KR101980560B1 - Energy ray-curable resin composition and cured product thereof - Google Patents

Abstract

[식 중 R₁은 각각 독립적으로 직접 결합 또는 탄소수 1~6개의 직쇄 또는 분기쇄상의 탄화 수소기를 나타내고, R₂는 탄소수 1~15개의 직쇄 또는 분기쇄상의 탄화 수소기 또는 지환, 방향환, 복소환 또는 축합환을 포함하는 탄화 수소기를 나타내고, R₃은 각각 독립적으로 탄소수 1~6개의 직쇄 또는 분기쇄상 탄화 수소기를 나타내고, n은 0(제로) 또는 평균값이며 1~5의 정수를 나타낸다]The present invention relates to a compound (A) having at least two oxetane rings in a molecule, for example, an energy ray curable resin composition for an organic EL element sealing material containing two or more kinds of the following formula (1) It is useful as a solid sealing material for solid sealing in an organic EL element because it is a cured product having a small shrinkage, excellent visible light transmittance and light fastness, high Tg and low water vapor permeability.

Wherein R < ₁ > Each independently represents a direct bond or a linear or branched hydrocarbon group having 1 to 6 carbon atoms, and R ₂ represents Carbon number An alkyl group having 1 to 15 linear or branched hydrocarbon groups or aliphatic, aromatic, heterocyclic, or condensed rings; R ₃ each independently represents a linear or branched hydrocarbon group having 1 to 6 carbon atoms; , n is 0 (zero) or an average value and represents an integer of 1 to 5]

Description

TECHNICAL FIELD [0001] The present invention relates to an energy ray-curable resin composition,

Energy ray curable resin is generally excellent in workability because it can be processed with solvent. In addition, energy ray curing technology is an important technology for various industries including display materials in view of fast curing rate and low energy requirement. Description of the Related Art [0002] In recent years, displays have become widespread due to the introduction of thin type displays, particularly plasma display (PDP) and liquid crystal display (LCD), which are called flat panel displays (FPD). Further, an organic EL display (OLED) is expected as a next-generation self-emission type thin film display, and some products have already been put to practical use. The organic EL element of the organic EL display has a structure in which an element body made of a thin film stacked body including a light emitting layer sandwiched between a cathode and an anode is formed on a substrate such as glass on which a driving circuit such as a TFT is formed. A layer such as a light emitting layer or an electrode of an element portion is likely to be deteriorated by moisture or oxygen, and deterioration in brightness, life, and discoloration occurs due to deterioration. Therefore, the organic EL element is sealed so as to block intrusion of moisture or impurities from the outside. A sealing material with higher performance is desired for realizing an organic EL device of high quality and high reliability, and various sealing techniques have been studied in the past.

As a representative sealing method of the organic EL element, a method of fixing a metal or glass sealing cap into which a desiccant is previously inserted is fixed to a substrate of the organic EL element by using a sealing adhesive. In this method, an adhesive is applied to the outer periphery of the substrate of the organic EL element, a sealing cap is provided thereon, and then the adhesive is solidified to fix the substrate and the sealing cap, thereby sealing the organic EL element. In such a method, sealing with a glass sealing cap has become mainstream. However, the sealing cap made of glass tends to be expensive because it is manufactured by processing a dent for inserting a desiccant into a flat glass substrate. In addition, since the sealing by the sealing cap is performed by inserting the desiccant into the inside of the sealing cap, light can not be drawn out from the sealing cap side. That is, the light emitted from the light source is drawn out from the substrate side of the element, and is limited to the bottom-emission-type element. In the case of the bottom-emission type device, there is a problem that the aperture ratio is reduced by the driving circuit portion formed on the substrate and that the drawing efficiency is lowered due to a part of the light being blocked by the driving circuit portion. Therefore, development of a sealing method applicable to a top emission type device that draws light from the opposite side of the substrate of the organic EL device has been desired.

As a typical sealing method applicable to a top emission type device, there are a thin film sealing method and a solid sealing method. In the thin film sealing method, 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-proofing property to the device by this method, it is necessary to sequentially laminate a plurality of thin films on the device. Therefore, the thin film sealing method has a long film forming process and is expensive, and the initial investment tends to be expensive by introducing a large-sized vacuum gauge facility required for film formation.

On the other hand, the solid sealing method is a method in which a passivation film is formed so as to cover the entire element portion of the organic EL element, and a sealing transparent substrate is provided thereon through a sealing material. Generally, the passivation film is formed by vapor deposition or sputtering of an inorganic material, but it is often an incomplete film having pin holes or a film having weak mechanical strength. For this reason, in the solid sealing method, after the passivation film is formed on the element, a transparent substrate for sealing such as a glass substrate is provided through a sealing adhesive to improve the reliability of sealing. Such a solid sealing method is attracting attention as a method that can easily seal a top emission type device at a low cost.

In the sealing by the solid sealing method of the organic EL element, it is possible to use heat or a photo-curing resin as the sealing adhesive, but their characteristics are very important because they may significantly affect the performance of the element and the productivity of the sealing work . For example, if the water vapor transmission rate of the sealing adhesive is insufficient, there is a possibility that the adhesive penetrates into the element portion from the pin hole of the passivation film and deteriorates the element. In addition, if the curing reaction of the sealing material is slow, the curing process may take a long time and the productivity of the sealing operation may be lowered.

In addition to a high transmittance in a visible light region, a sealing adhesive used in these materials is required to have light resistance capable of withstanding light emission, low moldability and shrinkability for suppressing stable formability and residual stress, low water vapor transmittance for protecting a light emitting element from moisture, . It is possible to perform sealing by a solid sealing method using a known adhesive as an adhesive for sealing an organic EL device, but it is difficult to obtain a satisfactory result in both reliability and productivity, and it is suitable for a solid sealing method It has been desired to develop a sealing adhesive which can be used for sealing.

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 kinds of compounds each having at least two oxetane rings are used in combination is not known.

Japanese Patent No. 3876630 Japanese Patent No. 2679586 Japanese Patent No. 4421938 Japanese Patent No. 4655172 Japanese Patent Application Laid-Open No. 2000-169552

A resin composition suitable for a sealing material of an organic EL device has a small curing shrinkage ratio and a cured product obtained from the resin composition is required to have excellent visible light transmittance, light resistance and curability, high Tg and low water vapor permeability. An object of the present invention is to provide a resin composition suitable for a sealing material of an organic EL element which satisfies such a requirement and a cured product obtained from the resin composition.

As a result of intensive studies to solve the above problems, the present inventors have found that an energy ray-curable resin composition containing at least two compounds (A) having two or more oxetane rings in a molecule and a cured product thereof solve the above problems Thereby completing 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, which contains at least two kinds of compounds (A) having two or more oxetane rings in a molecule.

(2) The energy ray-curable resin composition according to item (1), wherein the energy ray-curable resin composition does not contain or contain an organic compound component having no reactive group having a weight average molecular weight of 10,000 g / mol or more, By weight based on the total weight of the composition.

(3) A process for producing a compound (A) having at least two oxetane rings in a molecule, wherein the compound (A) having an oxetane ring represented by the following general formula (1) or the following general formula And the energy ray curable resin composition for an organic EL device encapsulant.

Equation (1)

Wherein R ₁ is independently a direct bond or a straight or branched hydrocarbon group having 1 to 6 carbon atoms, R ₂ is a linear or branched hydrocarbon group having 1 to 15 carbon atoms or an alicyclic, aromatic ring, And R ₃ each independently represents a linear or branched hydrocarbon group having 1 to 6 carbon atoms and n is an average value and is an integer of 1 to 5,

Equation (2)

Wherein R ₄ is independently C 1 -C 6 straight chain or branched hydrocarbon groups, and R ₅ independently represents a chain having from 1 to 6 straight or branched chain hydrocarbon group, respectively;

(4) The organic EL device sealing material according to any one of (1) to (3), wherein the compound (A) having at least two oxetane rings in the molecule is a compound having an alicyclic or aromatic ring in the molecule Energy ray curable resin composition.

(5) The positive resist composition according to any one of (1) to (4), characterized by containing the compound of the formula (1) and the compound of the formula (2) as the compound (A) having two or more oxetane rings in the molecule By weight based on the total weight of the composition.

(6) The energy ray curing type organic EL device for sealing material 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 based on 1 part by mass of the compound of the formula Resin composition.

(7) The organic electroluminescent device described in any one of (1) to (5) above, wherein two or more compounds (A) having two or more oxetane rings in the molecule are contained, And having a molecular weight of 10,000 g / mol or less and being mutually soluble at 20 ° C to 80 ° C.

(8) The positive resist composition according to any one of (1) to (6), wherein the (meth) acrylate compound is not contained or is contained in an amount of less than 15 parts by mass based on 100 parts by mass of the total amount of the resin composition excluding the solvent Energy radiation curable resin composition for sealing material of organic EL device.

(9) The positive resist composition as described in any one of (1) to (8) above, which further comprises at least one or both of the epoxy compound (B) and the cationic polymerization initiator (C) (A) is contained in an amount of 30 to 99.9 parts by mass based on 100 parts by mass of the total amount of the resin composition excluding the solvent in the total amount thereof, Energy ray curable resin composition.

(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 (9) or (10), wherein the epoxy compound (B) is an alicyclic epoxy compound.

(12) The energy ray curable resin composition for an 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.

(13) The positive resist composition according to any one of (10) to (12), wherein the epoxy compound (B) is contained in an amount of 20 to 70 parts by mass per 100 parts by mass of the total amount of the compound (A) By weight based on the total weight of the composition.

(14) The positive resist composition as described in any one of (10) to (13) above, wherein the compound (A) having two or more oxetane rings in the molecule is added in an amount of 30 to 30 parts by mass based on 100 parts by mass of the total amount of the compound (A) By mass to 90% by mass of the composition.

(15) The energy ray curable resin composition for an organic EL device sealing material according to any one of (1) to (14), further comprising a photocationic polymerization initiator (C).

(16) The organic EL device sealing member according to (15), wherein the photocationic polymerization initiator (C) is at least one selected from the group consisting of sulfonium salts, iodonium salts, phosphonium salts, ammonium salts and antimonates Energy ray curable resin composition.

(17) The energy ray curable resin composition for an organic EL device sealing material according to any one of (1) to (16), further comprising fine particles (D).

(18) The energy ray curable resin composition for an organic EL device sealing material as described in (17) above, wherein the primary particle diameter 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 as measured by an E-type viscometer is 10 mPa · s or more.

(20) The energy ray curable resin composition for an organic EL device sealing material according to any one of (1) to (15), wherein a curing shrinkage ratio when the resin composition is cured is 5.5% or less.

(21) A cured product obtained by curing an energy ray curable resin composition for an organic EL device sealing material according to any one of (1) to (20).

(22) The cured product as described in (21) above, wherein the water vapor transmission rate at a thickness of 100 占 퐉 is 200 g / m2 占 day / 60 占 폚 or less.

(23) An organic EL display as described in (21) or (22), which has a cured product.

(Effects of the Invention)

The energy ray curable resin composition for an organic EL device sealing material of the present invention (hereinafter also simply referred to as the resin composition of the present invention) has a small curing shrinkage ratio, and the cured product of the resin composition has excellent visible light transmittance and light resistance, And is particularly suitable for a sealing material of an organic EL element because of its low transmittance.

The term " for an organic EL device sealing material " in the present invention means a use as a solid encapsulating material to be filled between a sealing substrate such as a glass and an organic EL element in the sealing of the organic EL element, particularly in solid sealing.

The resin composition of the present invention is characterized by containing two or more kinds of compounds (A) having two or more oxetane rings in the molecule.

By virtue of the above structure, two kinds of bifunctional oxetane compounds are introduced into the curing system at the time of curing, so that it is possible to simultaneously achieve the effects of heat resistance, rigidity, refractive index control, water resistance and low shrinkage, It becomes.

That is, it is difficult to achieve the above effects simultaneously by using one type of bifunctional oxetane compound or by using a monofunctional oxetane compound and one kind of bifunctional oxetane compound simultaneously. However, by using two kinds of bifunctional oxetane compounds, two or more kinds of oxetane compounds are introduced into the curing system intricately while maintaining a low shrinkage rate, high rigidity, high refractive index and high water resistance at the time of curing, It becomes possible to provide a cured product having extremely high heat resistance (high glass transition point (Tg)) which can not be attained only by the kind. It is extremely easy to control the heat resistance, stiffness, refractive index, and shrinkage ratio by using two or more of them.

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.

Methyl {(3-ethyl-3-oxetanyl) methoxy} methyl} benzene (commercially available product thereof as a main component (80% More than Included) doing AARON OXETAN ^{R TM} OXT-121) (TOAGOSEI CO., LTD.); (3-ethyloxetane-3-yl) methoxy] methyl} oxetane, di [2- (3-oxetanyl) butyl] ether, 1 Methoxy] benzene, 1,3-bis [(3-ethyloxetan-3-yl) methoxy] benzene, 1,2-bis [ Methoxy] benzene, 4,4'-bis [(3-ethyloxetan-3-yl) methoxy] biphenyl, 2,2'-bis [ 3-oxetanyl) methoxy] biphenyl, 3,3 ', 5,5'-tetramethyl [4,4'-bis (3-ethyloxetan- Methoxy] naphthalene, 1,6-bis [(3-ethyloxetan-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] Ethyl [3-oxetanyl] methoxy] ethylthio} ethane, 4,4'-bis [ 2-ethyl-2 - [(3-ethyloxetan-3-yl) methyl] thiobenzene thioether, 2,3-bis [ Toxic Methyl-propane-1,3-diol, 2,2-dimethyl-1,3-O-bis [(3- Ethyl] -1,3-O-bis [(3-ethyloxetan-3-yl) methyl] -propane Diol, 2,4,6-O-tris [(3-ethyloxetan-3-yl) methyl] Ethyloxetan-3-yl) methyl] cyanuric acid and the like. These are preferably two or more kinds, and at least one of them is preferably an oxetane compound having an alkyleneoxy group.

Preferred oxetane compounds having at least two oxetane rings used in the present invention include oxetane compounds in which at least two oxetane rings are linked by a crosslinking group containing at least one ether bond. In the present invention, at least two oxetane compounds are preferably used. In the preferred embodiment, two different types are used. In one preferred embodiment, the above-mentioned crosslinking group containing an ether bond is an oxetane compound which is a chain crosslinking group not containing a cyclic structure and an oxetane compound which is a chain crosslinking group containing a cyclic structure are used in combination . The above effects can be achieved more favorably by using the two kinds of oxetane compounds in combination.

Examples of the oxetane compound in which at least two oxetane rings are connected by a crosslinking group containing at least one ether bond include compounds represented by the above general formula (1) or (2). The "crosslinking group" in the present invention means a divalent group connecting two atoms.

As a combination of two 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-ethyloxetan-3-yl) methoxy] methyl} oxetane is particularly preferred in view of availability from the market.

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

Wherein R ₁ represents a direct bond or a linear or branched hydrocarbon group having 1 to 6 carbon atoms (hydrocarbon bond), R ₂ is a linear or branched hydrocarbon group having 1 to 15 carbon atoms R ₃ represents a linear or branched hydrocarbon group having 1 to 6 carbon atoms and n is an average value of 1 to 5, Lt; / RTI > represents an integer.

R ₁ and R ₂ in the formula (1) are divalent hydrocarbon groups and R ₃ is a monovalent hydrocarbon group as is clear from the structural formula.

As R _{1, a} straight or branched chain hydrocarbon group having 1 to 6 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is particularly preferable.

R _{2 is preferably a} straight chain alkylene group having from 1 to 12 carbon atoms, a branched alkylene group having from 1 to 12 carbon atoms, or an alkylene group having from 3 to 12 carbon atoms or a cycloalkylene group, and a phenylene group having from 6 to 12 carbon atoms (Preferably an alkylene group having 1 to 4 carbon atoms) is particularly preferable.

R ₃ is preferably an alkyl group having 1 to 3 carbon atoms.

n is preferably 1 to 3.

In addition, the oxide having a cyclic structure such as alicyclic, aromatic ring or heterocyclic ring, condensed ring and to R ₂ (e.g., a phenylene group, a naphthalene group, a carbon number of 3 to 8 cycloalkylene group) in the compound of formula (1) Use of the cetyl compound is preferable because the curing shrinkage is reduced and the Tg (glass transition point), rigidity and refractive index of the cured product are improved.

As specific examples of the compound of the formula (1), compounds represented by 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 may be an alicyclic ring (aliphatic ring), an aromatic ring, a heterocyclic ring or a condensed ring. and n is an average value and represents an integer of 1 to 5.

As the cyclic group having 3 to 12 carbon atoms for Z, a bivalent aliphatic group or aromatic group is preferable, and a phenylene group is particularly preferable.

By using the compound of the above formula (3), it becomes possible to keep the hardening shrinkage rate lower.

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

In the formula, each R ₄ independently represents a linear or branched hydrocarbon group having 1 to 6 carbon atoms, and R ₅ independently represents a linear or branched hydrocarbon group having 1 to 6 carbon atoms. R ₄ is a bivalent hydrocarbon group having 1 to 6 carbon atoms and R ₅ is a monovalent hydrocarbon group as is clear from the structural formula.

In the 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.

R ₅ is preferably a straight chain hydrocarbon group having 1 to 3 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms.

When 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) is used as one of the components, Tg (glass transition point), rigidity and refractive index are improved. More preferably, it is an oxetane compound in which the ring structure is an alicyclic or aromatic ring. Specifically, it is a compound represented by the above general formula (3). The content of the component (A) of the present invention is 30 to 100 parts by mass, more preferably 30 to 90 parts by mass, relative to 100 parts by mass of the total amount of the component (A) + the component (B) 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 remainder is component (B).

The content of the component (A) relative 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 99.5 parts by mass More preferably 50 to 99.5 parts by mass.

The functional group equivalent of the component (A) is preferably 10 to 500 g / eq, more preferably 50 to 250 g / eq.

The oxetane compound (preferably a compound represented by the formula (2)) having a functional group equivalent of 50 to 150 g / eq and an oxetane compound having an aromatic ring having a functional group equivalent of 100 to 200 g / A compound having a high Tg (glass transition point) and a high refractive index can be obtained by combining a compound represented by the formula (3), more preferably a compound wherein Z in the formula (3) is a phenylene group).

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 the compound (1) Is generally in the range of 0.6 to 1.5 parts by mass, preferably 0.7 to 1.3 parts by mass, more preferably 0.8 to 1.2 parts by mass, and most preferably 0.9 to 1.1 parts by mass.

As the compound (B) having an epoxy group (hereinafter also referred to as an epoxy compound (B) or the component (B)) contained in the resin composition of the present invention, either a monofunctional epoxy compound or a polyfunctional epoxy compound may be used. Further, any of an epoxy compound (aromatic epoxy compound) containing an aromatic ring and an aliphatic epoxy compound containing no aromatic ring may be used. In the present invention, an epoxy compound (an aliphatic ring-containing epoxy compound) containing an aromatic epoxy compound or an aliphatic ring is preferable. Particularly, 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, -Butylene oxide, 1,3-butadiene monoxide, 1,2-epoxydecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene Oxide, 3-acryloyloxymethyl cyclohexene oxide, 3-vinylcyclohexene oxide, and the like.

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 diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexyl Methyl-3 ', 4'-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane- Epoxy cyclohexylmethyl) adipate, vinyl cyclohexene oxide, 4-vinyl epoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4- Hexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxy (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate), dioctylhexahydrophthalic acid dioctyl, epoxyhexa Hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether, polyethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, Epoxycyclohexyl ether, cyclic ether, polypropylene glycol diglycidyl ether, 1,1,3-tetradecadienooxide, limonene dioxide, 1,2,7,8-diepoxy octane, 1,2,5,6-diepoxy cyclo Octane and the like.

Examples of the alicyclic epoxy include all compounds containing cyclohexene oxide or cyclopentene oxide. Specific examples of the alicyclic epoxy include compounds having the following structures.

[Wherein n is an average value and represents an integer of 1 to 5]

The epoxy compound (B) to be used in the present invention is not limited to those exemplified above as long as it is an epoxy resin usually used.

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. Of the alicyclic epoxy compounds, bifunctional alicyclic epoxy compounds are preferred, and 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate is particularly preferred.

The epoxy compound (B) may be used alone or in combination of two or more. The content of the component (B) of the present invention is generally 0 to 70 parts by mass, preferably 10 to 70 parts by mass, relative to 100 parts by mass of the total amount of the component (A) + the component (B) Is 20 to 70 parts by mass, particularly preferably 25 to 50 parts by mass. In some cases, it is more preferably 10 to 60 parts by mass.

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

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 [diphenyl Diphenylsulfide-bis hexafluorophosphate, 4,4'-bis [di (? - hydroxyethoxy) phenylsulfonio] diphenylsulfide-bishexafluoroantimonate, 7 - [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluorophosphate, 7- [di (p- tolyl) sulfonio] -2-isopropylthioxanthone hexafluorophosphate (Pentafluorophenyl) borate, phenylcarbonyl-4'-diphenylsulfono-diphenylsulfate (diphenylphosphoryl) diphenylsulfate Diphenylsulfide-hexafluoroantimonate, 4-tert-butylphenylcarbonyl-4'-tert-butylphenylphosphonate, 4-tert-butylphenylcarbonyl-4'-diphenylsulfo-diphenylsulfide-hexafluoroantimonate, 4-tert-butyl Diphenylsulfone-diphenylsulfide-tetrakis (pentafluorophenyl) borate, thiophenyldiphenylsulfonium hexafluoroantimonate, thiophenyldiphenylsulfonium hexafluoro Phosphate, 4- {4- (2-chlorobenzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate, a halide of thiophenyldiphenylsulfonium hexafluoroantimonate, 4,4 ', 4 "-tris (? -Hydroxyethoxyphenyl) sulfonium hexafluoroantimonate, 4,4'-bis [diphenylsulfonio] diphenylsulfide-bis hexafluoro Antimonates, diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotris pentafluoroethyl phosphate, tris [4- (4-acetylphenylsulfam ) Phenyl] methyl sulfonium tris [(trifluoromethyl) and the like sulfonyl] meth arsenide.

Among the aromatic sulfonium complex salts, thiophenyldiphenylsulfonium hexafluoroantimonate which is highly sensitive and easy to obtain from the market, 4- {4- (2-chlorobenzoyl) phenylthio} phenylbis (4-fluorophenyl) (Phenylthio) phenyl] sulfonium trifluorotris pentafluoroethyl phosphate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tris [ Trifluoromethyl) sulfonyl] methanide and the like are preferable.

Given the environmental and human health hazards and the regulations of each country, it has been found that diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotris pentafluoroethyl phosphate, tris [4- -Acetylphenylsulfanyl) phenyl] sulfoniumtris [(trifluoromethyl) sulfonyl] methanide is most preferably used.

The content of the component (C) of the present invention is 0.1 to 10 parts by mass, preferably 0.5 to 3 parts by mass based on 100 parts by mass of the total amount of the component (A) + the component (B).

The ratio of the component (C) 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. The content ratio of the component (C) relative to 100 parts by mass of the component (A) is also preferably in the above-described range.

In the resin composition of the present invention, the cationic polymerization initiator (C) may be used singly or in combination of a plurality of kinds.

In addition, a radical type photopolymerization initiator can be used in combination. As the radical type photopolymerization initiator, any photopolymerization initiator may be used, 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. The fine particles (D) may be used singly or in combination of two or more of them, if necessary, in consideration of required light transmittance, hardness, scratch resistance, curing shrinkage and refractive index. By using the fine particles (D), the curing shrinkage ratio of the resin composition of the present invention and the moisture permeability of the cured product of the resin composition can be lowered, and the liquid refractive index can be increased.

On the other hand, from the viewpoint of improving the transmittance of light (particularly transmittance of light in a wavelength range of 380 nm to 780 nm) of the cured product, it is preferable that the resin composition of the present invention does not contain the fine particles (D).

Examples of the organic fine particles to be used in the present invention include organic polymer beads such as polystyrene resin beads, acrylic resin beads, urethane resin beads and polycarbonate resin beads, porous polystyrene resin beads, porous acrylic resin beads, porous urethane beads, porous polycarbonate resin beads , Resin powder of benzoguanamine-melamine-formalin condensate, resin powder of urea-formalin condensate, powder of aspartic acid ester derivative, powder of zinc stearate, powder of stearic acid Acid amide powder, epoxy resin powder, polyethylene powder and the like, and 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, or can be prepared by referring to known documents.

Examples of the inorganic fine particles usable 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, gallium doped zinc oxide, Comments, and the like.

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 complex, zirconium oxide / tin oxide / antimony pentoxide composite , Titanium oxide / zirconium oxide / tin oxide composite, and the like.

Examples of other inorganic fillers used in the present invention include calcium oxide, calcium chloride, zeolite, and silica gel.

As the fine particles to be used in the present invention, fine particles having excellent hardness and scratch resistance and having a high refractive index are preferable, and titanium oxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, titanium oxide / zirconium oxide / tin oxide / Metal oxide fine particles such as zirconium oxide / zirconium oxide / antimony pentoxide composite, titanium oxide / zirconium oxide / tin oxide composite, etc. are suitably used. Further, since the optical sheet used in the display is required to have a high light transmittance, the primary particle size of the fine particles is preferably 100 nm or less. These blending ratios are generally from 0 to 30 parts by mass based on 100 parts by mass of the total amount of the component (A) + the component (B), and usually from 1 to 30 parts by mass, preferably from 5 to 20 parts by mass.

It is also possible to use a polycarboxylic acid-based dispersing agent, a silicon-based dispersing agent such as a silane coupling agent, a titanate-based coupling agent, a modified silicone oil, or a dispersant of an organic copolymerization system as a dispersing agent for the fine particles. These compounding ratios are about 0 to 30 mass%, preferably about 0.05 to 5 mass%, based on the total mass of the resin composition of the present invention (total amount of the resin composition excluding the solvent).

The primary particle diameter means the smallest particle diameter of the particles when the aggregation is collapsed. That is, in the case of elliptical fine particles, the minor diameter is set to be the primary particle diameter. The primary particle diameter can be measured by a dynamic light scattering method or an electron microscope observation. Specifically, the primary particle diameter can be measured under a condition of an acceleration voltage of 30 kV using a JSM-7700F Field Emission Scanning Electron Microscope (JEOL Ltd.).

In the present invention, it is preferable that the primary particle diameter is 100 nm or less. Fine particles having a particle size of 5 to 100 nm can be suitably used. 100 nm or less, it is possible to provide a cured product in which the resin composition has a low hardening shrinkage and moisture permeability and a relatively high light transmittance.

These fine particles can be used dispersed in a solvent. In particular, inorganic fine particles may be commercially available in a form dispersed in water or an organic solvent. Examples of the organic solvent used for dispersing the inorganic fine particles include a hydrocarbon solvent, an ester solvent, an ether solvent or a ketone solvent.

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 thereof, such as petroleum ether, white gasoline and solvent naphtha have.

Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate, cyclic esters such as? -Butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl (Mono- or poly) alkylene glycol monoalkyl (meth) acrylates such as ethylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monoacetate, ethylene glycol monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate and butylene glycol monomethyl ether monoacetate Polycarboxylic acid alkyl esters such as ether monoacetates, dialkyl glutarates, dialkyl succinates, dialkyl adipates, and the like.

Examples of the ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, ketones such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol Glycol ethers such as diethyl ether, and cyclic ethers such as tetrahydrofuran.

Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

In the resin composition of the present invention, a reactive compound other than the component (A) and the component (B) may be used in consideration of the viscosity, refractive index and adhesion of the resin composition of the present invention. Specific examples thereof include (meth) acrylate compounds.

Examples of the (meth) acrylate compound include monofunctional (meth) acrylates, bifunctional (meth) acrylates, polyfunctional (meth) acrylates having three or more (meth) acryloyl groups in the molecule, urethane (Meth) acrylate, epoxy (meth) acrylate, and the like can be used.

In the present invention, from the viewpoint of keeping the curing shrinkage ratio small, the amount of the (meth) acrylate compound contained or not contained is not increased so much as to not increase the curing shrinkage ratio, for example, 100 parts by mass of the total amount of the resin composition excluding the solvent Is generally not more than 15 parts by mass, preferably not more than 10 parts by mass, more preferably not more than 5 parts by mass, and most preferably not more than 2 parts by mass. In the present invention, from the viewpoint of keeping the curing shrinkage ratio small, the embodiment not including the (meth) acrylate compound is most preferable.

Examples of the monofunctional (meth) acrylate include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl Alicyclic (meth) acrylates such as cyclohexyl (meth) acrylate; (Meth) acrylate having a heterocycle such as tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate and morpholine (meth) acrylate; (Meth) acrylates such as benzyl (meth) acrylate, ethoxy-modified cresol (meth) acrylate, propoxy-modified cresol (meth) acrylate, neopentyl glycol benzoate Phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-phenylphenol (meth) acrylate, p- (Meth) acrylate having an aromatic ring such as phenol polyethoxy (meth) acrylate, o-phenylbenzyl acrylate, p-phenylbenzyl acrylate and the like; (Meth) acrylate having a heterocycle such as carbazole (poly) ethoxy (meth) acrylate, carbazole (poly) propoxy (meth) acrylate, and (poly) caprolactone modified carbazole ; Naphthyl (meth) acrylate, naphthyl (poly) ethoxy (meth) acrylate, naphthyl (poly) propoxy (meth) acrylate, (poly) caprolactone modified naphthyl (Meth) acrylate, naphthol (poly) ethoxy (meth) acrylate, binaphthol (poly) propoxy (meth) acrylate, (poly) caprolactone modified binaphthol Acrylate having a condensed ring such as naphthol (poly) ethoxy (meth) acrylate, naphthol (poly) propoxy (meth) acrylate, and (poly) caprolactone modified naphthol (meth) ; Imide (meth) acrylate having an imide ring structure; Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (Meth) acrylate having a hydroxyl group such as dipropylene glycol (meth) acrylate; Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, octafluoropentyl (meth) acrylate, (Meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (Meth) acrylate having an alkyl group such as isostearyl (meth) acrylate, isomyristyl (meth) acrylate, or lauryl (meth) acrylate; (Meth) acrylates of polyhydric alcohols such as ethoxydiethylene glycol (meth) acrylate, 2-ethylhexylcarbitol (meth) acrylate, polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate; And the like.

Examples of the (meth) acrylate monomer having two functional groups include (meth) acrylate having a heterocycle such as hydro-pivalicdehyde-modified trimethylolpropane di (meth) acrylate; (Meth) acrylate, (poly) propoxy-modified bisphenol A di (meth) acrylate, (poly) ethoxy-modified bisphenol F di (meth) acrylate, (Meth) acrylates such as modified bisphenol F di (meth) acrylate, (poly) ethoxy modified bisphenol S di (meth) acrylate, (poly) propoxy modified bisphenol S di (meth) acrylate, hexahydrophthalic acid di (Meth) acrylate having an aromatic ring such as bisphenoxy (poly) ethoxyfluorene and biphenyl dimethanol di (meth) acrylate; (Meth) acrylate, naphthol di (meth) acrylate, binaphthol (poly) ethoxydi (meth) acrylate, binaphthol (poly) propoxydi (Meth) acrylate having a condensed ring such as; (Meth) acrylate, bisphenol fluorene di (meth) acrylate, bisphenol fluorene di (meth) acrylate, bisphenol fluorene di (Meth) acrylate having a polycyclic aromatic group such as acrylate; Acrylates of isocyanates such as diacyl isocyanurate; Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and polytetramethylene glycol di (meth) (Meth) acrylate having a linear methylene structure; (Meth) acrylate such as tricyclodecane dimethanol (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylates of polyhydric alcohols such as (meth) acrylate.

Examples of polyfunctional (meth) acrylate monomers include multifunctional (meth) acrylate monomers having an isocyanurate ring such as tris (acryloxyethyl) isocyanurate and (poly) caprolactone modified tris (acryloxyethyl) Acrylate; (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, (poly) ethoxy-modified pentaerythritol tetra (Poly) propoxy modified penta (meth) acrylate, (poly) caprolactone modified dipentaerythritol penta (meth) acrylate, (poly) ethoxy modified dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, (poly) caprolactone modified dipentaerythritol hexa (metha) acrylate, (poly) ethoxy modified dipentaerythritol hexa ) Propoxy-modified dipentaerythritol hexa (meth) acrylate, polypentaerythritol poly (meth) acrylate, trimethylol propane (Meth) acrylate, trimethylol propane tri (meth) acrylate, (poly) ethoxy modified trimethylol propane tri (meth) acrylate, (poly) propoxy modified trimethylol propane tri Polyfunctional (meth) acrylates of polyhydric alcohols such as tri (meth) acrylate; Polyfunctional (meth) acrylates such as phosphoric acid tri (meth) acrylate; Polyfunctional (meth) acrylates having an aromatic group such as trimethylolpropane benzoate (meth) acrylate; Acid-modified polyfunctional (meth) acrylates such as 2,2,2-trisacryloyloxymethylsuccinic acid and the like; And polyfunctional (meth) acrylates having a silicon skeleton such as silicone hexa (meth) acrylate.

Examples of the urethane (meth) acrylate include a reaction product obtained by reacting a diol compound (including polyester diol below) with an organic polyisocyanate followed by addition of 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- Octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1,5-pentanediol, 2,4- 2-ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A polyethoxydiol, bisphenol A polypropoxydiol, And polyester diols which are reactants of the anhydrides (for example, succinic acid, adipic acid, azelaic acid, dimeric acid, isophthalic acid, terephthalic acid, 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, Cyclic saturated hydrocarbon isocyanates such as isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, , 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylenediisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-isopropyl- Aromatic polyisocyanates such as isocyanate and 1,5-naphthalene diisocyanate It can be a bit like.

Examples of the epoxy (meth) acrylate include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolak type epoxy resins, biphenyl type phenol aralkyl resins, terminal glycidyl ether of a propylene oxide adduct of bisphenol A, Resins, bisphenol S type epoxy resins, and the like, and reaction products of (meth) acrylic acid.

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

Among them, as the (meth) acrylate usable in the resin composition of the present invention, a material having a low hardening shrinkage ratio is suitably used. Specifically, (meth) acrylate having a cyclic structure is preferable, and 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, benzyl (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, hydroxyphenyl (meth) acrylate, phenylphenol Modified trimethylol propane di (meth) acrylate, and biphenyl dimethanol di (meth) acrylate. (Meth) acrylate, tricyclodecane dimethanol (meth) acrylate, hydropaldehyde-modified trimethylolpropane di (meth) acrylate having a high Tg of the cured product and a low hardening shrinkage Biphenylethanol di (meth) acrylate.

In the resin composition of the present invention, (meth) acrylate, which is another component, may be added as needed, and used alone or in combination of two or more kinds.

In the present invention, when the component (A) + the component (B) is 100 parts by mass, the compounding ratio of the (meth) acrylate compound is usually 0 to 200 parts by mass and 10 to 200 parts by mass, 50 to 100 parts by mass may be used, but it is preferably not used in the resin composition of the present invention, or at least, if possible.

When a (meth) acrylate compound is used, it is preferable to use a photopolymerization initiator other than the above-mentioned photopolymerization initiator. Specific examples 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-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, oligo [2-hydroxy- Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone]; Anthraquinones such as 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, 2-chloro anthraquinone, and 2-amylanthraquinone; Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide and 4,4'-bismethylaminobenzophenone; (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, and the like Pin oxide and the like. Preferably acetophenones, more preferably 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl-phenylketone. In the resin composition of the present invention, the photopolymerization initiator may be used singly or a plurality of types may be mixed and used.

The content of the photopolymerization initiator is usually 0 to 10 parts by mass based on 100 parts by mass of the resin composition. When it is 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 the desired refractive index, durability, viscosity and adhesion, but when the content of the component (A) + the component (B) is taken as 100 parts by mass, Is generally 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 the component (B) is generally 0 to 70 parts by mass, preferably 20 to 70 parts by mass, more preferably 25 to 50 parts by mass or 30 to 60 parts by mass. The resin composition of the present invention usually contains 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 optional and may be not included. However, the component (D) may be included if necessary, and if it is included, it is preferably 1 to 30 parts by mass, more preferably 5 to 30 parts by mass, per 100 parts by mass of the total amount of the component (A) To 20 parts by mass.

As a preferred embodiment of the present invention, there can be mentioned an embodiment including (i) the above compound (A) and (ii) either or both of the epoxy compound (B) and the cationic polymerization initiator (C). In this case, the content of the compound (A) in (i) relative to 100 parts by mass of the total amount of the resin composition excluding the solvent is generally 30 to 99.9 parts by mass, preferably 40 to 99.5 parts by mass, more preferably Preferably 50 to 99.5 parts by mass, and more preferably 40 to 90 parts by mass, more preferably 50 to 80 parts by mass. The content of the component (B) and / or the component (C) in the above (ii) is generally from 0.1 to 70 parts by mass, preferably from 0.5 to 60 parts by mass relative to 100 parts by mass of the total amount of the resin composition excluding the solvent And if necessary, it is preferably from 10 to 60 parts by mass, more preferably from 20 to 50 parts by mass.

To the resin composition of the present invention, additives such as mold release agents, antifoaming agents, leveling agents, light stabilizers, antioxidants, polymerization inhibitors, plasticizers, and antistatic agents may be added, if necessary, And may be contained in combination.

The content of various additives is usually 0 to 10 parts by mass based on 100 parts by mass of the resin composition. When it is used, it is usually 0.001 to 10 parts by mass, preferably 0.01 to 8 parts by mass.

Further, there are many examples in which a plasticizer is used to obtain durability and flexibility. The plasticizer to be used is selected according to desired viscosity, durability, transparency and flexibility. Specific examples thereof include olefin-based polymers such as polyethylene and polypropylene, aliphatic polymers such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, dicyclohexyl Phthalate esters such as phthalate, ethyl phthalyl ethyl glycolate and butyl phthalyl butyl glycolate, trimellitic acid 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 Aliphatic dibasic acid esters such as bis (2-ethylhexyl) sebacate and diethyl succinate, trimethyl phosphate, triethyl phosphate, tributyl phosphate (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, and 2-ethylhexyldiphenyl phosphate, and methyl acetyl ricinoleate Polyesters such as ricinolic acid ester and poly (1,3-butanediol adipate), acetic acid esters such as glyceryl triacetate, sulfonamides such as N-butylbenzenesulfonamide, polyethylene glycol benzoate, polyethylene glycol dibenzoate, (Dibenzoate) such as polypropylene glycol benzoate, polypropylene glycol dibenzoate, polytetramethylene glycol benzoate and polytetramethylene glycol benzoate, polypropylene glycol, polyethylene glycol, polytetramethylene glycol and the like Polyether, polyethoxy-modified bisphenol A, polypropylene Polyalkoxy-modified bisphenol F such as polyoxy-modified bisphenol F, polypropoxy-modified bisphenol F and the like, polycyclic aromatics such as naphthalene, phenanthrene and anthracene, (non-naphthol) Naphthol derivatives such as (poly) ethoxy-modified (non) naphthol, (poly) propoxy-modified (non) naphthol, (poly) tetramethylene glycol- But are not limited to, sulfide, sulfide, diphenyl polysulfide, benzothiazolyl disulfide, diphenyl thiourea, morpholinodithiobenzothiazole, cyclohexyl benzothiazol-2-sulfenamines, tetramethyl thiuram disulfide, And sulfur compounds such as disulfide, tetrabutyl thiuram disulfide, tetrakis (2-ethylhexyl) thiuram disulfide, tetramethyl thiuram monosulfide, and dipentamethylenethiuram tetrasulfide. Preferred are (poly) ethylene glycol dibenzoate, (poly) propylene glycol dibenzoate, binaphthol, (poly) ethoxy-modified binaphthol, (poly) propoxy-modified binaphthol, diphenylsulfide.

If necessary, a softening system such as polymers such as acrylic polymers, polyester elastomers, urethane polymers and nitrile rubbers may be added.

The content of the plasticizer or the softening agent is usually 0 to 90 parts by mass based on 100 parts by mass of the resin composition, 1 to 90 parts by mass, preferably 2 to 80 parts by mass, when used.

The organic compound component having no reactive group in the present invention includes an organic compound that does not contain an ion reactive or radical reactive group such as an oxetanyl group, an epoxy group, a radical-reactive unsaturated bond-containing group, and the like. , Additives other than the components (A) to (D), and the like. From the viewpoint of compatibility, they preferably have a weight average molecular weight of 10,000 g / mol or less, particularly preferably 5,000 g / mol or less. In the present invention, when the organic compound not having a reactive group having a weight average molecular weight of 10,000 g / mol or more is not contained in the resin composition of the present invention or is contained in the resin composition of the present invention, its content is preferably 1.5% By weight, more preferably 1.0% by weight or less, and particularly preferably 0.5% by weight or less. By weight or less and 1.5% by weight or less, it is possible to prevent components having no reactive group from being miscible and remaining as an insoluble component such as a solid or gel phase, and thus it is possible to prevent degradation of transparency and heat resistance . Further, an organic metal compound such as alkyl aluminum may be added to lower the water vapor permeability. Although a solvent can be added, it is preferable not to add a solvent.

The weight average molecular weight of each component of the organic compound used in the resin composition of the present invention is preferably 10,000 g / mol or less, more preferably 5,000 g / mol or less. Since the 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 is indispensable to be uniformly transparent. In addition, excellent characteristics are required for the transmittance. Specifically, it is preferable that the light transmittance of each wavelength at a wavelength of 380 to 780 nm is 80% or more. The light transmittance can be measured by a measuring device such as a spectrophotometer U-3900H manufactured by Hitachi High-Technologies Corporation.

Some preferred embodiments of the resin composition for an organic EL device sealing material of the present invention are listed below. In the following, the total amount of the resin composition refers to the total amount excluding the solvent when the resin composition includes a solvent.

I. An energy ray curable resin composition for an organic EL device sealing material comprising at least two compounds (A) having at least two oxetane rings in the molecule, wherein at least two of the compounds (A) having two or more oxetane rings in the molecule The combination of two kinds is a combination of the compound represented by the general formula (2) and the compound represented by the general formula (3), and the compound represented by the general formula (2) is added to 1 part by mass of the compound represented by the general formula (3) 0.6 to 1.5 parts by mass.

Ⅱ. In the above I, the content ratio of the compound represented by the general formula (2) is 0.8 to 1.2.

Ⅲ. (I) or (II) further comprises a photocationic polymerization initiator (C) in a proportion of 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the compound (A).

IV. An embodiment wherein any one of I to III above further contains an epoxy compound (B) in an amount of 10 to 70 parts by mass based on 100 parts by mass of the total amount of the compound (A) and the epoxy compound (B).

Ⅴ. The embodiment of any one of I to IV above wherein the content of the compound (A) is 50 parts by mass or more based on 100 parts by mass of the total amount of the resin composition.

VI. In any one of the above I to V, the (meth) acrylate compound is not contained or is contained in an amount of less than 15 parts by mass based on 100 parts by mass of the total amount of the resin composition.

VII. An embodiment wherein any one of I to VI above has a curing shrinkage of 5.5% or less.

VIII. In any one of the above I to VI, the curing shrinkage ratio is 5% or less.

Ⅸ. An embodiment in any one of I to VI above, wherein the organic EL element sealing material is easily adhered to the 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, it can be obtained by injecting each component into a round bottom flask equipped with a stirrer and a thermometer, and stirring at 20 to 80 캜, preferably 40 to 80 캜, for 0.5 to 6 hours.

The viscosity of the resin composition of the present invention is not specifically limited as long as it is sufficient to form a coating film for bonding a solid organic EL sealing material (for example, glass), and may be 10 mPa · s or more at 25 ° C, preferably 10 to 3,000 mPa · s s. The viscosity of the resin composition of the present invention not containing the fine particles (D) is about 10 to 150 mPa · s and preferably about 20 to 120 mPa · s. The viscosity of the resin composition of the present invention containing the fine particles (D) is preferably about 300 to 3000 mPa · s, and more preferably about 500 to 2500 Pa · s.

In addition, as a viscosity suitable for the workability of transferability and workability of the shape when the optical lens to be molded on the substrate is produced, it is preferably 10 mPa · s or more at 25 ° C.

The resin composition of the present invention can be easily cured by an energy ray. Specific examples of the energy ray include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X rays, gamma rays and laser rays, particle beams such as alpha rays, beta rays and electron rays. In the present invention, ultraviolet rays, laser beams, visible rays or electron beams are preferred among these.

The cured product of the present invention can be obtained by irradiating the resin composition of the present invention with the energy ray according to the conventional method. In order to make the refractive index of the cured layer of the resin composition of the present invention high, the resin composition of the present invention preferably has a high refractive index and a refractive index of 1.45 to 1.55, preferably 1.48 to 1.52. The liquid refractive index can be measured by Abbe's refractive index meter (model: DR-M2, manufactured by ATAGO CO., LTD.).

When the resin composition of the present invention is cured, the curing shrinkage ratio is preferably 5.5% or less, preferably 5% or less, more preferably 4.7% or less, and most preferably 4.5% or less. The smaller the lower limit, the better, but in the present invention, the lower limit is usually about 4%.

When the resin composition of the present invention is used as a cured film having a thickness of 100 占 퐉, the water vapor transmission rate at 60 占 폚 is preferably 200 g / m2 day or less, more preferably 100 g / m2 day or less, more preferably 60 g / Is particularly preferable. Within the above range, it is possible to effectively prevent damage to the device due to permeation of moisture.

The solid encapsulation of the organic EL device using the resin composition of the present invention is usually carried out by a step of forming a passivation film on the organic EL element formed on the substrate, a step of applying the resin composition (sealing adhesive) of the present invention on the passivation film, A step of providing a sealing transparent substrate on the coating layer, and a step of curing the coating layer. As a transparent substrate for sealing normally, a transparent substrate which does not allow moisture permeation such as glass is used.

The organic EL element to be sealed comprises a substrate (support substrate) for supporting an element body serving as the element, a lower electrode, an organic EL layer including at least a light emitting layer, and an element body including an upper electrode. The substrate may be formed of a transparent organic material such as glass substrate, cycloolefin or polycarbonate, polymethylmethacrylate, or the like, or an organic / inorganic hybrid transparent substrate in which the transparent organic material is highly rigidified with glass fiber or the like, Substrate. As typical constitution of the element unit main body, the following can be given.

(1) Lower electrode / light emitting layer / upper electrode

(2) lower electrode / electron transporting layer / light emitting layer / upper electrode

(3) Lower electrode / light emitting layer / hole transporting layer / upper electrode

(4) lower electrode / electron transporting layer / light emitting layer / hole transporting layer / upper electrode

For example, in the organic EL device having the layer structure of (4), a lower electrode (cathode) made of an Al-Li alloy or the like is formed on one surface of a substrate by a resistance heating deposition method or a sputtering method, An electron transport layer composed of an oxadiazole derivative or a triazole derivative or the like, a light emitting layer, a hole transport layer made of TPD (triphenyldiamine) or the like, and an upper electrode (anode) are formed sequentially by a thin film forming method such as resistance heating deposition method or ion beam sputtering method As shown in Fig. The layer structure or material of the organic EL element is not particularly limited as long as it functions as a display element. Further, the solid sealing method according to the present invention can be applied to any organic EL element having any structure.

The passivation film is formed so as to cover the organic EL element. The passivation film can be formed by an inorganic material such as silicon nitride or silicon oxide by vapor deposition or sputtering. The passivation film is formed to prevent moisture, ionic impurities, and the like from entering the organic EL device. The thickness of the passivation film is preferably in the range of 10 nm to 100 탆, and more preferably in the range of 100 nm to 10 탆.

The passivation film is generally an incomplete film having a pinhole or a film having a weak mechanical strength, depending on the film forming method. Therefore, in the solid sealing method, an adhesive is further applied on the passivation film, the adhesive is compressed by using a sealing transparent substrate, and the reliability of sealing is enhanced by curing the adhesive.

An organic EL display having a cured product of the resin composition of the present invention can be obtained by mounting (mounting) the sealed organic EL element obtained as described above to a display device.

Example

The present invention will now be described in more detail by way of examples. The present invention is not limited by the following examples. The numerical unit "part" represents the mass part.

The resin composition and the cured product of the present invention were obtained from 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. For the examples containing an organic solvent, evaluation was carried out after sufficiently volatilizing the organic solvent with this distributor.

(1) Viscosity: Measured at 25 캜 using an E-type viscometer (TV-200, manufactured by TOKI SANGYO CO., LTD.).

(2) Liquid refractive index: The refractive index (25 DEG C) of the resin composition to which the resin composition was added was measured by Abbe's refractive index meter (DR-M2: manufactured by ATAGO CO., LTD.).

(3) Water vapor permeability: The ultraviolet curable resin was sandwiched with a glass substrate, the thickness of the film was adjusted using a spacer of 100 mu m, and the specimen was cured with a high pressure mercury lamp (80 W / cm, ozone) at 3000 mJ / cm2. The obtained test pieces were measured for moisture permeability at 60 DEG C x 90% RH by Lyssy water vapor permeability meter L80-5000 (manufactured by Systech instruments Ltd and Illinois instruments, Inc.).

(4) Tg (glass transition point): The Tg point of the cured ultraviolet-curable resin layer was measured with a viscoelasticity measurement system EXSTAR DMS-6000 (manufactured by SII NanoTechnology Inc.), a tensile mode, a frequency of 1 Hz, a scan rate; And was measured at room temperature from 2 占 폚 / min.

(5) Curing shrinkage: An ultraviolet curable resin layer was applied on a substrate and cured by irradiation with 3000 mJ / cm 2 using a high-pressure mercury lamp (80 W / cm, ozone) to prepare a cured product for measuring the specific gravity of the film.

The specific gravity (DS) of the cured product was measured in accordance with JIS K7112 B method. The specific gravity (DL) of the resin composition was measured at 23 占 占 폚, and the curing shrinkage ratio was calculated by the following formula. The measurement result is expressed by an average value of four measurement results.

Cure shrinkage (%) = (DS-DL) / DS x 100

(6) Brittleness: Thickness was measured in a manner similar to that of Example 1 except that this adhesive PET was applied on the adhesive PET (A4300 100 m thickness: TOYOBO CO., LTD.) With a Meyer bar coater in a thickness of 20 탆 and a high pressure mercury lamp (80W / cm, ozone) Irradiated and cured to obtain a test piece. Thereafter, evaluation was carried out by bending the test piece by 180 °.

He ... No cracks

X ... Cracks occur

(7) Light transmittance: The ultraviolet curable resin was sandwiched between glass substrates, and the film thickness was adjusted using a spacer of 60 m and cured at 3000 mJ / cm2 using a high-pressure mercury lamp (80 W / cm, ozone) . The obtained test piece was measured for light transmittance of each wavelength at a wavelength of 380 to 780 nm by a spectrophotometer U-3900H (light source C) manufactured by Hitachi High-Technologies Corporation, and the value at 400 nm was regarded as a transmittance.

In the above table, Comparative Example 1 only shows items which can be measured in liquid phase because they were not cured at a high pressure mercury lamp (80 W / cm, ozone) at an irradiation of 3000 mJ / cm 2.

OXT-121: TOAGOSEI CO., LTD. Zinc silylene bisoxetane

OXT-221: TOAGOSEI CO., LTD. 3-Ethyl-3 - {[(3-ethyloxetan-3- yl) methoxy] methyl} oxetane

SEJ-01R: Nippon Kayaku Co., Ltd. 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate

GSID 26-1: Tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tris [(trifluoromethyl) sulfonyl] methanide (manufactured by BASF Japan Co.,

SZR-K: SAKAI CHEMICAL INDUSTRY CO., LTD. MEK dispersed zirconium oxide (solid content 30%, primary particle size 4 nm)

OXT-101: TOAGOSEI CO., LTD. 3-ethyl-3-hydroxymethyloxetane

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 small curing shrinkage, a cured product thereof has a high Tg and a low water vapor permeability. Therefore, it is suitable, for example, as a sealing material for various sealing materials, particularly an organic EL device, and can be used as an adhesive for bonding a sealing transparent substrate in solid sealing of the organic EL device.

INDUSTRIAL APPLICABILITY The resin composition of the present invention is suitable as a sealing material for various sealing materials, particularly, organic EL devices, because it has a small curing shrinkage ratio and is excellent in visible light transmittance and light resistance, high in Tg and low in water vapor permeability, And can be used as an adhesive for bonding transparent substrates for sealing in solid sealing.

Claims (23)

(EN) Disclosed is an energy ray curable resin composition for an organic EL device sealing material which does not contain a (meth)
(A) containing two or more oxetane rings in a molecule and an alicyclic epoxy compound (B)
The content of the compound (B) is 20 to 70 parts by mass based on 100 parts by mass of the total amount of the compound (A) and the compound (B)
The compound (A) having two or more oxetane rings in the molecule is a compound having an oxytetane ring represented by the following general formula (1) and the following general formula (2)
Wherein the content of the compound represented by the following formula (2) is in the range of 0.6 to 1.5 parts by mass based on 1 part by mass of the compound represented by the following general formula (1).
In general formula (1)

Wherein R ₁ represents a direct bond or a linear or branched hydrocarbon group having 1 to 6 carbon atoms, R ₂ represents a hydrocarbon group containing an alicyclic ring, an aromatic ring, a heterocyclic ring or a condensed ring, R ₃ each independently represent a linear or branched hydrocarbon group having 1 to 6 carbon atoms and n is an average value and represents an integer of 1 to 5,
In general formula (2)

[Wherein, R ₄ each independently represent C 1 -C 6 straight-chain or branched hydrocarbon group of, R ₅ are independently represents a hydrocarbon group having 1 to 6 carbon atoms of straight-chain or branched-chain, respectively; The method according to claim 1,
The energy ray-curable resin composition according to any one of claims 1 to 3, wherein the energy ray-curable resin composition contains no organic compound component having no reactive group having a weight average molecular weight of 10,000 g / mol or more, Energy radiation curable resin composition for an EL element sealing material. The method according to claim 1,
Wherein the compound (A) having at least two oxetane rings in the molecule is a compound having at least an alicyclic or aromatic ring in the molecule. 3. The method according to claim 1 or 2,
Wherein the total organic compound components contained in the resin composition have a weight average molecular weight of 10,000 g / mol or more and are mutually soluble at 20 ° C to 80 ° C. 3. The method according to claim 1 or 2,
Wherein the content of the epoxy compound (B) and the cationic polymerization initiator (C) in the total amount is 0.1 to 70 parts by mass relative to 100 parts by mass of the total amount of the resin composition excluding the solvent , And the compound (A) is contained in an amount of 30 to 99.9 parts by mass based on 100 parts by mass of the total amount of the resin composition excluding the solvent. The method according to claim 1,
Wherein the epoxy compound (B) is a compound having two or more epoxy groups in the molecule. The method according to claim 1,
Characterized by containing 30 to 90 parts by mass of a compound (A) having two or more oxetane rings in a molecule in a total amount of 100 parts by mass of the compound (A) and the epoxy compound (B) Curable resin composition. 3. The method according to claim 1 or 2,
An energy ray curable resin composition for an encapsulating material for an organic EL device, which further contains a cationic ion polymerization initiator (C). 9. The method of claim 8,
The energy ray curable resin composition for an organic EL device sealing material according to claim 1, wherein the cationic ion polymerization 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 salt. 3. The method according to claim 1 or 2,
And further contains fine particles (D). The energy ray curable resin composition for an organic EL device sealing material according to claim 1, 11. The method of claim 10,
Wherein the particle diameter of the fine particles (D) is 100 nm or less. 3. The method according to claim 1 or 2,
Wherein the viscosity at 25 DEG C measured by an E-type viscometer is 10 mPa • s or more. 3. The method according to claim 1 or 2,
And the curing shrinkage ratio when the resin composition is cured is 5.5% or less. A cured product obtained by curing an energy ray curable resin composition for an organic EL device sealing material according to claim 1. 15. The method of claim 14,
And a water vapor permeability at a thickness of 100 占 퐉 is 200 g / m2 占 day / 60 占 폚 or less. An organic EL display having the cured product according to claim 14 or 15.
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