; bisphenyl fluorenediglycidyl ether and bisphenylfluoreneethanoldi Epoxy compounds having a fluorene skeleton such as glycidyl ether; glycidyloxynaphthalene, 1,6-bis (2,3-epoxypropan-1-yloxy) naphthalene, binaphthalene Ether, epoxy compounds and the like having a naphthalene skeleton such as bi-naphthalene diglycidyl ether and binaphthol ethanol diglycidyl ether.

As the oxetane compound or epoxy compound having an aromatic ring, an epoxy compound having a skeleton selected from the group consisting of phenyl, biphenyl, bisphenol A, bisphenol F, bisphenol S and naphthalene is preferable. An epoxy compound having a skeleton selected from the group consisting of biphenyl, bisphenol A and naphthalene is particularly preferable in that the viscosity of the resin composition is low, the moisture permeability of the cured product is low, and the light transmittance is excellent. When using the oxetane compound or epoxy compound which has an aromatic ring for the resin composition of this invention, preferable content is 20 with respect to 100 mass parts of total amounts of the component (A) and component (B) which are reactive compounds. -80 parts by mass, more preferably 30-70 parts by mass. In order to achieve low moisture permeability of the cured product, the functional group equivalent of the oxetane compound or epoxy compound having an aromatic ring is preferably 10 to 1000 g / eq, and more preferably 50 to 500 g / eq.
In addition, since the resin composition of the present invention can impart rigidity to the coating film, an oxetane compound or an epoxy compound having a condensed aromatic ring structure such as fluorene or carbazole is also preferably used. These oxetane compounds or epoxy compounds may be used alone or in combination of two or more.

In addition, in the resin composition of the present invention, in consideration of the viscosity, refractive index, adhesion and the like of the resin composition of the present invention to be obtained, the component (A), the component (B) and the oxetane compound having the aromatic ring or A reactive compound may be used in addition to the epoxy compound. Specific examples of the reactive compound include (meth) acrylate.
As the (meth) acrylate, monofunctional (meth) acrylate, bifunctional (meth) acrylate, polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in the molecule, polyester (meth) acrylate, and epoxy (Meth) acrylate or the like can be used.

Examples of the monofunctional (meth) acrylate include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate and cyclohexyl (meth). Alicyclic (meth) acrylates such as acrylate; Tetrahydrofurfuryl (meth) acrylate, Caprolactone-modified tetrahydrofurfuryl (meth) acrylate and morpholine (meth) acrylate and other (meth) acrylates; benzyl (meth) acrylate , Ethoxy modified cresol (meth) acrylate, propoxy modified cresol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, o-phenylphenol (meth) Acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-phenylphenol (meth) acrylate, p-phenylphenol monoethoxy (meth) acrylate, p-phenylphenol polyethoxy (Meth) acrylates having aromatic rings such as (meth) acrylate, o-phenylbenzyl acrylate and p-phenylbenzyl acrylate; carbazole (poly) ethoxy (meth) acrylate, carbazole (poly) propoxy (meth) acrylate and (poly) (Meth) acrylate having a heteroaromatic ring such as caprolactone-modified carbazole (meth) acrylate; naphthyl (meth) acrylate, naphthyl (poly) ethoxy (meth) acrylate Naphthyl (poly) propoxy (meth) acrylate, (poly) caprolactone modified naphthyl (meth) acrylate, binaphthol (meth) acrylate, binaphthol (poly) ethoxy (meth) acrylate, binaphthol (poly) propoxy (meth) acrylate, ( Poly) caprolactone-modified binaphthol (meth) acrylate, naphthol (meth) acrylate, naphthol (poly) ethoxy (meth) acrylate, naphthol (poly) propoxy (meth) acrylate, and (poly) caprolactone modified naphthol (meth) acrylate (Meth) acrylate having imide ring structure; imide (meth) acrylate having imide ring structure; butanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (Meth) acrylate having a hydroxyl group such as hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and dipropylene glycol (meth) acrylate; dimethylaminoethyl (meth) acrylate, Butoxyethyl (meth) acrylate, caprolactone (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, octafluoropentyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) ) Acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, iso (Meth) acrylates having alkyl groups such as listyl (meth) acrylate and lauryl (meth) acrylate; ethoxydiethylene glycol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, polyethylene glycol (meth) acrylate and polypropylene glycol (meth) ) (Meth) acrylates of polyhydric alcohols such as acrylates.

Examples of the (meth) acrylate monomer having the above two functional groups include (meth) acrylate having a heterocycle such as hydropivalaldehyde-modified trimethylolpropane di (meth) acrylate; (poly) ethoxy-modified bisphenol A di (meta) ) Acrylate, (poly) propoxy modified bisphenol A di (meth) acrylate, (poly) ethoxy modified bisphenol F di (meth) acrylate, (poly) propoxy modified bisphenol F di (meth) acrylate, (poly) ethoxy modified bisphenol S di (Meth) acrylates having aromatic rings such as (meth) acrylate, (poly) propoxy-modified bisphenol S di (meth) acrylate, hexahydrophthalic acid di (meth) acrylate and bisphenoxy (poly) ethoxyfluorene A (meth) acrylate having a heteroaromatic ring such as biphenyldimethanol di (meth) acrylate; binaphthol di (meth) acrylate, binaphthol (poly) ethoxydi (meth) acrylate, binaphthol (poly) propoxy di (meth) acrylate and (poly ) Caprolactone-modified (meth) acrylate having a condensed ring such as binaphthol di (meth) acrylate; bisphenol full orange (meth) acrylate, bisphenoxymethanol full orange (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate and bisphenoxycaprolactone (Meth) acrylates having polycyclic aromatics such as full orange (meth) acrylate; acrylates of isocyanates such as diacrylated isocyanurates Linear methylene such as 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate (Meth) acrylate having a structure; alicyclic (meth) acrylate such as tricyclodecane dimethanol (meth) acrylate; ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate And di (meth) acrylates of polyhydric alcohols such as polypropylene di (meth) acrylate.

Examples of the polyfunctional (meth) acrylate monomers include polyfunctional (meth) acrylates having an isocyanurate ring such as tris (acryloxyethyl) isocyanurate and (poly) caprolactone-modified tris (acryloxyethyl) isocyanurate; pentaerythritol tris (Meth) acrylate, pentaerythritol tetra (meth) acrylate, (poly) ethoxy modified pentaerythritol tetra (meth) acrylate, (poly) propoxy modified pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, (poly ) Caprolactone-modified dipentaerythritol penta (meth) acrylate, (poly) ethoxy-modified dipentaerythritol penta (meth) acrylate, (poly) pro Xyl modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (poly) caprolactone modified dipentaerythritol hexa (meth) acrylate, (poly) ethoxy modified dipentaerythritol hexa (meth) acrylate, (poly ) Propoxy-modified dipentaerythritol hexa (meth) acrylate, polypentaerythritol poly (meth) acrylate, trimethylolpropane tri (meth) acrylate, (poly) ethoxy modified trimethylolpropane tri (meth) acrylate, (poly) propoxy modified tri Multivalent alcohols such as methylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate and glycerol tri (meth) acrylate Polyfunctional (meth) acrylates of alcohol; polyfunctional (meth) acrylates containing phosphorus such as tri (meth) acrylate phosphate; polyfunctional (meth) acrylates having aromatics such as trimethylolpropane benzoate (meth) acrylate; Examples include acid-modified polyfunctional (meth) acrylates such as 2,2,2-trisacryloyloxymethyl succinic acid; polyfunctional (meth) acrylates having a silicone skeleton such as silicone hexa (meth) acrylate. .

As the urethane (meth) acrylate, for example, a polyester diol which is a reaction product of a diol compound or the diol compound and a dibasic acid or an anhydride thereof, and an organic polyisocyanate are reacted, and then a hydroxyl group-containing (meth) The reaction product etc. which added the acrylate are mentioned.
Examples of the diol compound include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,8- Octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2 -Ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A polyethoxydiol, bisphenol A polypropoxydiol, and the like.
Examples of the dibasic acid or anhydride thereof include dibasic acids such as succinic acid, adipic acid, azelaic acid, dimer acid, isophthalic acid, terephthalic acid, and phthalic acid; or anhydrides thereof.
Examples of the organic polyisocyanate include chain saturated hydrocarbon isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate; isophorone diisocyanate, Cyclic saturated hydrocarbon isocyanates such as norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylenebis (4-cyclohexylisocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate and hydrogenated toluene diisocyanate; 2,4-tolylene diisocyanate, 1,3-xylylene Range isocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-di Isocyanate, aromatic polyisocyanates such as 6-isopropyl-1,3-phenyl diisocyanate, and 1,5-naphthalene diisocyanate.

Examples of the polyester (meth) acrylate include a polyester diol which is a reaction product of a diol compound and a dibasic acid or an anhydride thereof, and a reaction product of (meth) acrylic acid.

Among them, as the (meth) acrylate that can be used for the resin composition of the present invention, a material having a low curing shrinkage rate is suitably used. Specifically, (meth) acrylate having a ring structure is preferable, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, Cyclohexyl (meth) acrylate, p-cumylphenol (poly) ethoxy (meth) acrylate, naphthol (poly) ethoxy (meth) acrylate, naphthol (poly) propoxy (meth) acrylate, phenylphenol (poly) ethoxy (meth) acrylate , Phenylphenol (poly) propoxy (meth) acrylate, benzyl (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, hydropivalaldehyde-modified trimethylolpropane di (meth) Acrylate and biphenyl dimethanol di (meth) acrylate. Particularly preferred are phenylphenol (poly) ethoxy (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, hydropivalaldehyde-modified trimethylolpropane di (meth) acrylate having a high Tg of the cured product and a low cure shrinkage rate. And biphenyldimethanol di (meth) acrylate.
In addition, in the resin composition of this invention, when using the said (meth) acrylate which is another component, it may be used independently and may be used in mixture of multiple types. A preferable blending amount when (meth) acrylate is used in the resin composition of the present invention is 10 to 200 parts by mass, more preferably 100 parts by mass with respect to the total amount of component (A) and component (B). 50 to 150 parts by mass.

Moreover, when using the said (meth) acrylate in the resin composition of this invention, it is preferable to use photoinitiators other than the said photocationic polymerization initiator.
Specific examples of photopolymerization initiators other than the cationic photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2- Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl-phenylketone, 2- Acetophenones such as methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] Class; 2 Anthraquinones such as ethyl anthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; acetophenone dimethyl ketal and benzyl Ketals such as dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide and 4,4′-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2, Phosphines such as 4,6-trimethylbenzoyl) -phenylphosphine oxide and diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide And oxides. Preferred photopolymerization initiators other than the cationic photopolymerization initiator are preferably acetophenones, and more preferably 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl-phenyl ketone. it can. When a photopolymerization initiator is used in the resin composition of the present invention, the amount is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylate component. More preferably, it is 1 to 5 parts by mass. In addition, in the resin composition of this invention, a photoinitiator may be used independently and may be used in mixture of multiple types.

The use ratio of each component of the resin composition of the present invention is determined in consideration of a desired refractive index, durability, viscosity, adhesion, and the like. Usually, when the total amount of component (A) and component (B) is 100 parts by mass, the content of component (A) is 20 to 80 parts by mass, preferably 30 to 70 parts by mass. The content of (B) is 20 to 80 parts by mass, preferably 30 to 70 parts by mass. In this case, the content of the component (C) is usually 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass in the case of a photocationic polymerization initiator or a thermal cationic polymerization initiator. .
Usually, the total amount of the component (A) and the component (B) is preferably 50 to 99% by mass, more preferably 70 to 99% by mass, and still more preferably based on the total amount of the resin composition of the present invention. 80 to 99% by mass, optionally 90 to 99% by mass, and further 95 to 99% by mass. The balance is the above component (C) and optional additive components.

In addition to the above components, the resin composition of the present invention includes a mold release agent, an antifoaming agent, a leveling agent, a light stabilizer, an antioxidant, a polymerization inhibitor, and a plasticizer in order to improve convenience during handling. In addition, other additives such as an antistatic agent can be used in combination depending on the situation.

In the resin composition of the present invention, a plasticizer may be used in order to obtain durability and flexibility. The plasticizer material used is selected depending on the desired viscosity, durability, transparency, flexibility, and the like. Specific examples include olefin polymers such as polyethylene and polypropylene; dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, dicyclohexyl phthalate, ethyl phthalyl ethyl glycolate. Phthalates such as butyl phthalyl butyl glycolate; trimellitic esters such as tris (2-ethylhexyl) trimellitate; dibutyl adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, bis (2 -(2-butoxyethoxy) ethyl) adipate, bis (2-ethylhexyl) azelate, dibutyl sebacate , Aliphatic dibasic acid esters such as bis (2-ethylhexyl) sebacate and diethyl succinate; trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl Orthophosphates such as phosphate, cresyl diphenyl phosphate and 2-ethylhexyl diphenyl phosphate; ricinoleate such as methylacetylricinoleate; polyester such as poly (1,3-butanediol adipate); acetate such as glyceryl triacetate; Sulfonamides such as N-butylbenzenesulfonamide; polyethylene glycol benzoate, polyethylene glycol dibenzoate, polyp Polyalkylene oxide (di) benzoates such as pyrene glycol benzoate, polypropylene glycol dibenzoate, polyteroramethylene glycol benzoate and polytetramethylene glycol benzoate; polyethers such as polypropylene glycol, polyethylene glycol and polytetramethylene glycol; polyethoxy modified bisphenol A and Polyalkoxy modified bisphenol A such as polypropoxy modified bisphenol A; polyalkoxy modified bisphenol F such as polyethoxy modified bisphenol F and polypropoxy modified bisphenol F; polycyclic aromatic hydrocarbons such as naphthalene, phenanthrene and anthracene; (bi) naphthol, (Poly) ethoxy modified (bi) naphthol, (poly) propoxy modified ( Bi) naphthol, (poly) tetramethylene glycol modified (bi) naphthol and (poly) caprolactone modified (bi) naphthol derivatives such as naphthol; diphenyl sulfide, diphenyl polysulfide, benzothiazolyl disulfide, diphenylthiourea, morpholino dithiobenzothiazole Sulfur-containing compounds such as cyclohexylbenzothiazole-2-sulfenamine, tetramethylthiuram disulfide, tetraethylthiuramdisulfide, tetrabutylthiuram disulfide, tetrakis (2-ethylhexyl) thiuram disulfide, tetramethylthiuram monosulfide and dipentamethylenethiuram tetrasulfide Compounds. Preferred plasticizers include (poly) ethylene glycol dibenzoate, (poly) propylene glycol dibenzoate, binaphthol, (poly) ethoxy modified binaphthol, (poly) propoxy modified binaphthol and diphenyl sulfide.

A coupling agent may be added to the resin composition of the present invention for the purpose of improving the adhesive force. Although there is no special limitation in the coupling agent to be used, it is preferable to contain a silane coupling agent.
Examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3 -Black Propyl methyl dimethoxy silane, 3-chloropropyl trimethoxy silane, and the like.
Coupling agents other than silane coupling agents include isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate, Titanium coupling agents such as neoalkoxytri (pN- (β-aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneodeca Noyl zirconate, neoalkoxy tris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxy tris (ethylenediaminoethyl) zirconate, neoalkoxy Tris (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al- acetylacetonate, zirconium or aluminum coupling agents such as Al- methacrylate and Al- propionate and the like.
These coupling agents may be used alone or in combination of two or more. Of these coupling agents, silane coupling agents are preferred, and aminosilane coupling agents or epoxysilane coupling agents are more preferred. By using a coupling agent, it is possible to obtain a sealing material that is excellent in moisture resistance reliability and has little decrease in adhesive strength after moisture absorption. When the coupling agent is used in the resin composition of the present invention, the content is about 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the resin composition.

In the resin composition of the present invention, polymers such as acrylic polymer, polyester elastomer, urethane polymer and nitrile rubber can be further added as necessary. About the component which does not have a reactive group, it is preferable that a weight average molecular weight is 10,000 g / mol from a compatible point. An organometallic compound such as alkylaluminum can also be added to reduce the water vapor permeability. Although a solvent can also be added, what does not add a solvent is preferable.

The resin composition of the present invention is preferably a resin composition having a weight average molecular weight of 10,000 g / mol or less, and more preferably 5,000 g / mol or less. Since a component having a large weight average molecular weight does not dissolve with other components, the prepared resin composition becomes a turbid liquid. This is incompatible because it is essential that the resin composition used in the display is uniformly transparent.
Further, the resin composition of the present invention is required to have excellent properties with respect to transmittance. Specifically, when the resin composition of the present invention is cured to obtain a cured product having a film thickness of 100 μm, the light transmittance of each wavelength at a wavelength of 380 to 780 nm of the cured product is preferably 90% or more. The light transmittance can be measured with a measuring instrument such as a spectrophotometer U-3900H manufactured by Hitachi High-Technologies Corporation.

The resin composition of the present invention can be prepared by mixing and dissolving each component according to a conventional method. For example, each component can be charged into a round bottom flask equipped with a stirrer and a thermometer and stirred at 40 to 80 ° C. for 0.5 to 6 hours.

The viscosity of the resin composition of the present invention is preferably a viscosity suitable for workability in processability when producing a display or the like, particularly a viscosity suitable for surface sealing in an organic EL device. The organic EL element is usually surrounded by a dam material, on a substrate such as glass, in order from the substrate side, a metal electrode (lower electrode), an organic EL layer including at least an organic light emitting layer, an ITO electrode ( Upper electrode) and a passivation film are stacked, and the passivation film is filled with a fill material (surface sealing resin composition), and the top is further sealed with a sealing substrate such as glass. It has become. The fill material fills the space between the metal electrode side substrate and the sealing substrate on the opposite side and protects the organic light emitting layer from external moisture and the like, and is usually a curable resin. A composition is used. After filling the filling material which is the curable resin composition and placing a sealing substrate such as glass, the resin composition is cured to seal the organic light emitting layer. The resin composition used as the filling material is a resin composition for surface sealing. Therefore, it is preferable that the resin composition for surface sealing has a low viscosity so that the space between the substrates can be completely sealed.
The viscosity of the resin composition for surface sealing of the organic EL device of the present invention is preferably 15 Pa · s measured at 25 ° C. using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.). Below, more preferably 3500 mPa · s or less, still more preferably 1000 mPa · s or less, particularly preferably 500 mPa · s or less, and most preferably 300 mPa · s or less. The lower limit of the viscosity is not particularly limited, but is about 50 mPa · s.

In the present invention, a resin composition containing a curing agent that initiates a curing reaction with energy rays as the curing agent (C) can be easily cured with energy rays. Specific examples of energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays and laser rays; particle rays such as alpha rays, beta rays and electron rays. Of these, ultraviolet rays, laser beams, visible rays, or electron beams are preferred in the present invention.

According to a conventional method, the cured product of the present invention can be obtained by irradiating the resin composition of the present invention with the energy beam. The liquid refractive index of the resin composition of the present invention is usually 1.45 to 1.70, preferably 1.50 to 1.65. The refractive index can be measured with an Abbe refractometer (model number: DR-M2, manufactured by Atago Co., Ltd.).
The resin composition of the present invention preferably has a smaller shrinkage ratio (curing shrinkage ratio) at the time of curing, preferably 5% or less, more preferably 4% or less, and still more preferably 3.5%. It is as follows.
Further, the cured product of the resin composition of the present invention preferably has a water vapor transmission rate of 45 g / m ² · 24 h (measured at 60 ° C. and a humidity of 90%, the same hereinafter) in order to protect the organic light emitting layer from external moisture and the like ) Or less, and more preferably 35 g / m ² · 24 h or less.
The glass transition temperature (Tg) of the cured product is preferably higher to some extent. In the resin composition of the present invention, the Tg is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, and most preferably 100 ° C. or higher.

Below, the preferable aspect of the resin composition of this invention is illustrated.
(I) A resin composition for surface sealing of an organic EL device comprising an alicyclic compound (A), a cyclic compound (B) and a curing agent (C),
Component (A) is a compound having a skeleton selected from the group described in (A-1) above and an epoxy group or oxetanyl group,
Component (B) is an aliphatic ring skeleton selected from the group described in (B-1) above or a heterocyclic skeleton selected from the group described in (B-3) above, and an epoxy group or oxetanyl group The resin composition which is a compound which is a compound which has a structure different from the compound used as a component (A).
(II) The resin composition according to the above (I), wherein the component (A) is a compound having a skeleton selected from the group described in the above (A-2) and an epoxy group or an oxetanyl group.
(III) The component (A) is an alicyclic epoxy compound, or an oxetane compound or an epoxy compound having a hydrogenated bisphenol A skeleton or a tricyclodecane skeleton, or an alicyclic having a cyclohexane skeleton in which an epoxy group is formed. The resin composition according to (I) or (II), which is an epoxy compound.
(IV) The resin composition according to any one of the above (I) to (III), which contains an epoxy compound having a tricyclodecane skeleton or an alicyclic epoxy compound having a cyclohexane skeleton as the component (A) object.
(V) Any of the above (I) to (IV) containing dicyclopentadiene dimethanol diglycidyl ether or 3,4-epoxycyclohexenylmethyl-3 ′, 4 ′ epoxycyclohexene carboxylate as component (A) The resin composition according to one item.

(VI) The component (B) is a compound having an aliphatic ring skeleton selected from the group described in the above (B-2) or a heterocyclic skeleton selected from the group described in the above (B-4) The resin composition according to any one of (I) to (V).
(VII) The component (B) is an alicyclic epoxy compound or an epoxy compound having a tricyclodecane skeleton, an adamantane skeleton, or an isocyanurate skeleton, according to any one of the above (I) to (VI) Resin composition.
(VIII) The above (I) to (I) containing an alicyclic epoxy compound selected from the group described in (b-1a), (b-1b) and (b-1c) as component (B) The resin composition according to any one of (VII).
(IX) The resin composition according to any one of (I) to (VIII) above, which contains an epoxy compound having an alicyclic epoxy compound having a cyclohexane skeleton as component (B).
(X) The compound according to any one of (I) to (IX) above, wherein the compound contained as component (A) or component (B) is a bifunctional oxetane compound or a bifunctional epoxy compound. Resin composition.
(XI) The above (I) containing dicyclopentadiene dimethanol diglycidyl ether as component (A) and 3,4-epoxycyclohexenylmethyl-3 ′, 4 ′ epoxycyclohexene carboxylate as component (B) The resin composition according to any one of to (X).

(XII) The resin composition according to any one of (I) to (XI) above, wherein the curing agent (C) is a photocationic polymerization initiator or a thermal cationic polymerization initiator.
(XIII) The resin composition according to any one of (I) to (XII), wherein the curing agent (C) is a photocationic polymerization initiator selected from the group (C-1).
(XIV) The resin composition according to any one of (I) to (XIII) above, wherein the curing agent (C) is a sulfonium salt.
(XV) The resin composition according to any one of (I) to (XIV) above, wherein the viscosity of the resin composition is 1000 mPa · s or less, preferably 500 mPa · s or less, more preferably 300 mPa · s or less. .
(XVI) The resin composition is cured to obtain a cured product having a thickness of 100 μm, and the moisture permeability (water vapor permeability) of the cured product measured at 60 ° C. and 90% relative humidity is 45 g / m ² · 24 hr or less. The resin composition according to any one of (I) to (XV) above.
(XVII) The resin composition according to any one of (I) to (XVI) above, wherein the glass transition point (Tg) of the cured product of the resin composition is 80 ° C. or higher, more preferably 100 ° C. or higher.
(XVIII) The resin composition according to any one of (I) to (XVII), which has a curing shrinkage rate of 4% or less.
(XIX) The resin composition according to any one of (I) to (XVIII) above, wherein the liquid refractive index of the resin composition is 1.45 to 1.7.
(XX) The content of the component (A) is 20 to 80 parts by mass and the content of the component (B) is 20 to 80 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). The resin composition according to any one of (I) to (XIX) above, wherein the content of the curing agent (C) is 0.05 to 5 parts by mass.

The organic EL device solid sealing method according to the present invention includes a step of forming a passivation film on an organic EL device formed on a substrate, a surface sealing resin composition is applied on the passivation film, and sealing is performed. And a step of curing the surface sealing resin composition, and using the curable resin composition according to the present invention described above as the surface sealing resin composition. To do.

The organic EL element to be surface-sealed includes a substrate, a lower electrode, an organic EL layer including at least a light emitting layer, and an element unit body including an upper electrode. The substrate is a flat substrate made of an electrically insulating material such as a glass substrate, a transparent organic material made of cycloolefin, polycarbonate, polymethyl methacrylate, or the like, or an organic / inorganic hybrid transparent substrate made of the transparent organic material made of high-rigidity glass fiber or the like. Use a suitable substrate. Moreover, the following are mentioned as a typical structure of an element part main body.
(1) Lower electrode / light emitting layer / upper electrode (2) Lower electrode / electron transport layer / light emitting layer / upper electrode (3) Lower electrode / light emitting layer / hole transport layer / upper electrode (4) Lower electrode / electron transport Layer / light emitting layer / hole transport layer / upper electrode For example, in the organic EL device having the layer structure of (4) above, a lower electrode (cathode) made of an Al—Li alloy or the like is deposited on one side of a substrate by resistance heating vapor deposition. Then, as an organic EL layer, an electron transport layer composed of an oxadiazole derivative or a triazole derivative, a light emitting layer, TPD (N, N′-diphenyl-N, N′-bis (3-methylphenyl) ) -1,1-biphenyl-4,4'-diamine), etc., and the upper electrode (anode) are sequentially stacked by thin film formation methods such as resistance heating vapor deposition or ion beam sputtering. Is possible. The layer structure or material of the organic EL element is not particularly limited as long as it functions as a display element. The solid sealing method according to the present invention can be applied to any structure of organic EL elements.

The passivation film is formed so as to cover the organic EL element. The passivation film can be formed by a method such as vapor deposition or sputtering of an inorganic material such as silicon nitride or silicon oxide. The passivation film is provided to prevent moisture, ionic impurities, and the like from entering the organic EL element. The thickness of the passivation film is preferably in the range of 10 nm to 100 μm, and more preferably in the range of 100 nm to 10 μm. The passivation film may be laminated for the purpose of improving reliability.

Passivation films are generally incomplete films with pinholes or films with low mechanical strength, although depending on the deposition method. Therefore, in the solid sealing method, the reliability of sealing is improved by further applying an adhesive on the passivation film, press-bonding using a transparent substrate for sealing, and curing the adhesive.

Next, the present invention will be described in more detail with reference to examples. The present invention is not limited in any way by the following examples. The unit “part” of the numerical value indicates part by mass.

The resin composition of the present invention having the composition shown in Table 1 below, the resin composition of Comparative Example 1 and the resin composition of Reference Example 1 were prepared, and cured products of the respective resin compositions were obtained by the following methods. . The obtained resin composition and cured product (cured film) were evaluated by the following evaluation methods and evaluation criteria.

(1) Viscosity: Using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.), the viscosity at 25 ° C. (unit: mPa · s) of each resin composition described in Table 1 below was measured. .

(2) Liquid refractive index: The refractive index (25 ° C.) of each resin composition described in Table 1 below was measured with an Abbe refractometer (DR-M2: manufactured by Atago Co., Ltd.).

(3) Water vapor permeability: Each resin composition described in Table 1 below was sandwiched between glass substrates, and the film thickness was adjusted using a 100 μm spacer. Next, for the resin compositions of Example 1, Example 2, Comparative Example 1 and Reference Example 1, by irradiating ultraviolet rays with an integrated irradiation amount of 3000 mJ / cm ^{2 with} a high pressure mercury lamp (80 W / cm, ozone-less), The resin composition of Example 3 was cured by heating at 100 ° C. for 1 hour to prepare test pieces. For each of the obtained test pieces, the moisture permeability (unit: g / m ² · 24 hr) in an environment of 60 ° C. and 90% RH was measured using a Lyssy water vapor permeability meter L80-5000 (manufactured by Systemech Illinois). did.

(4) Tg (glass transition point, unit: ° C.): Viscoelasticity measurement system EXSTAR DMS-6000 (SII NanoTechnology Co., Ltd.) is used to determine the Tg point of the cured product obtained by curing in the same manner as (3) above. (Manufactured by the company), tensile mode, frequency 1 Hz.

(5) Curing shrinkage rate: A resin layer made of each resin composition described in Table 1 below was applied on a substrate. Next, for the resin compositions of Example 1, Example 2, Comparative Example 1 and Reference Example 1, by irradiating ultraviolet rays with an integrated irradiation amount of 3000 mJ / cm ^{2 with} a high pressure mercury lamp (80 W / cm, ozone-less), For the resin composition of Example 3, the resin composition was cured by heating at 100 ° C. for 1 hour in a drier to produce a cured product for film specific gravity measurement. This was measured based on JIS K7112 B method, and the specific gravity (DS) of the cured product was measured. Further, the specific gravity (DL) of the resin composition was measured at 23 ± 2 ° C., and the cure shrinkage rate was calculated by the following formula. A measurement result is shown by the average value of four measurement results.
Curing shrinkage (%) = (DS−DL) / DS × 100

(6) Light transmittance In the same manner as in (3) above, the resin compositions of Examples 1 to 3 were cured to prepare test pieces having a film thickness of 100 μm. About each obtained test piece, the light transmittance (%) of each wavelength in wavelength 380-780 nm was measured using the spectrophotometer (The Hitachi High-Technologies Corporation make, product name U-3900H). The light transmittance of the cured films (thickness: 100 μm) of the resin compositions of Examples 1 to 3 was 90% or more at each wavelength.

EP-4088S: manufactured by ADEKA Corporation, dicyclopentadiene dimethanol diglycidyl ether SEJ-01R: manufactured by Nippon Kayaku Co., Ltd., 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate OXT-121 : Toagosei Co., Ltd., xylylene bisoxetane MA-DGIC: Shikoku Kasei Kogyo Co., Ltd., monoallyl diglycidyl isocyanurate GSID 26-1: BASF Japan Ltd., (Tris [4- (4-acetylphenylsulfanyl) ) Phenyl] sulfonium tris [(trifluoromethyl) sulfonyl] methanide sunaide SI-100 main agent: Benzylmethyl-p-hydroxyphenylsulfonium hexafluoroantimonate epolite 80 manufactured by Sanshin Chemical Industry Co., Ltd. F: manufactured by Kyoeisha Chemical Co., glycerine diglycidyl ether Epo write 100MF: Kyoeisha Chemical Co., Ltd., trimethylolpropane triglycidyl ether

As is clear from the evaluation results of Examples 1 to 3, Reference Example 1 and Comparative Example 1, the cured product obtained from the resin composition of the present invention having a specific composition has a high Tg, a curing shrinkage rate and a water vapor transmission rate. The degree is low. Therefore, the hardened | cured material obtained from the resin composition of this invention is suitable for the coating agent for barrier films, various sealing materials, especially the surface sealing material of an organic EL element, for example.

The resin composition of the present invention and its cured product are excellent in visible light transmittance and light resistance, have a high Tg, and have a low curing shrinkage and water vapor permeability. Suitable for fastening materials.

Claims

A resin composition for surface sealing of an organic EL device comprising an alicyclic compound (A) having an oxetanyl group or an epoxy group, a cyclic compound (B) having an oxetanyl group or an epoxy group and satisfying the following conditions:
Conditions for the cyclic compound (B):
The ring in the cyclic compound (B) is an aliphatic ring or a heterocycle, and when the ring is an aliphatic ring, the cyclic compound is a compound used as the alicyclic compound (A). It is a compound having a different structure.
The resin composition according to claim 1, wherein the alicyclic compound (A) has a skeleton selected from the group described in the following (A-1).
A-1: Tricyclodecane, isobornyl, adamantane, cyclopentane, cyclohexane, hydrogenated bisphenol A, hydrogenated bisphenol F, and hydrogenated bisphenol S.
The alicyclic compound (A) is an oxetane compound or an epoxy compound having a skeleton selected from the group consisting of tricyclodecane, adamantane, cyclohexane and hydrogenated bisphenol A as an aliphatic ring. 2. The resin composition according to 2.
The resin composition according to any one of claims 1 to 3, wherein the cyclic compound (B) has a skeleton selected from the group described in the following (B-1).
B-1: Tricyclodecane, isobornyl, adamantane, cyclopentane, cyclohexane, hydrogenated bisphenol A, hydrogenated bisphenol F, and hydrogenated bisphenol S.
The resin composition according to claim 4, wherein the cyclic compound (B) is an oxetane compound or an epoxy compound having a skeleton selected from the group consisting of tricyclodecane, adamantane, cyclohexane, and hydrogenated bisphenol A as an aliphatic ring. object.
The resin composition according to any one of claims 1 to 3, wherein the cyclic compound (B) has a skeleton selected from the group described in the following (B-3).
B-3: Morpholine, tetrahydrofuran, oxane, dioxane, triazine, carbazole, pyrrolidine and piperidine.
The resin composition according to claim 6, wherein the cyclic compound (B) is an epoxy compound having a skeleton selected from the group consisting of oxane, dioxane and triazine as a heterocycle.
The resin composition according to any one of claims 1 to 7, further comprising a curing agent (C).
The resin composition according to claim 8, wherein the curing agent (C) is a cationic photopolymerization initiator and the resin composition is an energy ray curable resin composition.
The energy ray-curable resin composition according to claim 9, wherein the cationic photopolymerization initiator is a compound selected from the group described in (C-1) below.
C-1: sulfonium salt, iodonium salt, phosphonium salt, ammonium salt and antimonate.
The resin composition according to claim 8, wherein the curing agent (C) is a thermosetting agent, and the resin composition is a thermosetting resin composition.
The thermosetting resin composition according to claim 11, wherein the thermosetting agent is a compound selected from the group described in the following (C-2).
C-2: Amine compound, acid anhydride compound, amide compound, phenol compound, carboxylic acid compound, imidazole compound, isocyanuric acid adduct, metal compound, sulfonium salt, ammonium salt, antimonate, phosphonium Salt and microcapsule type curing agents.
The alicyclic compound (A) is contained in an amount of 20 to 80 parts by mass with respect to 100 parts by mass of the total amount of the alicyclic compound (A) and the cyclic compound (B). The resin composition according to one item.
The cyclic compound (B) is contained in an amount of 20 to 80 parts by mass with respect to 100 parts by mass of the total amount of the alicyclic compound (A) and the cyclic compound (B). The resin composition described in 1.
The hardener (C) is contained in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of the alicyclic compound (A) and the cyclic compound (B). The resin composition according to item.
The resin composition according to any one of claims 1 to 15, wherein the viscosity measured at 25 ° C is 15 Pa · s or less.
An organic EL display whose surface is sealed with a cured product obtained by curing the resin composition according to any one of claims 1 to 16.
The film for surface sealing of the organic EL display which has the barrier performance formed by apply | coating and hardening the resin composition as described in any one of Claims 1 thru | or 16 on a base material.
Use of the resin composition according to any one of claims 1 to 16 for surface sealing of an organic EL device.