WO2014013716A1

WO2014013716A1 - Energy ray-curable resin composition and cured product thereof

Info

Publication number: WO2014013716A1
Application number: PCT/JP2013/004331
Authority: WO
Inventors: 伸彦内藤; 雄一朗松尾; 淳子市川; 貴文水口; 裕貴堤
Original assignee: 日本化薬株式会社
Priority date: 2012-07-19
Filing date: 2013-07-16
Publication date: 2014-01-23
Also published as: KR20150036071A; TWI603963B; CN104470971A; CN104470971B; JP2014019800A; KR101980560B1; JP5916220B2; TW201410660A

Abstract

The present invention relates to an energy ray-curable resin composition for organic EL element sealing materials, which contains two or more compounds (A), for example, compounds represented by formula (1), said compounds (A) having two or more oxetane rings in each molecule. This resin composition has small curing shrinkage and provides a cured product that has excellent visible light transmittance, excellent light resistance, high Tg and low water vapor transmission rate. Consequently, this resin composition is useful as a solid sealing material for solid sealing of organic EL elements. (In formula (1), each R₁ independently represents a direct bond or a linear or branched chain hydrocarbon group having 1-6 carbon atoms; R₂ represents a linear or branched chain hydrocarbon group having 1-15 carbon atoms or a hydrocarbon group containing an alicyclic ring, an aromatic ring, a heterocyclic ring or a fused ring; each R₃ independently represents a linear or branched chain hydrocarbon group having 1-6 carbon atoms; and n represents 0 (zero) or an integer having an average of 1-5.)

Description

Energy ray curable resin composition and cured product thereof

Energy beam curable resin is generally excellent in workability because it can be processed without solvent. Further, since the curing speed is fast and the energy requirement is low, the energy beam curing technique is an important technique in various industries including display peripheral materials. 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 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. Yes. 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. 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. 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 the sealing of organic EL elements by the solid sealing method, it is possible to use a heat or photo-curing resin as an adhesive for sealing. This is very important because it can have a significant impact. 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.
Several curable resin compositions containing an oxetane compound are known (for example, Patent Documents 1 to 5). However, a cured resin composition used for organic EL in which at least two compounds having at least two oxetane rings are used in combination is not known.

Japanese Patent No. 3876630 Japanese Patent No. 2679586 Japanese Patent No. 442138 Patent No. 4655172 JP 2000-169552 A

A resin composition suitable for an organic EL device sealing material has a low curing shrinkage rate, and a cured product obtained from the resin composition has excellent visible light transmittance, light resistance and curability, and a high Tg. The water vapor permeability is required to be low. The objective of this invention is providing the resin composition suitable for the sealing material of an organic EL element which satisfy | fills such a request | requirement, and the hardened | cured material obtained from this resin composition.

As a result of intensive studies to solve the above problems, the present inventors have found that an energy beam curable resin composition containing at least two kinds of compounds (A) having two or more oxetane rings in the molecule and a cured product thereof. The inventors have found that the above problems can be solved and completed the present invention.

That is, the present invention relates to the following (1) to (23).
(1) An energy ray curable resin composition for an organic EL device sealing material containing two or more compounds (A) having two or more oxetane rings in the molecule.
(2) The energy ray curable resin composition does not contain an organic compound component that does not have a reactive group having a weight average molecular weight of 10,000 g / mol or more, or if included, its content is the resin composition. The energy ray-curable resin composition for an organic EL device sealing material according to (1), which is less than 1.5% by weight based on the total amount of the product.
(3) A compound in which the compound (A) having two or more oxetane rings in the molecule has an oxetane ring represented by at least the following general formula (1) or the following general formula (2):
Formula (1)

(In the formula, each R ₁ independently represents a direct bond or a linear or branched hydrocarbon group having 1 to 6 carbon atoms, and R ₂ represents a linear or branched carbon group having 1 to 15 carbon atoms. A hydrogen group or a hydrocarbon group containing an alicyclic ring, an aromatic ring, a heterocyclic ring or a condensed ring, and R ₃ each independently represents a straight or branched hydrocarbon group having 1 to 6 carbon atoms, n Represents an average value of an integer of 1 to 5),
Formula (2)

(Wherein R ₄ is independently a linear or branched hydrocarbon group having 1 to 6 carbon atoms, and R ₅ is each independently a linear or branched hydrocarbon group having 1 to 6 carbon atoms. Group),
The energy ray-curable resin composition for an organic EL device sealing material according to the above (1) or (2).

(4) The organic EL according to any one of (1) to (3), wherein the compound (A) having two or more oxetane rings in the molecule is a compound having at least an alicyclic ring or an aromatic ring in the molecule. An energy ray curable resin composition for an element sealing material.
(5) The compound (A) having two or more oxetane rings in the molecule, the compound of the above formula (1) and the compound of the above formula (2), any one of (1) to (4) Energy beam curable resin composition for organic EL device sealing material according to 2.
(6) The organic EL device package according to (5), wherein the content of the compound of the formula (2) is in the range of 0.6 to 1.5 parts by mass with respect to 1 part by mass of the compound of the formula (1) An energy ray curable resin composition for a stopper.
(7) It contains two or more compounds (A) having two or more oxetane rings in the molecule, the total organic compound component contained in the resin composition has a weight average molecular weight of 10,000 g / mol or less, and The energy ray-curable resin composition for an organic EL device sealing material according to any one of the above (1) to (5), which is composed of components mutually soluble at 20 ° C. to 80 ° C.
(8) Any one of (1) to (6) above, which does not contain (meth) acrylate compound or is contained but is less than 15 parts by mass with respect to 100 parts by mass of the total amount of the resin composition excluding the solvent. The energy ray-curable resin composition for organic EL device sealing material according to Item.

(9) Further, either or both of the epoxy compound (B) and the photocationic polymerization initiator (C) are contained, and the content thereof is 0.1% with respect to 100 parts by mass of the total amount of the resin composition excluding the solvent. (1) to (8), wherein the compound (A) is 30 to 99.9 parts by mass with respect to 100 parts by mass of the total amount of the resin composition excluding the solvent. The energy-beam curable resin composition for organic electroluminescent element sealing materials as described in any one of these.
(10) The energy ray-curable resin composition for an organic EL device sealing material according to any one of (1) to (8), further comprising an epoxy compound (B).
(11) The energy ray-curable resin composition for an organic EL device sealing material according to the above (9) or (10), wherein the epoxy compound (B) is an alicyclic epoxy compound.
(12) The energy ray curable type for organic EL device sealing material according to any one of (9) to (11), wherein the epoxy compound (B) is a compound having two or more epoxy groups in the molecule. Resin composition.
(13) Any one of (10) to (12), wherein the epoxy compound (B) is contained in an amount of 20 to 70 parts by mass with respect to 100 parts by mass of the total amount of the compound (A) and the epoxy compound (B). Energy beam curable resin composition for organic EL device sealing material according to 2.
(14) The compound (A) having 30 to 90 parts by mass of the compound (A) having two or more oxetane rings in the molecule with respect to 100 parts by mass in total of the compound (A) and the epoxy compound (B) (10 ) To (13) The energy ray-curable resin composition for an organic EL device sealing material according to any one of the above.

(15) The energy ray-curable resin composition for an organic EL device sealing material according to any one of (1) to (14) 11, further comprising a cationic photopolymerization initiator (C).
(16) The organic EL device package according to (15), wherein the cationic photopolymerization initiator (C) is at least one selected from the group consisting of a sulfonium salt, an iodonium salt, a phosphonium salt, an ammonium salt, and an antimonate. An energy ray curable resin composition for a stopper.
(17) The energy ray-curable resin composition for an organic EL device sealing material according to any one of (1) to (16), further containing fine particles (D).
(18) The energy ray-curable resin composition for organic EL device sealing material according to (17), wherein the primary particle size of the fine particles (D) is 100 nm or less.
(19) The energy ray-curable resin composition for an organic EL device sealing material according to any one of (1) to (18), wherein the viscosity at 25 ° C. measured with an E-type viscometer is 10 mPa · s or more. object.
(20) The energy shrinkage type for an organic EL device sealing material according to any one of (1) to (15), wherein a curing shrinkage rate when the resin composition is cured is 5.5% or less. Resin composition.
(21) A cured product obtained by curing the energy ray-curable resin composition for an organic EL device sealing material according to any one of (1) to (20).
(22) The cured product according to (21), wherein the water vapor transmission rate at a thickness of 100 μm is 200 g / m ² · day / 60 ° C. or less.
(23) An organic EL display having the cured product according to (21) or (22).

The energy ray-curable resin composition for organic EL device sealing material of the present invention (hereinafter also simply referred to as the resin composition of the present invention) has a low curing shrinkage, and the cured product of the resin composition has a visible light transmittance, Since it has excellent light resistance, high heat resistance, and low water vapor permeability, it is particularly suitable as a sealing material for organic EL elements.

The term “for organic EL element sealing material” in the present invention is a solid sealing agent filled between a sealing substrate such as glass and an organic EL element in sealing of an organic EL element, particularly in solid sealing. Means use.
The resin composition of the present invention is characterized by containing two or more compounds (A) having two or more oxetane rings in the molecule.
With the above configuration, two types of bifunctional oxetane compounds are mutually introduced into the curing system at the time of curing, and heat resistance, rigidity, refractive index control, water resistance, low shrinkage ratio that could not be achieved with one type It is possible to simultaneously achieve the effects.
That is, it was difficult to achieve the above-mentioned effects simultaneously by using one type of bifunctional oxetane compound or using a monofunctional oxetane compound and one type of bifunctional oxetane compound. However, by using two types of bifunctional oxetane compounds, two or more types of oxetane compounds are complicated in the curing system while maintaining low shrinkage, high rigidity, high refractive index, and high water resistance during curing. Since it is introduced, it becomes possible to provide a cured product having extremely high heat resistance (high glass transition point (Tg)) that cannot be achieved by only one kind as a synergistic effect. Furthermore, by using two or more types, it becomes extremely easy to control the heat resistance, rigidity, refractive index, and shrinkage rate.

As the compound (A) having at least two oxetane rings in the molecule contained in the resin composition of the present invention, any compound having at least two oxetane rings in the molecule can be used. .
Examples of the compound (A) having at least two oxetane rings in the molecule include 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene (commercially available as a main component thereof) Aron oxetane ^RTM OXT-121) (contains 80% or more) (Toagosei Co., Ltd.); xylylene bisoxetane), 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane , Di [2- (3-oxetanyl) butyl] ether, 1,4-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,3-bis [(3-ethyloxetan-3-yl) Methoxy] benzene, 1,2-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 4,4′-bis [(3-ethyloxetane-3- L) 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-ethyloxetane-3-yl) methoxy] naphthalene, 1,6-bis [(3-ethyloxetane-3-yl) methoxy] -2, 2,3,3,4,4,5,5-octafluorohexane, 3 (4), 8 (9) -bis [(1-ethyl-3-oxetanyl) methoxymethyl] -tricyclo [5.2.1 .2.6] decane, 1,2-bis {[2- (1-ethyl-3-oxetanyl) methoxy] ethylthio} ethane, 4,4′-bis [(1-ethyl-3-oxetanyl) methyl] thio Dibenzenethioether, 2, -Bis [(3-ethyloxetane-3-yl) methoxymethyl] norbornane, 2-ethyl-2-[(3-ethyloxetane-3-yl) methoxymethyl] -1,3-O-bis [(1- Ethyl-3-oxetanyl) methyl] -propane-1,3-diol, 2,2-dimethyl-1,3-O-bis [(3-ethyloxetane-3-yl) methyl] -propane-1,3- Diol, 2-butyl-2-ethyl-1,3-O-bis [(3-ethyloxetane-3-yl) methyl] -propane-1,3-diol, 1,4-O-bis [(3- And ethyl oxetane-3-yl) methyl] -butane-1,4-diol, 2,4,6-O-tris [(3-ethyloxetane-3-yl) methyl] cyanuric acid. Two or more of these are preferably used, and at least one is preferably an oxetane compound having an alkyleneoxy group.

Examples of the oxetane compound having at least two oxetane rings used in the present invention include oxetane compounds in which at least two oxetane rings are connected by a bridging group containing at least one ether bond. In the present invention, preferably, at least two kinds of the oxetane compounds are used. In a preferred embodiment, two different types are used. In a preferred embodiment, two types of the oxetane compound in which the above-described crosslinking group containing an ether bond is a chain-like crosslinking group not containing a ring structure and the oxetane compound being a chain-like crosslinking group containing a ring structure are used in combination. It is an aspect. By using the two kinds of oxetane compounds in combination, the above effects can be achieved better.
Examples of the oxetane compound in which at least two oxetane rings are linked by a bridging group containing at least one ether bond include the compounds of the above general formula (1) or general formula (2). The “crosslinking group” in the present invention means a divalent group that bonds between two atoms.
As the two kinds of combinations of the oxetane compounds, a combination of the compound of the general formula (1) and the compound of the general formula (2) is preferable. In particular, the combination of xylylene bisoxetane and 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane is particularly preferable because it is easily available from the market.

One preferred compound used as the bifunctional oxetane compound in the present invention is represented by the general formula (1)

(Wherein R ₁ independently represents a direct bond or a linear or branched hydrocarbon group having 1 to 6 carbon atoms (hydrocarbon bond), and R ₂ represents a linear or branched group having 1 to 15 carbon atoms. A chain hydrocarbon group (hydrocarbon bond) or a hydrocarbon group containing an alicyclic ring, an aromatic ring, a heterocyclic ring or a condensed ring, wherein R ₃ is each independently a straight chain or branched chain having 1 to 6 carbon atoms Represents a chain hydrocarbon group, and n represents an integer of 1 to 5 on average.)
An oxetane compound represented by:
In addition, R ₁ and R ₂ in the above formula (1) are divalent hydrocarbon groups as is clear from the above structural formula, and R ₃ is a monovalent hydrocarbon group.
R ₁ is preferably a linear or branched hydrocarbon group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably an alkylene group having 1 to 3 carbon atoms.
R ₂ is preferably an alkylene group having a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 1 to 12 carbon atoms, a phenylene group having 3 to 12 carbon atoms or a cycloalkylene group, and having 6 carbon atoms. An alkylene group having -12 phenylene groups (preferably an alkylene group having 1 to 4 carbon atoms) is particularly preferred.
R ₃ is preferably an alkyl group having 1 to 3 carbon atoms.
n is preferably 1 to 3.
In the compound of the above formula (1), R ₂ has an oxetane having a ring structure such as an alicyclic ring, an aromatic ring, a heterocyclic ring or a condensed ring (for example, a phenylene group, a naphthalene group or a cycloalkylene group having 3 to 8 carbon atoms). Use of a compound is preferable because the curing shrinkage ratio is reduced and the Tg (glass transition point), rigidity, and refractive index of the cured product are improved.
Here, in the compound of the above formula (1), as a particularly preferred specific example, the following general formula (3)

(Wherein R ₃ represents the same meaning as in the formula (1) and may be the same or different. Z represents a cyclic group having 3 to 12 carbon atoms, and the ring is an alicyclic ring (aliphatic ring); (Aromatic ring, heterocyclic ring or condensed ring may be used, and n represents an integer of 1 to 5 on average.)
It is a compound represented by these.
As the cyclic group having 3 to 12 carbon atoms of Z, a divalent aliphatic ring group or an aromatic ring group is preferable, and a phenylene group is particularly preferable.
By using the compound of the above formula (3), the curing shrinkage rate can be kept lower.

The oxetane compound represented by the following general formula (2) is as follows.

In the formula, each R ₄ is independently a linear or branched hydrocarbon group having 1 to 6 carbon atoms, and R ₅ is each independently a linear or branched hydrocarbon group having 1 to 6 carbon atoms. Represents. As is clear from the above structural formula, R ₄ is a divalent hydrocarbon group having 1 to 6 carbon atoms, and R ₅ is a monovalent hydrocarbon group.
In the above formula (2), R ₄ is a straight-chain hydrocarbon group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms.
In R ₅ , a straight-chain hydrocarbon group having 1 to 3 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is particularly preferable.

Further, if one of the components is an oxetane compound having a ring structure such as an alicyclic ring, an aromatic ring, a heterocyclic ring, or a condensed ring (for example, a phenylene group, a naphthalene group, or a cycloalkylene group having 3 to 8 carbon atoms), This is preferable because Tg (glass transition point), rigidity, and refractive index are improved. More preferably, it is an oxetane compound whose ring structure is an alicyclic ring or an aromatic ring. Specifically, it is a compound represented by the general formula (3). The content of the component (A) of the present invention is 30 to 100 parts by weight, more preferably 30 to 90 parts by weight, based on 100 parts by weight of the total amount of the component (A) + component (B) as the reactive compound. Particularly preferred is 40 to 90 parts by mass. In some cases, the content of the component (A) is preferably 30 to 80 parts by mass, more preferably 50 to 75 parts by mass. The balance is component (B).
Further, the content ratio of the component (A) to 100 parts by mass of the total amount of the resin composition of the present invention (excluding the solvent when a solvent is included) is usually 30 to 99.9 parts by mass, more preferably 40 to 99. The functional group equivalent of component (A) is preferably 10 to 500 g / eq, more preferably 50 to 250 g / eq.
The oxetane compound having a functional group equivalent of 50 to 150 g / eq (preferably a compound represented by the formula (2)) and an oxetane compound having an aromatic ring having a functional group equivalent of 100 to 200 g / eq (preferably A resin composition having a high refractive index while having a high Tg (glass transition point) by combining a compound represented by formula (3), more preferably a compound in which Z is a phenylene group in formula (3) Can be obtained.
When the compound of the formula (1) (preferably the compound of the formula (3)) and the compound of the formula (2) are used in combination, the ratio of both is the formula (2) with respect to 1 part by mass of the compound of the formula (1). ) In the range of usually 0.6 to 1.5 parts by weight, preferably 0.7 to 1.3 parts by weight, more preferably 0.8 to 1.2 parts by weight, most preferably 0.8. The range is 9 to 1.1 parts by mass.

The compound (B) having an epoxy group contained in the resin composition of the present invention (hereinafter also referred to as epoxy compound (B) or component (B)) may be any of a monofunctional epoxy compound and a polyfunctional epoxy compound. Moreover, any of an epoxy compound containing an aromatic ring (aromatic epoxy compound) and an aliphatic epoxy compound not containing an aromatic ring may be used. In the present invention, an aromatic epoxy compound or an epoxy compound containing an aliphatic ring (aliphatic ring-containing epoxy compound) is preferred. In particular, an alicyclic epoxy in which an epoxy group is formed on an aliphatic ring is preferable.

Examples of the monofunctional epoxy compound include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, and 1,3-butadiene monooxide. 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, etc. It is done.

Examples of polyfunctional epoxy compounds include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S di Glycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-methane-dioxane, bis (3,4-epoxy Hexylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy- 6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate) ), Dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether Ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8- Examples include diepoxyoctane and 1,2,5,6-diepoxycyclooctane.

As examples of the alicyclic epoxy, any compound containing cyclohexene oxide or cyclopentene oxide can be used. Specific examples of the alicyclic epoxy include compounds having the following structure.

(In the formula, n is an average value and represents a positive number of 1 to 5.)

The epoxy compound (B) used in the present invention is not limited to those exemplified above as long as it is a commonly used epoxy resin.
Among the above epoxy compounds, aromatic epoxy compounds and alicyclic epoxy compounds are preferable from the viewpoint of excellent curing speed, and alicyclic epoxy compounds are particularly preferable. Among the alicyclic epoxy compounds, bifunctional alicyclic epoxy compounds are preferable, and 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate is particularly preferable.
The said epoxy compound (B) may be used independently and may use 2 or more types. The content of the component (B) of the present invention is usually 0 to 70 parts by weight, preferably 10 to 70 parts by weight, based on 100 parts by weight of the total amount of the component (A) + component (B) as the reactive compound. More preferably, it is 20 to 70 parts by mass, and particularly preferably 25 to 50 parts by mass. In some cases, 10 to 60 parts by mass is more preferable.
The epoxy equivalent of the epoxy compound (B) used in the present invention is preferably 50 to 500 g / eq, more preferably 100 to 300 g / eq.

Examples of the photocationic polymerization initiator (C) contained in the resin composition of the present invention include aromatic iodonium complex salts and aromatic sulfonium complex salts.

Specific examples of the aromatic iodonium complex salt include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and the like.

Specific examples of the aromatic sulfonium complex salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide— Bishexafluorophosphate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenylsulfide-bishexafluoroantimonate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoro Phosphate, 7- [Di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoroantimonate, 7- [Di (p-toluyl) sulfonio] -2- Sopropyltetrakis (pentafluorophenyl) borate, phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-hexafluorophosphate, phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-hexafluoroantimonate, 4-tert-butyl Phenylcarbonyl-4′-diphenylsulfonio-diphenylsulfide-hexafluorophosphate, 4-tert-butylphenylcarbonyl-4′-diphenylsulfonio-diphenylsulfide-hexafluoroantimonate, 4-tert-butylphenylcarbonyl-4 ′ -Diphenylsulfonio-diphenylsulfide-tetrakis (pentafluorophenyl) borate, thiophenyldiphenylsulfonium hex Safluoroantimonate, thiophenyldiphenylsulfonium hexafluorophosphate, 4- {4- (2-chlorobenzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, halogen of thiophenyldiphenylsulfonium hexafluoroantimonate 4,4 ′, 4 ″ -tri (β-hydroxyethoxyphenyl) sulfonium hexafluoroantimonate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide-bishexafluoroantimonate, diphenyl [4- ( Phenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tris Can be exemplified (trifluoromethyl) sulfonyl] methanides like.

Among aromatic sulfonium complex salts, thiophenyldiphenylsulfonium hexafluoroantimonate, 4- {4- (2-chlorobenzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoro, which is highly sensitive and easily available from the market Antimonate, diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tris [(trifluoromethyl) sulfonyl] methanide and the like are preferable.
Furthermore, in view of the harm to the environment and the human body and the regulations of each country, diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate, tris [4- (4-acetyl), which does not contain an antimony element. Most preferably, phenylsulfanyl) phenyl] sulfonium tris [(trifluoromethyl) sulfonyl] methanide is used.
The content of the component (C) of the present invention is 0.1 to 10 parts by weight, preferably 0.5 to 3 parts by weight with respect to 100 parts by weight as a total of component (A) + component (B). .
Moreover, the ratio of the component (C) with respect to 100 parts by mass of the total amount of the resin composition (excluding the solvent when the solvent is included) is also preferably in the same range as described above. Furthermore, the content ratio of the component (C) with respect to 100 parts by mass of the component (A) is preferably in the same range as above.
In addition, in the resin composition of this invention, a photocationic polymerization initiator (C) may be used independently, and multiple types may be mixed and used for it.
Moreover, a radical type photoinitiator can be used together. Any photopolymerization initiator may be used as long as it is a radical photopolymerization initiator, and examples thereof include 2-hydroxy-2-methyl-phenylpropan-1-one or 1-hydroxycyclohexyl-phenylketone.

Examples of the fine particles (D) used in the present invention include organic fine particles and inorganic fine particles. In addition, the fine particles (D) may be used alone or as a mixture of a plurality of types as required in consideration of the required light transmittance, hardness, scratch resistance, curing shrinkage rate, and refractive index. it can. By using the fine particles (D), the curing shrinkage rate of the resin composition of the present invention and the moisture permeability of the cured product of the resin composition can be reduced, and the liquid refractive index can be increased.
On the other hand, from the viewpoint of improving the light transmittance of the cured product (particularly the light transmittance in the wavelength range of 380 nm to 780 nm), the resin composition of the present invention should not contain the fine particles (D). preferable.

The organic fine particles 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, and porous urethane resin. Porous organic polymer beads such as beads, porous polycarbonate resin beads, resin powder of benzoguanamine-formalin condensate, resin powder of benzoguanamine-melamine-formalin condensate, resin powder of urea-formalin condensate, powder of aspartate derivative , Zinc stearate powder, stearamide powder, epoxy resin powder, polyethylene powder, etc. Crosslinked polymethyl methacrylate resin beads and crosslinked polymethyl methacrylate / styrene resin beads Etc. are preferred. 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 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-doped oxide. Examples include zinc and fluorine-doped tin oxide.

Examples of the transparent metal oxide 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 / oxidation. Examples thereof include a tin / antimony pentoxide composite and a titanium oxide / zirconium oxide / tin oxide composite.

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

The fine particles used in the present invention are preferably fine particles having excellent hardness and scratch resistance and a high refractive index. Titanium oxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, titanium oxide / zirconium oxide / tin oxide / five Metal oxide fine particles such as antimony oxide composite, zirconium oxide / tin oxide / antimony pentoxide composite, and 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. The blending ratio of these is usually 0 to 30 parts by mass with respect to 100 parts by mass of the total amount of component (A) + component (B), and is usually 1 to 30 parts by mass, preferably 5 ~ 20 parts by mass.

In addition, as a fine particle dispersant, a polycarboxylic acid dispersant, a silane coupling agent, a titanate coupling agent, a silicone dispersant such as a modified silicone oil, or an organic copolymer dispersant may be used in combination. Is possible. The blending ratio thereof is about 0 to 30% by mass, preferably about 0.05 to 5% by mass with respect to the total mass of the resin composition of the present invention (total amount of the resin composition excluding the solvent).

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 can be measured under the condition of an acceleration voltage of 30 kV using a JSM-7700F field emission scanning electron microscope manufactured by JEOL Ltd.
In the present invention, the primary particle size is preferably 100 nm or less. Fine particles having a size of 5 to 100 nm can be preferably used. By being 100 nm or less, it becomes possible to provide a cured product having a low curing shrinkage rate and moisture permeability and a relatively high light transmittance of the resin composition.

These fine particles can be used by being dispersed in a solvent. In particular, inorganic fine particles can be obtained commercially in a form dispersed in water or an organic solvent. Examples of the organic solvent used for dispersing the inorganic fine particles include hydrocarbon solvents, ester solvents, ether solvents, and ketone solvents.
Examples of hydrocarbon solvents include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane, and decane, and mixtures of petroleum ether, white gasoline, Solvent naphtha etc. are mentioned.
Examples of ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, 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, butylene glycol monomethyl ether monoacetate, dialkyl glutarate, dialkyl succinate, Polycarboxylic acid alkyl ester such as dialkyl adipate Kind, and the like.
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. Examples include ethers and cyclic ethers such as tetrahydrofuran.
Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

The resin composition of the present invention uses a reactive compound in addition to the component (A) and the component (B) in consideration of the viscosity, refractive index, adhesion and the like of the resin composition of the present invention to be obtained. May be. Specific examples include (meth) acrylate compounds.
As the (meth) acrylate compound, monofunctional (meth) acrylate, bifunctional (meth) acrylate, polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in the molecule, urethane (meth) acrylate, Polyester (meth) acrylate, epoxy (meth) acrylate, and the like can be used.
In the present invention, from the viewpoint of keeping the curing shrinkage rate small, these (meth) acrylate compounds are not included, or if included, to the extent that the curing shrinkage rate is not increased, for example, the resin composition excluding the solvent The total amount is usually less than 15 parts by mass, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and most preferably 2 parts by mass or less with respect to 100 parts by mass. In the present invention, from the viewpoint of keeping the curing shrinkage rate small, an embodiment not containing the (meth) acrylate compound is most preferable.

Examples of monofunctional (meth) acrylates include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and cyclohexyl (meth) acrylate. Alicyclic (meth) acrylates such as: tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, (meth) acrylate having a heterocycle such as morpholine (meth) acrylate; 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, p-phenylbenzyl acrylate; carbazole (poly) ethoxy (meth) acrylate, carbazole (poly) propoxy (meth) acrylate, (poly) (Meth) acrylate having a heterocyclic ring such as caprolactone-modified carbazole (meth) acrylate; naphthyl (meth) acrylate, naphthyl (poly) ethoxy (meth) acrylate, naphthyl ( Re) 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 It has a condensed ring such as binaphthol (meth) acrylate, naphthol (meth) acrylate, naphthol (poly) ethoxy (meth) acrylate, naphthol (poly) propoxy (meth) acrylate, (poly) caprolactone-modified naphthol (meth) acrylate (meta) ) Acrylate; imide (meth) acrylate having an imide ring structure; butanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylates having hydroxyl groups such as (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 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, isomyristyl (meth) acrylate (Meth) acrylates having alkyl groups such as relate and lauryl (meth) acrylate; ethoxydiethylene glycol (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, etc. And (meth) acrylates of polyhydric alcohols.

Examples of the (meth) acrylate monomer having two functional groups include (meth) acrylate having a heterocycle such as hydropivalaldehyde-modified trimethylolpropane di (meth) acrylate; (poly) ethoxy-modified bisphenol A di (meth) 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 (meta) ) Acrylate, (poly) propoxy-modified bisphenol S di (meth) acrylate, hexahydrophthalic acid di (meth) acrylate, bisphenoxy (poly) ethoxyfluorene, biphenyldimethanol di (meth) acrylate (Meth) acrylate having an aromatic ring such as binaphthol di (meth) acrylate, binaphthol (poly) ethoxydi (meth) acrylate, binaphthol (poly) propoxy di (meth) acrylate, (poly) caprolactone-modified binaphthol di (meth) acrylate, etc. (Meth) acrylates having the following condensed rings: polycyclic rings such as bisphenol full orange (meth) acrylate, bisphenoxymethanol full orange (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate, and bisphenoxycaprolactone full orange (meth) acrylate (Meth) acrylate having an aromatic; acrylated isocyanate such as diacrylated isocyanurate; 1,4-butanediol di (meth) acrylate, 1,6 (Meth) acrylate having a linear methylene structure such as hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate; tricyclodecane dimethanol (meth) Di (meth) acrylate of polyhydric alcohol such as alicyclic (meth) acrylate such as acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene di (meth) acrylate ) Acrylate;

As the polyfunctional (meth) acrylate monomer, polyfunctional (meth) acrylate having an isocyanurate ring such as tris (acryloxyethyl) isocyanurate, (poly) caprolactone-modified tris (acryloxyethyl) isocyanurate; pentaerythritol tri ( (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) propoxy 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 trimethylol Of polyhydric alcohols such as propane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate and glycerol tri (meth) acrylate Functional (meth) acrylate; phosphorus-containing polyfunctional (meth) acrylate such as phosphoric acid tri (meth) acrylate; aromatic polyfunctional (meth) acrylate such as trimethylolpropane benzoate (meth) acrylate; Examples include acid-modified polyfunctional (meth) acrylates such as 2-trisacryloyloxymethyl succinic acid; polyfunctional (meth) acrylates having a silicone skeleton such as silicone hexa (meth) acrylate; and the like.

Examples of the urethane (meth) acrylate include a reaction product obtained by reacting a diol compound (including the following polyester diol) with an organic polyisocyanate and then adding a hydroxyl group-containing (meth) acrylate.
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, and 1,8-octane. Diol, 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, etc., or these diol compounds and dibasic acids Properly its anhydride (e.g., succinic acid, adipic acid, azelaic acid, dimer acid, isophthalic acid, terephthalic acid, phthalic acid or anhydrides thereof) and reactant polyester diol and the like can be mentioned is the.
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, hydrogenated toluene diisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene Range isocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diiso Aneto, 6-isopropyl-1,3-phenyl diisocyanate, 1,5-naphthalene diisocyanate and aromatic polyisocyanates such as may be exemplified in.

Epoxy (meth) acrylates include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, biphenyl type phenol aralkyl resin, terminal glycidyl ether of bisphenol A propylene oxide adduct, fluorene epoxy resin, bisphenol S. And a reaction product of epoxy resin such as epoxy resin and (meth) acrylic acid.

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) a Examples include acrylate and biphenyldimethanol 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. Biphenyldimethanol di (meth) acrylate.
In addition, in the resin composition of this invention, the (meth) acrylate which is another component may be added as needed, may be used independently, and may be used in mixture of multiple types.
In the present invention, when the component (A) + component (B) is 100 parts by mass, the blending ratio of the (meth) acrylate compound is usually 0 to 200 parts by mass, and in some cases 10 to 200 parts by mass. Yes, and may be 50 to 100 parts by mass, but if possible, it is not included in the resin composition of the present invention, or the minimum use is preferable.

Moreover, when using a (meth) acrylate compound, it is preferable to use photoinitiators other than the said photocationic polymerization initiator. Specifically, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, 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-methyl-1- [4- (methylthio) phenyl]- Acetophenones such as 2-morpholinopropan-1-one and oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone]; 2-ethylanthraquinone, 2-tert-butylant Anthraquinones such as quinone, 2-chloroanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone Benzophenones such as 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl)- Examples thereof include phosphine oxides such as phenylphosphine oxide and diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide. Preferred are acetophenones, and more preferred are 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl-phenyl ketone. 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 content ratio of the photopolymerization initiator is usually 0 to 10 parts by mass with respect to 100 parts by mass of the resin composition. When used, it is usually 0.001 to 10 parts by mass, preferably 0.01 to 8 parts by mass.

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, etc., but the component (A) + component (B) is 100 parts by mass. In this case, the content of component (A) is usually 30 to 100 parts by mass, preferably 30 to 80 parts by mass, more preferably 40 to 70 parts by mass, or 50 to 75 parts by mass. The content of component (B) is usually 0 to 70 parts by weight, preferably 20 to 70 parts by weight, more preferably 25 to 50 parts by weight, or 30 to 60 parts by weight. In the resin composition of the present invention, it is usually preferable to include the component (C), and the content of the component (C) is 0.1 to 10 parts by mass, preferably 0.5 to 3 parts by mass. The component (D) is an optional component and may be omitted, but may be included as necessary. When included, the component (D) is included in an amount of 1 to 30 masses per 100 parts by mass of the total amount of the component (A) + component (B). Part, preferably 5 to 20 parts by weight.
As one of the preferable embodiments of the present invention, there can be mentioned an embodiment containing either or both of (i) the compounds (A) and (ii) the epoxy compound (B) and the cationic photopolymerization initiator (C). . In that case, with respect to 100 parts by mass of the total amount of the resin composition excluding the solvent, the content of the compound (A) in (i) is usually 30 to 99.9 parts by mass, preferably 40 parts by mass. To 99.5 parts by mass, more preferably 50 to 99.5 parts by mass. In some cases, 40 to 90 parts by mass are preferable, and 50 to 80 parts by mass are more preferable. In addition, the content of component (B) and / or component (C) in (ii) above is the total amount, usually 0.1 to 70 with respect to 100 parts by mass of the total amount of the resin composition excluding the solvent. Part by mass, preferably 0.5 to 60 parts by mass, and in some cases, 10 to 60 parts by mass is preferable, and 20 to 50 parts by mass is more preferable.

In addition to the above components, the resin composition of the present invention may include a release agent, an antifoaming agent, a leveling agent, a light stabilizer, an antioxidant, a polymerization agent, as necessary, in order to improve convenience during handling. Additives such as inhibitors, plasticizers and antistatic agents can be used in combination depending on the situation.
The content of various additives is usually 0 to 10 parts by mass with respect to 100 parts by mass of the resin composition. When used, it is usually 0.001 to 10 parts by mass, preferably 0.01 to 8 parts by mass.

In many cases, plasticizers are used to obtain durability and flexibility. The plasticizer used is selected depending on the desired viscosity, durability, transparency, flexibility and the like. Specifically, olefinic 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, (2-ethylhexyl) sebacate, aliphatic dibasic acid esters such as diethyl succinate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate Orthophosphoric acid esters such as cresyl diphenyl phosphate and 2-ethylhexyl diphenyl phosphate, ricinoleic acid esters such as methylacetylricinoleate, polyesters such as poly (1,3-butanediol adipate), acetate esters such as glyceryl triacetate, N -Sulfonamides such as butylbenzenesulfonamide, polyethylene glycol benzoate, polyethylene glycol dibenzoate, polypropylene Polyalkylene oxide (di) benzoate such as recall benzoate, polypropylene glycol dibenzoate, polytetramethylene glycol benzoate, polytetramethylene glycol benzoate, polyether such as polypropylene glycol, polyethylene glycol, polytetramethylene glycol, polyethoxy modified bisphenol A, poly Polyalkoxy-modified bisphenol A such as propoxy-modified bisphenol A, polyethoxy-modified bisphenol F, polyalkoxy-modified bisphenol F such as polypropoxy-modified bisphenol F, polycyclic aromatics such as naphthalene, phenanthrene and anthracene, (bi) naphthol Ethoxy modified (bi) naphthol, (poly) propoxy modified (bi) naphthol, (poly) te Naphthol derivatives such as tramethylene glycol modified (bi) naphthol, (poly) caprolactone modified (bi) naphthol, diphenyl sulfide, diphenyl polysulfide, benzothiazolyl disulfide, diphenylthiourea, morpholinodithiobenzothiazole, cyclohexylbenzothiazole-2- And sulfur-containing compounds such as sulfenamine, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetrakis (2-ethylhexyl) thiuram disulfide, tetramethylthiuram monosulfide and dipentamethylenethiuram tetrasulfide. Preferred are (poly) ethylene glycol dibenzoate, (poly) propylene glycol dibenzoate, binaphthol, (poly) ethoxy modified binaphthol, (poly) propoxy modified binaphthol, and diphenyl sulfide.

Further, if necessary, softening agents such as polymers such as acrylic polymer, polyester elastomer, urethane polymer and nitrile rubber can be added.
The content of the plasticizer or softening agent is usually 0 to 90 parts by mass with respect to 100 parts by mass of the resin composition, and when used, it is 1 to 90 parts by mass, preferably 2 to 80 parts by mass. .

The organic compound component having no reactive group in the present invention includes an organic compound not containing an ion reactive or radical reactive group such as an oxetanyl group, an epoxy group, or a radical reactive unsaturated bond-containing group. , Organic fine particles in the fine particles (D), additives other than the components (A) to (D), and the like. These have a weight average molecular weight of preferably 10,000 g / mol or less, particularly preferably 5,000 g / mol or less, from the viewpoint of compatibility. In the present invention, the organic compound having no reactive group having a weight average molecular weight of 10,000 g / mol or more is not included in the resin composition of the present invention, or when it is included, the content thereof is an organic solvent. It is preferably 1.5% by weight or less, more preferably 1.0% by weight or less, and particularly preferably 0.5% by weight or less, based on the total amount of the resin composition excluding. By setting the amount to 1.5% by weight or less, it is possible to prevent the component having no reactive group from being incompatible and remaining as an insoluble component such as a solid or gel, and thus curing. It is preferable because the physical properties can be prevented from being inferior in transparency and heat resistance. 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.

In the resin composition of the present invention, the weight average molecular weight of each component of the organic compound used is preferably 10,000 g / mol or less, more preferably 5,000 g / mol or less. Since a component having a large weight average molecular weight is difficult to dissolve, the prepared resin composition becomes a turbid liquid. This is not preferable because the resin composition used for the display must be uniformly transparent. In addition, excellent characteristics are also required for the transmittance, and specifically, the light transmittance at each wavelength in the wavelength range of 380 to 780 nm is preferably 80% or more. The light transmittance can be measured with a measuring instrument such as a spectrophotometer U-3900H manufactured by Hitachi High-Technologies Corporation.

Some of the preferable aspects of the resin composition for organic EL element sealing materials of this invention are mentioned below. In the following description, when the total amount of the resin composition is referred to, when the resin composition contains a solvent, it means the total amount excluding it.
I. In the energy ray-curable resin composition for organic EL device sealing material containing at least two kinds of compounds (A) having two or more oxetane rings in the molecule, the molecule has two or more oxetane rings. A combination of at least two kinds of the compound (A) is a combination of the compound represented by the general formula (2) and the compound of the general formula (3), and with respect to 1 part by mass of the compound of the general formula (3), An embodiment comprising the compound represented by the general formula (2) in a proportion of 0.6 to 1.5 parts by mass.
II. The embodiment according to I above, wherein the content ratio of the compound represented by the general formula (2) is 0.8 to 1.2.
III. Further, the embodiment according to the above I or II, wherein the photocationic polymerization initiator (C) is contained at a ratio of 0.1 to 10 parts by mass with respect to 100 parts by mass of the total content of the compound (A).
IV. Further, according to any one of the above I to III, which further contains an epoxy compound (B) and contains 10 to 70 parts by mass with respect to 100 parts by mass of the total amount of the compound (A) and the epoxy compound (B). Description aspect.
V. The embodiment according to any one of I to IV above, wherein the content of the compound (A) is 50 parts by mass or more with respect to 100 parts by mass of the total amount of the resin composition.
VI. The embodiment according to any one of the above items I to V, which contains no (meth) acrylate compound or contains less than 15 parts by mass with respect to 100 parts by mass of the total amount of the resin composition.
VII. The embodiment according to any one of the above I to VI, wherein the cure shrinkage is 5.5% or less.
VIII. The embodiment according to any one of the above I to VI, wherein the cure shrinkage is 5% or less.
IX. The aspect according to any one of the above I to VI, wherein the organic EL element sealing material is for bonding a transparent substrate for sealing.

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 20 to 80 ° C., preferably 40 to 80 ° C. for 0.5 to 6 hours.

The viscosity of the resin composition of the present invention is only required to be able to form a coating film for adhering a solid organic EL sealing material (for example, glass or the like), and may be 10 mPa · s or more at 25 ° C. It is preferably about 10 to 3000 mPa · s. The viscosity of the resin composition of the present invention that does not contain fine particles (D) is about 10 to 150 mPa · s, preferably about 20 to 120 mPa · s. The viscosity of the resin composition of the present invention containing fine particles (D) is preferably about 300 to 3000 mPa · s, more preferably about 500 to 2500 Pa · s.
Moreover, as a viscosity suitable for the transferability of the shape at the time of manufacturing the optical lens shape | molded on a base material, and workability | operativity of workability, 10 mPa * s or more is preferable at 25 degreeC.

The resin composition of the present invention can be easily cured by 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. In order to increase the refractive index of the cured layer of the resin composition of the present invention, the liquid refractive index of the resin composition of the present invention is preferably high, and the liquid refractive index is usually 1.45 to 1.55. It is preferably 1.48 to 1.52. The liquid refractive index can be measured with an Abbe refractometer (model number: DR-M2, manufactured by Atago Co., Ltd.).
The curing shrinkage when the resin composition of the present invention is cured is preferably 5.5% or less, preferably 5% or less, more preferably 4.7% or less, and most preferably 4.5% or less. . The lower limit is preferably as small as possible, but is usually about 4% in the present invention.
When the resin composition of the present invention is a cured film having a thickness of 100 μm, the water vapor transmission rate at 60 ° C. is preferably 200 g / m ² · day or less, and preferably 100 g / m ² · day or less. More preferably, it is particularly preferably 60 g / m ² · day or less. By being in the said range, it becomes possible to prevent effectively that a device is damaged by permeation | transmission of a water | moisture content.

The solid sealing of the organic EL element using the resin composition of the present invention is usually a step of forming a passivation film on the organic EL element formed on the substrate, the resin composition of the present invention on the passivation film. It can be performed by applying a (sealing adhesive), a step of providing a sealing transparent substrate on the coating layer, and a step of curing the coating layer. Usually, as the transparent substrate for sealing, a transparent substrate such as glass that does not transmit moisture is used.

An organic EL element to be sealed includes a substrate (supporting substrate) that supports an element body that functions as the element, a lower electrode, an organic EL layer that includes at least a light emitting layer, and an element body that includes an upper electrode. Consists of The substrate is made of an electrically insulating material such as a glass substrate, a transparent organic material made of cycloolefin, polycarbonate, polymethylmethacrylate, or the like, or an organic / inorganic hybrid transparent substrate in which the transparent organic material is made highly rigid with glass fiber or the like. A flat substrate is used. 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, a hole transport layer composed of TPD (triphenyldiamine), etc., and an upper electrode (anode) Can be produced by sequentially laminating them by a thin film forming method such as resistance heating vapor deposition or ion beam sputtering. 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 is generally an incomplete film having pinholes or a film having low mechanical strength, although it depends on the film forming method. Therefore, in the solid sealing method, the reliability of sealing is improved by further applying an adhesive on the passivation film, press-bonding using a transparent substrate for sealing, and curing the adhesive.
An organic EL display having a cured product of the resin composition of the present invention can be obtained by incorporating (mounting) the sealed organic EL element obtained as described above into a display device.

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 and cured product of the present invention were obtained with the compositions shown in the following examples (Table 1). The evaluation method and evaluation criteria for the resin composition and the cured film were as follows. In addition, about the Example containing an organic solvent, it evaluated, after volatilizing an organic solvent fully with an evaporator.

(1) Viscosity: Viscosity was measured at 25 ° C. using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.).

(2) Liquid refractive index: The refractive index (25 ° C.) of the blended resin composition was measured with an Abbe refractometer (DR-M2: manufactured by Atago Co., Ltd.).

(3) Moisture permeability: UV curable resin was sandwiched between glass substrates, the thickness was adjusted using a 100 μm spacer, and cured at 3000 mJ / cm ² with a high-pressure mercury lamp (80 W / cm, ozone-less) to produce a test piece. . The moisture permeability of the obtained test piece was measured with a Lyssy water vapor permeability meter L80-5000 (manufactured by Systech Illinois), 60 ° C. × 90% RH.

(4) Tg (glass transition point): Viscoelasticity measurement system EXSTAR DMS-6000 (manufactured by SII Nanotechnology Co., Ltd.), tension mode, frequency 1 Hz, scan rate rate); measured at 2 ° C./min from room temperature.

(5) Curing shrinkage rate: An ultraviolet curable resin layer was applied on the substrate, and cured by irradiating 3000 mJ / cm ² with a high-pressure mercury lamp (80 W / cm, ozone-less) to produce a cured product for measuring film specific gravity. .
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) Brittleness: Easy-adhesion PET (A4300 100 μm thickness: manufactured by Toyobo Co., Ltd.) is applied with a Meyer bar coater with a thickness of 20 μm, and irradiated with 3000 mJ / cm ² with a high-pressure mercury lamp (80 W / cm, ozone-less). A test piece was obtained by curing. Thereafter, the test piece was evaluated by bending it 180 °.
○ ・・・ No crack occurrence × ・・・ Crack occurrence

(7) Light transmittance: An ultraviolet curable resin is sandwiched between glass substrates, the thickness is adjusted using a 60 μm spacer, and cured at 3000 mJ / cm ² with a high-pressure mercury lamp (80 W / cm, ozone-less) to produce a test piece. did. The light transmittance of each wavelength at wavelengths of 380 to 780 nm was measured using a spectrophotometer U-3900H (light source C) manufactured by Hitachi High-Technologies Corporation, and the numerical value at 400 nm was taken as the transmittance.

Table 1

In the above table, since Comparative Example 1 was not cured by irradiation at 3000 mJ / cm ^{2 with} a high-pressure mercury lamp (80 W / cm, ozone-less), only items that can be measured in liquid form were described.

OXT-121: Xylylenebisoxetane OXT-221 manufactured by Toagosei Co., Ltd .: 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane SEJ-01R manufactured by Toagosei Co., Ltd. 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate GSID 26-1 manufactured by Yakuhin Co., Ltd. (Tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tris [ (Trifluoromethyl) sulfonyl] methanide SZR-K: MEK dispersed zirconium oxide manufactured by Sakai Chemical Industry Co., Ltd. (solid content concentration 30%, primary particle size 4 nm)
OXT-101: 3-ethyl-3-hydroxymethyloxetane manufactured by Toagosei Co., Ltd.

As is clear from the evaluation results of Examples 1 to 3 and Comparative Examples 1 to 4, the resin composition of the present invention having a specific composition has a low cure shrinkage, the cured product has a high Tg, and a water vapor permeability. Low. Therefore, for example, it is suitable as various sealing materials, especially as a sealing material for organic EL elements, and can be used as an adhesive for bonding a transparent substrate for sealing in solid sealing of organic EL elements.

The resin composition of the present invention has a low curing shrinkage, and the cured product has excellent visible light transmittance and light resistance, high Tg, and low water vapor permeability. It is suitable as a sealing material and can be used as an adhesive for bonding a transparent substrate for sealing in solid sealing of an organic EL element.

Claims

An energy ray-curable resin composition for an organic EL device sealing material containing two or more compounds (A) having two or more oxetane rings in the molecule.
The energy ray curable resin composition does not contain an organic compound component that does not have a reactive group having a weight average molecular weight of 10,000 g / mol or more, or if included, the content is the total amount of the resin composition. The energy ray-curable resin composition for an organic EL device sealing material according to claim 1, wherein the content is less than 1.5% by weight.
A compound in which the compound (A) having two or more oxetane rings in the molecule has an oxetane ring represented by at least the following general formula (1) or the following general formula (2);
Formula (1)

(In the formula, each R 1 independently represents a direct bond or a linear or branched hydrocarbon group having 1 to 6 carbon atoms, and R 2 represents a linear or branched carbon group having 1 to 15 carbon atoms. A hydrogen group or a hydrocarbon group containing an alicyclic ring, an aromatic ring, a heterocyclic ring or a condensed ring, and R 3 each independently represents a straight or branched hydrocarbon group having 1 to 6 carbon atoms, n Represents an average value of an integer of 1 to 5),
Formula (2)

(Wherein R 4 is independently a linear or branched hydrocarbon group having 1 to 6 carbon atoms, and R 5 is each independently a linear or branched hydrocarbon group having 1 to 6 carbon atoms. Group),
The energy ray curable resin composition for organic EL device sealing materials according to claim 1 or 2.
The organic EL device sealing according to any one of claims 1 to 3, wherein the compound (A) having two or more oxetane rings in the molecule is a compound having at least an alicyclic ring or an aromatic ring in the molecule. Energy ray curable resin composition for materials.
The compound (A) having two or more oxetane rings in the molecule includes the compound of the above formula (1) and the compound of the above formula (2). An energy ray curable resin composition for an organic EL device sealing material.
The organic EL device sealing material according to claim 5, wherein the content of the compound of the formula (2) is in the range of 0.6 to 1.5 parts by mass with respect to 1 part by mass of the compound of the formula (1). Energy ray curable resin composition.
2 or more kinds of compounds (A) having two or more oxetane rings in the molecule, the total organic compound component contained in the resin composition has a weight average molecular weight of 10,000 g / mol or less, and 20 ° C. 6. The energy ray-curable resin composition for an organic EL device sealing material according to any one of claims 1 to 5, comprising components mutually soluble at -80 ° C.
It is less than 15 mass parts with respect to 100 mass parts of total amounts of the resin composition except a solvent even if it does not contain a (meth) acrylate compound, The solvent as described in any one of Claims 1 thru | or 6 An energy ray curable resin composition for an organic EL device sealing material.
Further, it contains one or both of the epoxy compound (B) and the photocationic polymerization initiator (C), and the content thereof is 0.1 to 70 parts by mass with respect to 100 parts by mass of the total amount of the resin composition excluding the solvent. The amount of the compound (A) is 30 to 99.9 parts by mass with respect to 100 parts by mass of the total amount of the resin composition excluding the solvent. The energy ray-curable resin composition for organic EL device sealing material according to Item.
Furthermore, the energy-beam curable resin composition for organic electroluminescent element sealing materials as described in any one of Claims 1 thru | or 8 containing an epoxy compound (B).
The energy ray-curable resin composition for an organic EL device sealing material according to claim 9 or 10, wherein the epoxy compound (B) is an alicyclic epoxy compound.
The energy ray curable resin composition for organic EL device sealing materials according to any one of claims 9 to 11, wherein the epoxy compound (B) is a compound having two or more epoxy groups in the molecule.
The organic compound according to any one of claims 10 to 12, wherein the epoxy compound (B) is contained in an amount of 20 to 70 parts by mass with respect to 100 parts by mass of the total amount of the compound (A) and the epoxy compound (B). An energy ray curable resin composition for an EL element sealing material.
The compound (A) having two or more oxetane rings in the molecule is contained in an amount of 30 to 90 parts by mass with respect to 100 parts by mass of the total amount of the compound (A) and the epoxy compound (B). The energy ray curable resin composition for organic EL element sealing materials according to any one of 13.
Furthermore, the energy-beam curable resin composition for organic EL element sealing materials as described in any one of Claims 1 thru | or 14 containing a photocationic polymerization initiator (C).
The energy for an organic EL device sealing material according to claim 15, wherein the cationic photopolymerization initiator (C) is at least one selected from the group consisting of a sulfonium salt, an iodonium salt, a phosphonium salt, an ammonium salt, and an antimonate. A linear curable resin composition.
Furthermore, the energy-beam curable resin composition for organic EL element sealing materials as described in any one of Claims 1 thru | or 16 containing microparticles | fine-particles (D).
The primary particle size of the fine particles (D) is 100 nm or less, The energy ray-curable resin composition for an organic EL device sealing material according to claim 17.
The energy ray curable resin composition for organic EL device sealing materials according to any one of claims 1 to 18, wherein the viscosity at 25 ° C measured with an E-type viscometer is 10 mPa · s or more.
The energy shrinkable resin composition for an organic EL device sealing material according to any one of claims 1 to 15, wherein a curing shrinkage ratio when the resin composition is cured is 5.5% or less. .
A cured product obtained by curing the energy ray-curable resin composition for an organic EL device sealing material according to any one of claims 1 to 20.
The hardened | cured material of Claim 21 whose water-vapor-permeation rate in thickness of 100 micrometers is 200 g / m < 2 > * day / 60 degrees C or less.
An organic EL display having the cured product according to claim 21 or claim 22.