TW201410660A - Energy ray curable type resin composition and cured product thereof - Google Patents

Abstract

The present invention provides an energy ray curable type resin composition for organic EL element sealing material, the composition containing two or more compounds (A) having two or more oxetane rings in the molecule, for example the following formula (1) (wherein R1 each independently represents a direct bond or a linear or branched hydrocarbon group having 1 to 6 carbon atoms, R2 represents a linear or branched hydrocarbon group having 1 to 15 carbon atoms, or a hydrocarbon group containing an alicyclic ring, an aromatic ring, a heterocyclic ring or a condensed ring, R3 each independently represents a linear or branched hydrocarbon group having 1 to 6 carbon atoms, n represents 0 (zero) or an average value of an integer 1 to 5.) The resin composition has a small curing shrinkage rate, and the cured product thereof has excellent visible light transmittance and light resistance, high Tg, and low vapor permeability, therefore it is useful as a solid sealing material to solid seal organic EL element.

Description

Energy ray hardening resin composition and cured product thereof

The present invention relates to an energy ray-curable resin composition for use in sealing an organic EL element.

The energy ray-curable resin is generally solvent-free, and therefore has excellent workability. Moreover, since the hardening speed is fast and the energy required amount is low, the energy line hardening technique is an important technique in various industries including display peripheral materials. In recent years, in terms of displays, a thin display called a flat panel display (FPD) has been put on the market, and a plasma display (PDP) or a liquid crystal display (LCD) has been widely spread. Further, an organic EL display (OLED) is expected as a next-generation self-luminous thin film display, and some products have been put into practical use. The organic EL element of the organic EL display has a structure in which a device body including a thin film laminate including a light-emitting layer sandwiched between a cathode and an anode is formed on a substrate on which a driving circuit such as a TFT is formed. The layer in which the light-emitting layer or the electrode of the element portion is located is liable 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 to block intrusion of moisture or impurities from the outside. Various sealing technologies have been studied in the past to meet the high-performance organic EL elements with high quality, and a higher performance sealing material is desired.

As a typical sealing method of an organic EL element, a method of fixing a sealing cap made of metal or glass in which a desiccant is inserted in advance, and fixing it to a substrate of an organic EL element using an adhesive for sealing is studied. In this method, an adhesive is applied to the outer peripheral portion of the substrate of the organic EL element, a sealing cover is provided thereon, and then the adhesive is cured, whereby the substrate or the sealing cover is fixed, and the organic EL element is sealed. In such a method, the sealing is made mainstream by a sealing cover made of glass. However, since the sealing cap made of glass is produced by excavating a flat glass substrate for inserting a desiccant, it tends to be expensive. Further, since the desiccant is inserted into the inside of the seal cap by the seal of the seal cap, light cannot be taken out from the seal cap side. That is, the light emitted from the light source is taken out from the substrate side of the element, and is limited in terms of a bottom emission type element. In the case of a bottom-emission type element, there is a problem in that the aperture ratio is lowered by the driver circuit portion formed on the substrate, and the extraction efficiency is low because a part of the light is blocked by the driver circuit portion. Therefore, it has been desired to develop a sealing method applicable to a top emission type element which is suitable for taking out light from the opposite side of a substrate of an organic EL element.

Representative sealing methods that can be applied to top-emitting elements are film sealing methods and solid sealing methods. The film sealing method is a method in which a plurality of layers of an inorganic or organic material are laminated on an organic EL element to form a passivation film. When sufficient moisture resistance is imparted to the element by this method, it is necessary to sequentially laminate several layers of the film on the element. Therefore, the film sealing method has a long film forming step and a high cost, and tends to have a high initial investment due to introduction of a large vacuum system required for film formation.

On the other hand, the solid sealing method is provided with a passivation film so as to cover the entire element portion of the organic EL element, and a sealing material is provided thereon through the sealing material. The method of the substrate. In general, the passivation film is formed by vapor deposition or sputtering of an inorganic material, but most of them are incomplete films having pinholes or films having weak mechanical strength. Therefore, in the solid sealing method, since a transparent substrate for sealing such as a glass substrate is provided through a sealing adhesive after the passivation film is provided on the element, the reliability of sealing is improved. Such a solid sealing method focuses on a method of performing sealing of a top emission type element simply and at low cost.

In the sealing by the solid sealing method of the organic EL element, a heat or photocurable resin can be used as the sealing adhesive, but these characteristics may significantly affect the performance of the element and the productivity of the sealing operation, so it is very important. . For example, if the water vapor transmission rate of the sealing agent is insufficient, it may intrude into the element portion from the pinhole of the passivation film, resulting in deterioration of the element. Further, if the hardening reaction of the sealing material is slow, it takes time in the hardening step, and the productivity of the sealing operation may be lowered.

In order to protect the light-emitting element, the sealing agent used for such a seal has a high transmittance in the visible light region, and is resistant to light resistance, stable formability, and low hardening shrinkage for residual stress suppression. Isolation of low moisture vapor transmission rate of moisture, etc. Although it is possible to perform sealing by a solid sealing method using a known adhesive as an adhesive for an organic EL element, it is difficult to obtain a result that satisfies both reliability and productivity, and it is desired to develop a suitable one. An adhesive for sealing in a solid sealing method.

Several types of curable resin compositions containing an oxetane compound are known (for example, Patent Documents 1 to 5). However, it has not been known that a hardened resin composition is used for at least two kinds of compounds having at least two oxetane rings in combination with an organic EL.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent No. 3876630

[Patent Document 2] Japanese Patent No. 2679586

[Patent Document 3] Japanese Patent No. 4421938

[Patent Document 4] Japanese Patent No. 4557172

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2000-169552

The resin composition suitable for the sealing material of the organic EL element requires a small hardening shrinkage ratio, and the cured product obtained from the resin composition requires visible light transmittance, light resistance, and hardenability. Excellent, high Tg, 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 requirements, and a cured product obtained from the resin composition.

The inventors of the present invention have intensively studied to solve the above problems, and have found that an energy ray-curable resin composition containing at least two or more kinds of compounds (A) having two or more oxetane rings in a molecule and The cured product can solve the aforementioned problems, and the present invention has been completed.

That is, the present invention relates to the following (1) to (23).

(1) An energy ray-curable resin composition for an organic EL element sealing material, which contains two or more kinds of compounds (A) having two or more oxetane rings in a molecule.

(2) An energy ray-curable resin group for an organic EL element sealing material as described in (1) In the product, the energy ray-curable resin composition does not contain an organic compound component having no reactive group having a weight average molecular weight of 10,000 g/mol or more, or a content of the resin composition relative to the total amount of the resin composition. The system is less than 1.5% by weight.

(3) The energy ray-curable resin composition for an organic EL device sealing material according to the above aspect, wherein the compound (A) having two or more oxetane rings in the molecule is At least having the following general formula (1) or the following general formula (2); (wherein R ₁ each independently represents a direct bond or a linear or branched chain hydrocarbon group having 1 to 6 carbon atoms, and R ₂ represents a linear or branched chain hydrocarbon group having 1 to 15 carbon atoms, or a hydrocarbon group containing an alicyclic ring, an aromatic ring, a heterocyclic ring or a condensed ring, wherein R ₃ each independently represents a linear or branched chain hydrocarbon group having 1 to 6 carbon atoms, and n represents an integer having an average value of 1 to 5); (wherein R ₄ each independently represents a linear or branched chain hydrocarbon group having 1 to 6 carbon atoms, and R ₅ each independently represents a linear or branched chain hydrocarbon group having 1 to 6 carbon atoms).

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

(5) Energy for sealing an organic EL element according to any one of (1) to (4) The linear curable resin composition contains the compound of the above formula (1) and the compound of the above formula (2) as the compound (A) having two or more oxetane rings in the molecule.

(6) The energy ray-curable resin composition for an organic EL device sealing material according to the item (5), wherein the content of the compound of the formula (2) is 0.6 to 1 part by mass of the compound of the formula (1) A range of 1.5 parts by mass.

The energy ray-curable resin composition for an organic EL device sealing material according to any one of the above aspects, which contains two or more kinds of oxygen heterocyclic rings having two or more kinds in the molecule. The compound (A) of the butane ring has a total organic compound component contained in the resin composition of a weight average molecular weight of 10,000 g/mol or less, and is composed of a mutually soluble component at 20 ° C to 80 ° C.

(8) The energy ray-curable resin composition for an organic EL device sealing material according to any one of the above aspects, which does not contain a (meth) acrylate compound or even contains (methyl) The acrylate compound is also less than 15 parts by mass based on 100 parts by mass of the total amount of the resin composition from which the solvent is removed.

The energy ray-curable resin composition for an organic EL device sealing material according to any one of the above aspects, further comprising an epoxy compound (B) and a photocationic polymerization initiator ( Any one or both of C) is contained in an amount of 0.1 to 70 parts by mass based on 100 parts by mass of the total of the solvent-removing resin composition, and the above compound (A) is based on the total content thereof, relative to the solvent to be removed. The total amount of the resin composition is 100 parts by mass, and is 30 to 99.9 parts by mass.

The energy ray-curable resin composition for an organic EL device sealing material according to any one of the above aspects, further comprising an epoxy compound (B).

(11) The energy ray hardening of the organic EL element sealing material as described in (9) or (10) A resin composition in which the epoxy compound (B) is an alicyclic epoxy compound.

The energy ray-curable resin composition for an organic EL device sealing material according to any one of the above aspects, wherein the epoxy compound (B) has two or more rings in the molecule. A compound of an oxy group.

The energy ray-curable resin composition for an organic EL device sealing material according to any one of the above aspects, wherein the total of the compound (A) and the epoxy compound (B) The amount is 100 parts by mass, and the epoxy compound (B) is contained in an amount of 20 to 70 parts by mass.

The energy ray-curable resin composition for an organic EL device sealing material according to any one of the above aspects, wherein the compound having two or more oxetane rings in the molecule 100 parts by mass of the total of (A) and the epoxy compound (B), and 30 to 90 parts by mass of the compound (A).

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

(16) The energy ray-curable resin composition for an organic EL device sealing material according to the item (15), wherein the photocationic polymerization initiator (C) is an onium salt, an iodonium salt, a phosphonium salt or an ammonium salt. And at least one selected from the group consisting of citrate.

The energy ray-curable resin composition for an organic EL device sealing material according to any one of the above aspects, further comprising fine particles (D).

(18) The energy ray-curable resin composition for an organic EL element sealing material according to the item (17), wherein the primary particle diameter 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 any one of the above aspects, wherein the viscosity at 25 ° C is 10 mPa as measured by an E-type viscosity meter. s above.

The energy ray-curable resin composition for an organic EL device sealing material according to any one of the above aspects, wherein the curing shrinkage ratio when the resin composition is cured is 5.5% or less.

(21) A cured product obtained by curing the energy ray-curable resin composition of the organic EL element sealing material according to any one of the above (1) to (20).

(22) The cured product according to (21), wherein the water vapor permeability at a thickness of 100 μm is 200 g/m ² . Daily / 60 ° C or less.

(23) An organic EL display comprising the cured product according to (21) or (22).

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

In the present invention, the term "for an organic EL element sealing material" means a sealing of an organic EL element, in particular, a solid sealing agent filled in a solid sealing between a sealing substrate such as glass and an organic EL element.

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

According to the above configuration, the two types of bifunctional oxetane compounds can be introduced into the curing system at the time of curing, and can be simultaneously achieved in one type. Heat resistance, rigidity, refractive index control, water resistance, and low shrinkage.

In other words, when one type of bifunctional oxetane compound or a monofunctional oxetane compound is used in combination with one type of bifunctional oxetane compound, it is difficult to achieve the above effects at the same time. However, by using two kinds of bifunctional oxetane compounds, the low shrinkage ratio, high rigidity, high refractive index, and high water resistance at the time of curing are maintained, and two or more types of oxetane compounds are Since it is introduced in a hardening system intricately, it is possible to provide a cured product which is highly resistant to heat (high glass transition point (Tg) which cannot be achieved with only one type of oxetane compound in terms of the multiplication effect. ))By. Further, by using two or more types, heat resistance, rigidity, refractive index, and shrinkage ratio can be easily controlled.

The compound (A) having at least two oxetane rings in the molecule contained in the resin composition of the present invention may be any one as long as it has at least two oxetane rings in the molecule.

The compound (A) having at least two oxetane rings in the molecule may, for example, be 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl} Benzene (commercially available as ARONE OXETANE ^RTM OXT-121 as a main component (containing 80% or more)) (East Asia Synthetic Co., Ltd.); xylylene dioxetane), 3-ethyl-3 {[(3-Ethyloxetidin-3-yl)methoxy]methyl}oxetane, bis[2-(3-oxetanyl)butyl]ether, 1 , 4-bis[(3-ethyloxetan-3-yl)methoxy]benzene, 1,3-bis[(3-ethyloxetan-3-yl)methoxy Benzene, 1,2-bis[(3-ethyloxetan-3-yl)methoxy]benzene, 4,4'-bis[(3-ethyloxetane-3- Methoxy]biphenyl, 2,2'-bis[(3-ethyl-3-oxetanyl)methoxy]biphenyl, 3,3',5,5'- Tetramethyl[4,4'-bis(3-ethyloxetan-3-yl)methoxy]biphenyl, 2,7-bis[(3-ethyloxetane- 3-yl)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] Decane, 1, 2-bis{[2-(1-ethyl-3-oxetanyl)methoxy]ethylsulfanylethane, 4,4'-bis[(1-ethyl-3-oxa) Cyclobutane)methyl]thiodiphenyl sulfide, 2,3-bis[(3-ethyloxetan-3-yl)methoxymethyl]norbornane, 2-ethyl- 2-[(3-Ethyloxetan-3-yl)methoxymethyl]-1,3-O-bis[(1-ethyl-3-oxetanyl)methyl ]-propane-1,3-diol, 2,2-dimethyl-1,3-O-bis[(3-ethyloxetan-3-yl)methyl]-propane-1, 3-diol, 2-butyl-2-ethyl-1,3-O-bis[(3-ethyloxetan-3-yl)methyl]-propane-1,3-diol , 1,4-O-bis[(3-ethyloxetan-3-yl)methyl]-butane-1,4-diol, 2,4,6-O-para [[3 -Ethyloxetane-3-yl)methyl]cyanuric acid or the like. These are preferably two or more kinds, and preferably an oxetane compound having at least one epoxy group.

Preferred oxetane compounds having at least two oxetane rings used in the present invention include at least two oxetane ring systems having a crosslinking group containing at least one ether bond. And a linked oxetane compound. In the present invention, it is preferred to use at least two kinds of the oxetane compound. In the preferred aspect, two types of different types are used. A preferred embodiment is an oxetane compound having a crosslinking group containing the above-mentioned ether bond, a oxetane compound having a chain-crosslinking group having no ring structure, and an oxetane having a chain-crosslinking group having a ring structure. The two types of compounds are used together. The above effects can be more fully achieved by using the two types of oxetane compounds in combination.

The oxetane ring system in which at least two oxetane rings are linked by a crosslinking group containing at least one ether bond is a compound of the above formula (1) or (2). Further, in the present invention, "crosslinking group" means bonded to 2 atoms. The 2 valence between.

The combination of the two types of the oxetane compound is preferably a combination of the compound of the above formula (1) or the compound of the formula (2). In particular, in terms of ease of obtaining from the market, it is particularly preferred to be xylylene dioxetane and 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy A combination of a group of methyl}oxetane.

In the present invention, a preferred compound as a bifunctional oxetane compound is an oxetane compound represented by the formula (1): (wherein R ₁ each independently represents a direct bond or a linear or branched chain hydrocarbon group (hydrocarbon bond) having a carbon number of 1 to 6, and R ₂ represents a straight or branched chain having a carbon number of 1 to 15. a hydrocarbon group (hydrocarbon bond), 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 linear or branched chain hydrocarbon group having 1 to 6 carbon atoms, and n represents an average value. Is an integer from 1 to 5.)

Further, in the above formula (1), R ₁ and R ₂ are as defined in the above structural formula, and are a divalent hydrocarbon group, and R ₃ is a monovalent hydrocarbon group.

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

R _{2 is} preferably a linear alkylene group having 1 to 12 carbon atoms, a branched alkyl group having 1 to 12 carbon atoms, a stretching phenyl group having 3 to 12 carbon atoms or an alkylene group having a cycloalkyl group. Particularly preferred is an alkylene group having a pendant phenyl group having 6 to 12 carbon atoms (preferably an alkylene group having 1 to 4 carbon atoms).

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

n is preferably from 1 to 3.

Further, in the compound of the above formula (1), a ring structure having an alicyclic ring, an aromatic ring, a heterocyclic ring or a condensed ring is used for R ₂ (for example, a stretching phenyl group, an anthranyl group, and a carbon number of 3 to 8). The oxetane compound of the alkyl group is preferred because the hardening shrinkage ratio is small, and the Tg (glass transition point), rigidity, and refractive index of the cured product are improved.

Here, among the compounds of the above formula (1), a specific example is a compound represented by the following formula (3): (wherein R ₃ represents the same meaning as the above formula (1), and may be the same or different. Z represents a cyclic group having a carbon number of 3 to 12, and the ring system may be an alicyclic ring (aliphatic ring) Any of an aromatic ring, a heterocyclic ring or a condensed ring. n represents an integer having an average value of 1 to 5.

The cyclic group having 3 to 12 carbon atoms of Z is preferably a divalent aliphatic ring group or an aromatic ring group, and particularly preferably a phenyl group.

By using the compound of the above formula (3), a lower hardening shrinkage ratio can be maintained.

Further, the oxetane compound represented by the following formula (2) is as follows.

In the formula, R ₄ each independently represents a linear or branched chain hydrocarbon group having 1 to 6 carbon atoms, and R ₅ each independently represents a linear or branched chain hydrocarbon group having 1 to 6 carbon atoms. Further, R ₄ is as defined in the above structural formula, and 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} preferably a linear hydrocarbon group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms. In R ₅ , a linear hydrocarbon group having 1 to 3 carbon atoms is preferred, and an alkyl group having 1 to 3 carbon atoms is particularly preferred.

Further, when an oxetane compound having a ring structure of a left unalicyclic ring, an aromatic ring, a heterocyclic ring or a condensed ring (for example, a phenylene group, an extended naphthyl group, or a cycloalkyl group having 3 to 8 carbon atoms) is used as One of the components is preferable because the Tg (glass transition point), rigidity, and refractive index of the cured product are improved. More preferably, the tether is constructed as an alicyclic or aromatic oxetane compound. Specifically, it is a compound represented by the above formula (3).

The content of the component (A) of the present invention is from 30 to 100 parts by mass, more preferably from 30 to 90 parts by mass, particularly preferably 100 parts by mass based on the total of the component (A) + the component (B) of the reactive compound. 40 to 90 parts by mass. Further, as the case may be, the above content of the component (A) is also preferably from 30 to 80 parts by mass, more preferably from 50 to 75 parts by mass. The rest is ingredient (B).

In addition, the content ratio of the component (A) per 100 parts by mass of the total amount of the resin composition of the present invention (the solvent is removed in the case of a solvent) is usually 30 to 99.9 parts by mass, more preferably 40 to 99.5 parts by mass. It is particularly preferably from 50 to 99.5 parts by mass.

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

Further, the above-mentioned oxetane compound (preferably, the compound represented by the formula (2)) having a functional group equivalent of 50 to 150 g/eq is equivalent to a functional group equivalent of 100 to 200 g/eq and having an aromatic ring. An oxetane compound (preferably a compound represented by the formula (3), more preferably a compound of the formula (3) wherein Z is a phenylene group), can obtain a high Tg (glass transition point) and a high refractive index. The resin composition.

When a compound of the formula (1) (preferably a compound of the formula (3)) and a compound of the formula (2) are used in combination, the ratio of the two is relative to 1 part by mass of the compound of the formula (1), and the formula (2) The compound is usually in the range of 0.6 to 1.5 parts by mass, preferably in the range of 0.7 to 1.3 parts by mass, more preferably 0.8 to 1.2 parts by mass, most preferably in the range of 0.9 to 1.1 parts by mass.

The epoxy group-containing compound (B) (hereinafter also referred to as epoxy compound (B) or component (B)) contained in the resin composition of the present invention may be a monofunctional epoxy compound and a polyfunctional ring. Any of the oxygen compounds. Further, it may be any of an epoxy compound (aromatic epoxy compound) containing an aromatic ring or an aliphatic epoxy compound not containing an aromatic ring. In the present invention, it is preferably an aromatic epoxy compound or an epoxy compound containing an aliphatic ring (containing an aliphatic ring epoxy compound). It is particularly preferred to form an epoxy-based alicyclic epoxy compound on the aliphatic ring.

Examples of the monofunctional epoxy compound include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and allyl shrinkage. Glyceryl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2 - epoxy decane, styrene oxide, cyclohexene oxide, 3-methylpropenyloxymethylcyclohexene oxide, 3-propenyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, or the like.

Examples of the polyfunctional epoxy compound include bisphenol A diglycidyl ether, bisphenol E diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, and bromine. Bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenation double Phenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5 ,5-spiro-3,4-epoxy)cyclohexane-methane-two Alkane, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis(3,4-epoxy-6 -Methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6'-methylcyclohexanecarboxylate, Methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol bis(3,4-epoxycyclohexylmethyl)ether, ethylene bis ( 3,4-epoxycyclohexanecarboxylate), dioctyl epoxy hexahydrophthalate, di-2-ethylhexyl hexahydrophthalate, 1,4-butanediol Glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol dihydrate Glyceryl ether, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8-dicyclooxycyclooctane, 1,2,5,6-dicyclooxycyclooctane, and the like.

As an example of the alicyclic epoxy compound, any compound containing a cyclohexene oxide or a cyclopentene oxide can be used. Specifically, the alicyclic epoxy compound can be exemplified by a compound having the following structure.

(where n is the average value, indicating a positive number from 1 to 5)

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

Among the above epoxy compounds, an aromatic epoxy compound and an alicyclic epoxy compound are preferred in terms of excellent curing rate. Particularly preferred is an alicyclic epoxy compound. Among the alicyclic epoxy compounds, a bifunctional alicyclic epoxy compound is preferred, and 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexane is particularly preferred. Alkene carboxylate.

The epoxy compound (B) may be used singly or in combination of two or more. The content of the component (B) of the present invention is usually from 0 to 70 parts by mass, preferably from 10 to 70 parts by mass, based on 100 parts by mass of the total of the component (A) + the component (B) of the reactive compound, more preferably 20 to 70 parts by mass, particularly preferably 25 to 50 parts by mass. Further, it is preferably from 10 to 60 parts by mass, as the case may be.

The epoxy compound (B) used in the present invention preferably has an epoxy group equivalent of from 50 to 500 g/eq, more preferably from 100 to 300 g/eq.

The photocationic polymerization initiator (C) contained in the resin composition of the present invention may, for example, be an aromatic iodonium salt or an aromatic sulfonium salt.

Specific examples of the aromatic iodonium salt may, for example, be diphenyl iodonium (pentafluorophenyl) borate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroantimonate, Bis(4-nonylphenyl)iodonium hexafluorophosphate or the like.

Specific examples of the aromatic sulfonium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium (pentafluorophenyl) borate, and 4,4'- Bis[diphenylindenyl]diphenyl sulfide-bishexafluorophosphate, 4,4'-bis[bis(β-hydroxyethoxy)phenylindenyl]diphenyl sulfide-bis hexafluoro Citrate, 7-[bis(p-tolylmethyl)indolyl]-2-isopropylthioxanthone hexafluorophosphate, 7-[bis(p-tolylmethyl)indolyl]-2- Isopropyl thioxanthone hexafluoroantimonate, 7-[bis(p-tolylmethyl)indolyl]-2-isopropylindole (pentafluorophenyl)borate, phenylcarbonyl-4'- Diphenyldecyl-diphenylsulfide Ether-hexafluorophosphate, phenylcarbonyl-4'-diphenylfluorenyl-diphenyl sulfide-hexafluoroantimonate, 4-tert-butylphenylcarbonyl-4'-diphenylfluorenyl -diphenyl sulfide-hexafluorophosphate, 4-tert-butylphenylcarbonyl-4'-diphenyldecyl-diphenyl sulfide-hexafluoroantimonate, 4-tert-butylbenzene Alkylcarbonyl-4'-diphenylindenyl-diphenyl sulfide-indole (pentafluorophenyl)borate, thiophenyldiphenylphosphonium hexafluoroantimonate, thiophenyldiphenylphosphonium hexafluorophosphate Phosphate, 4-{4-(2-chlorobenzylidene)phenylthio}phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, thiophenyldiphenylphosphonium hexafluoroantimonate Halide, 4,4',4"-tris(β-hydroxyethoxyphenyl)phosphonium hexafluoroantimonate, 4,4'-bis[diphenylfluorenyl]diphenyl sulfide-double Hexafluoroantimonate, diphenyl[4-(phenylthio)phenyl]phosphonium trifluoropentafluoroethyl phosphate, ginseng [4-(4-ethylmercaptophenylthio)phenyl]anthracene Reference to [(trifluoromethyl)sulfonyl]methyl and the like.

Among the aromatic salts, it is preferably thiophenyldiphenylphosphonium hexafluorophosphate and 4-{4-(2-chlorobenzylidene)phenylthio}phenyl which are highly sensitive and easily available from the market. Bis(4-fluorophenyl)phosphonium hexafluoroantimonate, diphenyl[4-(phenylthio)phenyl]phosphonium trifluoropentafluoroethyl phosphate, ginseng [4-(4-ethyl fluorenyl) Phenylthio)phenyl]indole [(trifluoromethyl)sulfonyl]methyl and the like.

Further, in view of the environmental and human hazards, and the regulations of each country, it is most preferable to use diphenyl[4-(phenylthio)phenyl]phosphonium trifluoropentafluoroethyl phosphate which does not contain barium. And [4-(4-ethylmercaptophenylthio)phenyl]indole [(trifluoromethyl)sulfonyl]methyl.

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

In addition, the ratio of the component (C) is preferably in the same range as described above, with respect to 100 parts by mass of the total amount of the resin composition (the solvent is removed in the case of containing a solvent). Further, the component (C) content ratio relative to 100 parts by mass of the component (A) is also about the same as the above phase The same range is appropriate.

Further, in the resin composition of the present invention, the photocationic polymerization initiator (C) may be used singly or in combination of plural kinds.

Further, a radical type photopolymerization initiator can be used in combination. In the case of a radical type photopolymerization initiator, it may be any photopolymerization initiator such as 2-hydroxy-2-methyl-phenylpropan-1-one or 1-hydroxycyclohexyl-phenyl ketone.

The fine particles (D) used in the present invention may, for example, be organic fine particles or inorganic fine particles. Further, the fine particles (D) are used in consideration of the required light transmittance, hardness, scratch resistance, hardening shrinkage ratio, and refractive index, and may be used singly or in combination of plural kinds as needed. 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 refractive index of the liquid can be increased.

Further, from the viewpoint of increasing the transmittance of light of the cured product (especially, the transmittance of light having a wavelength range of from 380 nm to 780 nm), the resin composition of the present invention is preferably one which does not contain the fine particles (D). .

Examples of the organic fine particle system to be used in the present invention include organic polymer particles such as polystyrene resin particles, acrylic resin particles, urethane resin particles, and polycarbonate resin particles; porous polystyrene resin particles and porous Porous organic polymer particles such as acrylic resin particles, porous urethane resin particles, and porous polycarbonate resin particles; resin powder of benzoguanamine-formalin condensate, benzene Resin powder of guanamine-melamine-formalin condensate, resin powder of urea-formalin condensate, powder of aspartate derivative, powder of zinc stearate, powder of guanyl stearate, ring Oxygen resin powder, polyethylene powder, etc., preferably crosslinked polymethyl methacrylate resin Particles or crosslinked polymethyl methacrylate/styrene resin particles and the like. These organic fine particle systems can be easily obtained from commercially available products, and a known document can be prepared as a reference.

Examples of the inorganic fine particles 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 the like. Gallium-doped zinc oxide, fluorine-doped tin oxide, and the like. The transparent metal oxide used in the present invention may, for example, be silica, titania, zirconia, cerium oxide, zinc oxide, iron oxide, titanium oxide/zirconia/tin oxide/penta pentoxide complex, Zirconium oxide/tin oxide/penta pentoxide composite, titanium oxide/zirconia/tin oxide composite, and the like.

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 wear resistance and high refractive index, and are applicable to titanium oxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, titanium oxide/zirconia/tin oxide/five. Metal oxide fine particles such as cerium oxide composite, zirconia/tin oxide/penta pentoxide composite, and titanium oxide/zirconia/tin oxide composite. Further, since the optical sheet used for the display requires high light transmittance, the primary particle diameter of the fine particles is preferably 100 nm or less. The compounding ratio is usually from 0 to 30 parts by mass, and is usually from 1 to 30 parts by mass, preferably from 5 to 20 parts by mass, based on 100 parts by mass of the total of the component (A) + the component (B).

Further, as the dispersing agent for the fine particles, a polycarboxylic acid-based dispersing agent, a decane coupling agent, a titanate coupling agent, a modified polyfluorene oxide oil, or the like, or a polyorganosiloxane dispersing agent or an organic copolymer may be used in combination. Dispersing agents, etc. Relative to the resin of the present invention The total mass of the composition (the total amount of the resin composition from which the solvent is removed) is about 0 to 30% by mass, preferably about 0.05 to 5% by mass.

Further, the primary particle diameter means the smallest particle diameter of the particles when the aggregation collapses. That is, in the microscopic shape of the round shape, the short diameter is the primary particle diameter. The primary particle size can be measured by dynamic light scattering or electron microscopic observation. Specifically, a JSM-7700F electric field release scanning electron microscope manufactured by JEOL Ltd. was used, and the primary particle diameter was measured under an acceleration voltage of 30 kV.

In the present invention, the primary particle diameter is preferably 100 nm or less. Further, fine particles of 5 to 100 nm can be suitably used. By being 100 nm or less, it is possible to provide a cured product having a hardening shrinkage ratio and a low moisture permeability of the resin composition and a relatively high light transmittance.

The microparticles can be dispersed in a solvent for use. In particular, the inorganic fine particles can be obtained by dispersing in the form of water or an organic solvent to obtain a commercially available product. 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 the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane, and decane; and petroleum ethers of a mixture thereof; White gas, petroleum brain, etc.

Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate; cyclic esters such as γ-butyrolactone; ethylene glycol monomethyl ether acetate; and diethyl 2 Alcohol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol Monomethyl ether monoacetate, butanediol monomethyl ether monoacetate, etc. (single or poly) alkyl glycol monoalkyl ether monoacetate, glutaric acid dialkyl ester, succinic acid II Alkyl ester A polycarboxylic acid alkyl ester such as a dialkyl dicarboxylate.

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

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

Further, in the resin composition of the present invention, the viscosity, refractive index, adhesion, and the like of the obtained resin composition of the present invention are considered, and in addition to the component (A) and the component (B), reactivity may be used. Compound. Specifically, for example, a (meth) acrylate compound can be mentioned.

As the (meth) acrylate compound, a monofunctional (meth) acrylate, a bifunctional (meth) acrylate, and a polyfunctional group having three or more (meth) acryloxy groups in the molecule can be used. Acrylate, urethane (meth) acrylate, polyester (meth) acrylate, (meth) acrylate epoxy ester, and the like.

In the present invention, from the viewpoint of keeping the curing shrinkage ratio small, when the (meth) acrylate compound is not contained or contained, the degree of curing shrinkage is not increased, for example, the resin composition with respect to the solvent is removed. The total amount of the substance 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. In the present invention, from the viewpoint of keeping the hardening shrinkage ratio small, it is most preferable that the (meth) acrylate compound is not contained.

Examples of the monofunctional (meth) acrylate include isobornyl (meth)acrylate, dicyclopentanylmethacrylate (meth)acrylic acid, and dicyclopentenyl methacrylate (dicyclopentenyl methacrylate). (meth) propylene An alicyclic (meth) acrylate such as dicyclopentenyloxyethyl acid or cyclohexyl (meth)acrylate; tetrahydrofuran (meth) acrylate or caprolactone modified tetrahydrofuranyl (meth) acrylate (meth) acrylate having a heterocyclic ring such as morpholine (meth) acrylate; benzyl (meth) acrylate, ethoxy modified cresol (meth) acrylate, propoxy modified A Phenol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, o-phenyl phenol (meth) acrylate, o-phenyl phenol monoethoxy (meth) acrylate, adjacent Phenolic phenol polyethoxy (meth) acrylate, p-phenyl phenol (meth) acrylate, p-phenyl phenol monoethoxy (meth) acrylate, p-phenyl phenol polyethoxy (A (meth) acrylate having an aromatic ring such as acrylate, o-phenyl phenyl methacrylate or p-phenyl phenyl methacrylate; (poly) ethoxy methacrylate (meth) acrylate, ( (poly) (meth) acrylate having a heterocyclic ring such as acryloxy (meth) acrylate or (poly)caprolactone modified carbazole (meth) acrylate; (meth) methacrylate; (poly)ethoxy(methyl)propyl Naphthyl ester, (poly)propoxy (meth) methacrylate, (poly) caprolactone modified naphthyl (meth) acrylate, binaphthol (meth) acrylate, binaphthol (poly Ethoxy (meth) acrylate, binaphthol (poly) propoxy (meth) acrylate, (poly) caprolactone modified binaphthol (meth) acrylate, naphthol (methyl) Acrylate, naphthol (poly)ethoxy (meth) acrylate, naphthol (poly) propoxy (meth) acrylate, (poly) caprolactone modified naphthol (meth) acrylate (meth) acrylate having a condensed ring; quinone imine (meth) acrylate having a quinone ring structure; butane diol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, dipropylene glycol (meth)acrylate, etc. Acrylate; dimethylaminoethyl (meth)acrylate, butoxyethyl (meth)acrylate, caprolactone (meth)acrylate, isobutyl (meth)acrylate, (methyl) ) Third butyl acrylate, octafluoropentyl (meth) acrylate, octyl (meth) acrylate ,(Methacrylate Anthracene ester, isodecyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate Ethyl (meth) acrylate having an alkyl group such as ester, isomyristyl (meth) acrylate or lauryl (meth) acrylate; ethoxy diethylene glycol (meth) acrylate, 2-ethyl a (meth) acrylate of a polyhydric alcohol such as hexyl carbitol (meth) acrylate, polyethylene glycol (meth) acrylate or polypropylene glycol (meth) acrylate;

Examples of the (meth) acrylate monomer having two functional groups include hydrotrivalaldehyde modified trimethylolpropane di (metha) tacrylate, and the like. (meth) acrylate having a heterocyclic ring; (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 II Methyl) acrylate, (poly)propoxy modified bisphenol S di(meth) acrylate, hexahydrophthalic acid di(meth) acrylate, bisphenoxy (poly) ethoxy hydrazine, hydrazine (meth) acrylate having an aromatic ring such as phenyl dimethanol di(meth) acrylate; binaphthol di(meth) acrylate, binaphthol (poly) ethoxy di(meth) acrylate a condensed ring (meth) acrylate such as binaphthol (poly)propoxy di(meth) acrylate or (poly)caprolactone-modified binaphthol di(meth) acrylate; bisphenol Bismuth (meth) acrylate, bisphenoxy cresyl hydrazine (poly) aromatic (meth) acrylate such as di(meth) acrylate, bisphenoxyethanol hydrazine di(meth) acrylate, bisphenoxycaprolactone 茀 di(meth) acrylate Acrylate of isocyanate such as diacrylated isocyanate; 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol Di(meth)acrylate, polytetramethylene glycol di(meth)acrylate (meth) acrylate having a linear methylene structure; an alicyclic (meth) acrylate such as tricyclodecane dimethanol (meth) acrylate; ethylene glycol di(meth) acrylate, a di(meth)acrylate of a polyhydric alcohol such as polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate or polypropylene di(meth)acrylate; and the like.

Examples of the polyfunctional (meth) acrylate monomer include propylene (propylene oxy oxy) trimeric isocyanate and (poly) caprolactone modified ginseng (propylene oxyethyl) trimer isocyanate. a polyfunctional (meth) acrylate of a trimeric isocyanate ring; 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) ethoxylate Modified dipentaerythritol penta (meth) acrylate, (poly) propoxy modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (poly) caprolactone modified dipentaerythritol Hexa(meth)acrylate, (poly)ethoxy modified dipentaerythritol hexa(meth)acrylate, (poly)propoxy-modified dipentaerythritol hexa(meth) acrylate, (poly)pentaerythritol poly( Methyl) acrylate, trimethylolpropane tri(meth) acrylate, (poly)ethoxy modified trimethylolpropane (Meth)acrylate, (poly)propoxy modified trimethylolpropane tri(meth)acrylate, bis(trimethylolpropane)tetra(meth)acrylate, tris(meth)acrylic acid Polyfunctional (meth) acrylate of a polyhydric alcohol such as glyceride; phosphorus-containing polyfunctional (meth) acrylate such as tris(meth)acrylate; trimethylolpropane benzoate (meth)acrylic acid An aromatic polyfunctional (meth) acrylate such as an ester; an acid-modified polyfunctional (meth) acrylate such as 2,2,2-paranyloxymethyl succinic acid; a polyfunctional (meth) acrylate having a polysiloxane skeleton such as methyl acrylate; and the like.

The urethane (meth) acrylate may, for example, be diolated The compound (including the polyester diol described below) is reacted with an organic polyisocyanate, and then a reaction product obtained by adding a (meth) acrylate having a hydroxyl group or the like is added.

Examples of the diol compound include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol. 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl -1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A polyethoxylate a diol, a bisphenol A polypropoxy diol, or the like, or a diol compound and a dibasic acid or an anhydride thereof (for example, succinic acid, adipic acid, sebacic acid, dimer acid, or different) A polyester diol or the like which is a reaction product of citric acid, citric acid, citric acid or the like.

The above organic polyisocyanate may, for example, be tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate or 2,4,4-trimethylhexamethylene Chain-like saturated hydrocarbon isocyanate such as bis-isocyanate, isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylene bis(4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenation a cyclic saturated hydrocarbon isocyanate such as xylene diisocyanate or hydrogenated toluene diisocyanate; 2,4-toluene diisocyanate, 1,3-xylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl- An aromatic polyisocyanate such as 4,4'-diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate or 1,5-anaphthyl diisocyanate.

Examples of the epoxy group (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, biphenyl type phenol aralkyl resin, and bisphenol A. A reaction product of an epoxy resin such as a terminal glycidyl group, an anthracene epoxy resin or a bisphenol S-type epoxy resin of a propylene oxide adduct with (meth)acrylic acid.

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

Among them, as the (meth) acrylate used in the resin composition of the present invention, a material having a low curing shrinkage ratio can be suitably used. Specifically, it is preferably a (meth) acrylate having a ring structure, and examples thereof include isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth)acrylate. Dicyclopentyloxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, p-cumylphenol (poly)ethoxy (meth)acrylate, naphthol (poly)ethoxy (Meth) acrylate, naphthol (poly) propoxy (meth) acrylate, phenyl phenol (poly) ethoxy (meth) acrylate, phenyl phenol (poly) propoxy (methyl) Acrylate, benzyl (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, hydrogen trimethyl acetaldehyde modified trimethylolpropane di (meth) acrylate, biphenyl Dimethanol di(meth)acrylate and the like. Particularly preferred is a phenylphenol (poly) ethoxy (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, hydrogen trimethyl acetaldehyde with a high Tg and a low hardening shrinkage. Trimethylolpropane di(meth)acrylate, biphenyldimethanol di(meth)acrylate.

Further, in the resin composition of the present invention, the other component (meth) acrylate which may be added as needed may be used singly or in combination of plural 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 generally from 0 to 200 parts by mass, and optionally from 100 to 200 parts by mass, It is preferably 50 to 100 parts by mass, but it is preferably contained as much as possible or minimally used in the resin composition of the present invention.

Further, when a (meth) acrylate compound is used, a photopolymerization initiator other than the photocationic polymerization initiator is preferably used. Specifically, benzoin, Benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether and other benzoin; acetophenone, 2,2-diethoxy-2-benzene Ethyl benzene, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroethyl benzene, 2-hydroxy-2-methyl-phenylpropan-1-one, two Ethoxyethyl benzene, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one, oligo[2] -Hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone] and other acetophenones; 2-ethyl hydrazine, 2-tert-butyl fluorene, 2- Anthraquinones such as proguanil and 2-pentylhydrazine; thiazepines such as 2,4-diethylthianone, 2,4-diisopropylthiaxanone, and 2-chlorothiazepinone Anthracene; acetals such as acetophene acetal, benzyl dimethyl acetal; benzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 4 , 4'-bismethylaminobenzophenone and other benzophenones; 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethyl a phosphine oxide such as benzamidine)-phenylphosphine oxide or diphenyl-(2,4,6-trimethylbenzylidene)phosphine oxide. Preferably, it is an acetophenone benzene, and more preferably, for example, 2-hydroxy-2-methyl-phenylpropan-1-one or 1-hydroxycyclohexyl-phenyl ketone. Further, in the resin composition of the present invention, the photopolymerization initiator may be used singly or in combination of plural kinds.

The content ratio of the photopolymerization initiator is usually from 0 to 10 parts by mass based on 100 parts by mass of the resin composition. It is usually used in an amount of from 0.001 to 10 parts by mass, preferably from 0.01 to 8 parts by mass.

The ratio of use of each component of the resin composition of the present invention is determined by considering a desired refractive index, durability, viscosity, adhesion, etc., and when the component (A) + the component (B) is 100 parts by mass, the component ( The content of A) is usually from 30 to 100 parts by mass, preferably from 30 to 80 parts by mass, more preferably from 40 to 70 parts by mass, or from 50 to 75 parts by mass. The content of the component (B) is usually from 0 to 70 parts by mass, preferably from 20 to 70 parts by mass, more preferably from 25 to 50 parts by mass, or from 30 to 60 parts by mass. In the invention The resin composition generally contains the component (C), and the component (C) is contained in an amount of from 0.1 to 10 parts by mass, preferably from 0.5 to 3 parts by mass. The component (D) is an optional component or may not be contained, but may be contained as needed. When it is contained, it is preferably 1 to 30 parts by mass based on 100 parts by mass of the total of the component (A) + the component (B). It is 5 to 20 parts by mass.

One of the preferred aspects of the present invention includes the following: (i) any one of the above compound (A), and (ii) an epoxy compound (B) and a photocationic polymerization initiator (C). Or both. In this case, the content of the above compound (A) of (i) is usually 30 to 99.9 parts by mass, preferably 40 to 10,000 parts by mass based on 100 parts by mass of the total of the solvent-removing resin composition. 99.5 parts by mass, more preferably 50 to 99.5 parts by mass, and optionally 40 to 90 parts by mass, more preferably 50 to 80 parts by mass, as the case may be. In addition, the content of the component (B) and/or the component (C) of the above (ii) is generally 0.1 to 70 parts by mass based on 100 parts by mass of the total amount of the resin composition from which the solvent is removed. It is from 0.5 to 60 parts by mass, and optionally from 10 to 60 parts by mass, more preferably from 20 to 50 parts by mass, as the case may be.

In the resin composition of the present invention, in addition to the above-mentioned components, in order to improve the convenience during handling, etc., a release agent, an antifoaming agent, a leveling agent, a light stabilizer, an antioxidant, and a polymerization may be contained as needed. Additives such as inhibitors, plasticizers, and antistatic agents.

The content of each additive is generally from 0 to 10 parts by mass based on 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.

Further, there are many cases in which a plasticizer is used in order to obtain durability and flexibility. The plasticizer used can be selected according to the desired viscosity, light resistance, transparency or flexibility. Specifically, olefin polymerization such as polyethylene or polypropylene can be cited. Compound; dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis(2-ethylhexyl) phthalate, diisononyl phthalate, butyl benzyl phthalate, citric acid Diisodecyl ester, dicyclohexyl phthalate, ethyl phthalyl ethyl glycolate, butyl decyl glycolate, etc.; trimellitic acid ginseng (2- Trimellitic acid ester such as ethylhexyl) ester; dibutyl adipate, diisobutyl adipate, hexamethylene di(2-ethylhexyl) ester, diisononyl adipate, hexane Diisodecyl phthalate, bis(2-(2-butoxyethoxy)ethyl) adipate, bis(2-ethylhexyl) sebacate, dibutyl sebacate, bismuth An aliphatic dibasic acid ester such as bis(2-ethylhexyl) acid or diethyl succinate; trimethyl phosphate, triethyl phosphate, tributyl phosphate, and bis(2-ethylhexyl) phosphate. Orthodecyl phosphates such as triphenyl phosphate, tricresyl phosphate, tris(dimethylphenyl) phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate; methyl ethyl ricinoleate (methyl acetyl ricinoleate) and other ricinoleate, poly(1,3-butanediol adipate) Acetate such as polyester; glycidyl triacetate; sulfonamide such as N-butylbenzenesulfonamide; polyethylene glycol benzoate, polyethylene glycol dibenzoate, polypropylene glycol phthalate Polyoxyalkylene (di)benzoate such as ester, polypropylene glycol dibenzoate, polybutanediol benzoate, polybutanediol benzoate; polypropylene glycol, polyethylene glycol Polyethers such as alcohol and polybutanediol; polyalkoxy modified bisphenol A, polypropoxy modified bisphenol A and other polyalkoxy modified bisphenol A, polyethoxy modified bisphenol F, Polypropoxy modified bisphenol F such as polypropoxy modified bisphenol F; polycyclic aromatic such as naphthalene, phenanthrene and anthracene; (bin) naphthol, (poly)ethoxy modified (bi) naphthol, (poly)propoxy modified (bin) naphthol, (poly) butanediol modified (linked) naphthol, (poly) caprolactone modified (linked) naphthol and other naphthol derivatives, diphenyl Thioether, diphenyl polysulfide, benzothiazolyl disulfide, diphenylthiourea, morpholinyl dithiobenzothiazole, cyclohexylbenzothiazole-2-sulfinamide, tetramethyl Tetramethylthiuram disulfide (also known as tetramethylthiuram disulfide), tetraethyl Sulphate disulfide, tetrabutyl thio-disulfide, bismuth (2-ethylhexyl) thio-disulfide, tetramethyl thio-lane monosulfide, dipentamethylene thio-lanine tetrasulfide, etc. Sulfur compound. Preferred are polyethylene glycol dibenzoate, polypropylene glycol dibenzoate, binaphthol, (poly)ethoxy modified binaphthol, (poly)propoxy modified binaphthol, two Phenyl sulfide.

Further, a so-called softener such as a polymer such as an acrylic polymer, a polyester elastomer, a urethane polymer or a nitrile rubber may be added as needed.

The content of the plasticizer or even the softener is generally from 0 to 90 parts by mass based on 100 parts by mass of the resin composition. It is usually used in an amount of from 1 to 90 parts by mass, preferably from 2 to 80 parts by mass.

The organic compound component having no reactive group in the present invention contains an oxirane group, an epoxy group, a radical containing a radical reactive unsaturated bond, and the like which does not contain an ionic reactivity or a radical reactivity. The organic compound, the organic fine particles in the fine particles (D), and the additives other than the components (A) to (D). In terms of compatibility, the weight average molecular weight is preferably 10,000 g/mol or less, and particularly preferably 5,000 g/mol or less. In the present invention, the resin composition of the present invention contains no or contains an organic compound having a weight average molecular weight of not more than 10,000 g/mol of a reactive group, and the total amount of the resin composition relative to the organic solvent is removed. The content thereof 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. When it is 1.5% by weight or less, it is possible to prevent insoluble components from being incompatible with a component having no reactive group and to form an insoluble component such as a solid shape or a gel. Therefore, transparency can be prevented in terms of cured physical properties. The heat resistance is deteriorated, so it is preferable. Further, in order to reduce the water vapor permeability, an organometallic compound such as an aluminum alkyl may be added. Although a solvent may be added, it is preferred that the solvent is not added.

In the resin composition of the present invention, the organic compound used The weight average molecular weight of each component is preferably 10,000 g/mol or less, more preferably 5,000 g/mol or less. The component having a large weight average molecular weight is difficult to dissolve, so that the prepared resin composition is a turbid liquid. This is because the resin composition used for the display needs to be uniform and transparent, which is not suitable. Further, it is also required to have excellent characteristics regarding the transmittance, and specifically, it is preferable that the light transmittance at each wavelength of the wavelength of 380 to 780 nm is 80% or more. The light transmittance can be measured by a measuring machine such as a spectrophotometer U-3900H manufactured by Hitachi High Systems Co., Ltd.

The preferred embodiment of the resin composition for an organic EL device sealing material of the present invention is shown below. Moreover, the total amount of the resin composition described below means the total amount in the case where the resin composition contains a solvent.

I. An energy ray-curable resin composition for an organic EL device sealing material containing at least two types of compounds (A) having two or more oxetane rings in the molecule, and at least two types thereof The combination of the compound (A) having two or more oxetane rings in the molecule is a combination of the compound represented by the above formula (2) and the compound of the above formula (3) with respect to the formula ( The compound 1 part by mass of 3) contains the compound of the formula (2) in a ratio of 0.6 to 1.5 parts by mass.

II. The aspect described in the above 1, wherein the content ratio of the compound represented by the formula (2) is from 0.8 to 1.2.

The aspect of the above-mentioned I or II, wherein the photocationic polymerization initiator (C) is further contained in a ratio of 0.1 to 10 parts by mass based on 100 parts by mass of the total of the compound (A).

The aspect of any one of the above-mentioned items I to III, wherein the epoxy resin is further contained in an amount of 10 to 70 parts by mass based on 100 parts by mass of the total of the compound (A) and the epoxy compound (B). Compound (B).

The aspect of the present invention, 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.

The aspect of any one of the above-mentioned items I to V, wherein the (meth) acrylate compound is not contained or contained, and (meth) acrylate is contained in an amount of 100 parts by mass based on the total amount of the resin composition. The compound is less than 15 parts by mass.

VII. The aspect of any one of the above-mentioned, wherein the curing shrinkage ratio is 5.5% or less.

VIII. The aspect according to any one of the above 1 to 6, wherein the curing shrinkage ratio is 5% or less.

IX. The aspect of any one of the above-mentioned items I to IV, wherein the organic EL element sealing material is used for the sealing transparent substrate.

The resin composition of the present invention can be prepared by mixing and dissolving the components in accordance with a usual method. For example, each component is fed into a round bottom flask equipped with a stirring device 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 may be formed by coating a solid organic EL sealing material (for example, glass or the like) as long as it is 10 mPa at 25 ° C. More than s, preferably 10 to 3000 mPa. s or so. Further, the resin composition of the present invention containing no fine particles (D) has a viscosity of 10 to 150 mPa. s or so, preferably 20 to 120 mPa. s or so. The viscosity of the resin composition of the present invention containing the microparticles (D) is preferably from 300 to 3000 mPa. s or so, more preferably 500 to 2500mPa. s or so.

Moreover, the workability of the transferability or workability of the shape suitable for producing an optical lens formed on a substrate is preferably 10 mPa at 25 ° C. s above.

The resin composition of the present invention can be easily hardened by energy rays. Here, specific examples of the energy ray include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, γ rays, and laser rays; particle lines such as α rays, β rays, and electron beams. In the present invention, among these, ultraviolet rays, laser light rays, visible rays, or electron rays are preferred.

The cured product of the present invention can be obtained by irradiating the aforementioned energy ray by the resin composition of the present invention by a usual method. In order to make the refractive index of the cured layer of the resin composition of the present invention high, the liquid refractive index of the resin composition of the present invention is also preferably high, and the refractive index of the liquid is generally from 1.45 to 1.55, preferably from 1.48 to 1.52. . The liquid refractive index can be measured by an Abbe refractometer (Model: DR-M2, manufactured by Atago Co., Ltd.) or the like.

The curing shrinkage ratio at the time of curing the resin composition of the present invention 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, it is generally about 4%.

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 . Below the day, it is more suitable for 100g/m ² . Below the day, it is especially suitable for 60g/m ² . Below the day. In this range, the penetration of moisture can effectively prevent damage to components.

The solid sealing of the organic EL element using the resin composition of the present invention is generally carried out by the step of forming a passivation film on the organic EL element formed on the substrate, and coating the present invention on the passivation film. a step of forming a resin composition (adhesive for sealing), a step of providing a transparent substrate for sealing on the coating layer, and a step of curing the coating layer. In general, a transparent substrate for sealing can be a transparent substrate such as glass.

The sealed organic EL element is composed of a substrate (support substrate) that supports a main body of the element that functions as the element, and an element portion body that includes a lower electrode and an organic EL layer including at least a light-emitting layer. With the upper electrode. The substrate may be a glass substrate, a transparent organic material composed of a cycloolefin, a polycarbonate, or a polymethyl methacrylate, or an organic/inorganic hybrid transparently made of a transparent organic material such as glass fiber. A flat substrate made of an electrically insulating material such as a substrate. Moreover, the representative structure of the element part body is the following.

(1) Lower electrode / luminescent layer / upper electrode

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

(3) lower electrode / luminescent 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 the above (4), the lower electrode (cathode) composed of an Al-Li alloy or the like may be formed on one surface of the substrate by a resistance heating vapor deposition method or a sputtering method. Next, the film formation method such as resistance heating vapor deposition or ion beam sputtering is sequentially laminated by 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), and an upper electrode (anode) are used to form an organic EL layer. Further, the layer structure or material of the organic EL element is not particularly limited as long as it can function as a display element. Further, the solid sealing method of the present invention can also be applied to an organic EL element of an arbitrary structure.

The passivation film is formed by coating an organic EL element. The passivation film can be formed by a method such as vapor deposition or sputtering using an inorganic material such as tantalum nitride or hafnium oxide. The passivation film is provided to prevent intrusion of moisture or ionic impurities into the organic EL element. blunt The thickness of the film is preferably in the range of 10 nm to 100 μm, more preferably in the range of 100 nm to 10 μm.

The passivation film also differs depending on the film formation method, but in general, it is often a film having an incomplete pinhole or a film having a weak mechanical strength. Therefore, in the solid sealing method, an adhesive is further applied on the passivation film, and the sealing is performed using a transparent substrate for sealing, and the adhesive is cured to improve the reliability of the sealing.

By incorporating (mounting) the sealed organic EL element obtained in the above manner on a display device, an organic EL display having a cured product of the resin composition of the present invention can be obtained.

(Example)

Next, the present invention will be described in more detail by way of examples. The present invention is not limited by the following examples. Further, the unit "part" of the numerical value indicates the part by mass.

The composition shown in the following examples (Table 1) gave the resin composition and cured product of the present invention. Moreover, the evaluation methods and evaluation criteria of the resin composition and the cured film were carried out as follows. Further, the examples containing the organic solvent were evaluated by sufficiently evaporating the organic solvent with an evaporator.

(1) Viscosity: It 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 formulated resin composition was measured by an Abbe refractometer (DR-M2: manufactured by Atago Co., Ltd.).

(3) Moisture permeability: The ultraviolet curable resin was sandwiched between glass substrates, and the film thickness was adjusted using a spacer of 100 μm, and hardened by a high pressure mercury lamp (80 W/cm, no ozone) and 3000 mJ/cm ² to prepare a test. sheet. The moisture permeability of the obtained test piece was measured by a Lyssy water vapor permeability meter L80-5000 (manufactured by Systech Illinois Co., Ltd.) at 60 ° C × 90% RH.

(4) Tg (glass transition point): Measurement of viscoelasticity System EXSTAR DMS-6000 (manufactured by SII, Nanotechnology Co., Ltd.), tensile mode, frequency 1 Hz, scan rate; 2 ° C at room temperature / The Tg point of the hardened ultraviolet curable resin layer was measured.

(5) Hardening shrinkage ratio: an ultraviolet curable resin layer is applied onto a substrate, and is irradiated with a high-pressure mercury lamp (80 W/cm, no ozone) at 3000 mJ/cm ² to be hardened to prepare a cured product for measuring a specific gravity of the film. .

(6) The specific gravity (DS) of the cured product was measured in accordance with JIS K7112 B. Further, the specific gravity (DL) of the resin composition was measured at 23 ± 2 ° C, and the curing shrinkage ratio was calculated according to the following formula. The measurement results are the average values of the measurement results of 4 times.

Hardening shrinkage ratio (%) = (DS-DL) / DS × 100

Brittleness: coated with a wire bar coater at a thickness of 20 μm on a PET (A4300 100 μm thick: manufactured by Toyobo Co., Ltd.), and 3000 mJ with a high pressure mercury lamp (80 W/cm, no ozone). Irradiation of /cm ² was allowed to harden to obtain a test piece. Thereafter, the evaluation was performed by a 180° bending test piece.

○...no cracks occur

×...There is a crack

(7) Light transmittance: The ultraviolet curable resin was sandwiched between glass substrates, and the film thickness was adjusted using a spacer of 60 μm, and hardened with a high-pressure mercury lamp (80 W/cm, no ozone) at 3000 mJ/cm ² to prepare a test piece. . The light transmittance of each of the obtained test pieces at wavelengths of 380 to 780 mm was measured by a spectrophotometer U-3900H (light source C) manufactured by Hitachi High Technologies Co., Ltd., and the value at 400 nm was used as the transmittance.

In the above table, since Comparative Example 1 was irradiated with a high-pressure mercury lamp (80 W/cm, no ozone) at 3000 mJ/cm ^{2 and was} not cured, only items which can be measured in a liquid form were described.

OXT-121: East Asia Synthetic Co., Ltd. X-Methoxy Dioxetane

OXT-221: 3-Ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane manufactured by Toagosei Co., Ltd.

SEJ-01R: 3,4-Epoxycyclohexenylmethylate manufactured by Nippon Kayaku Co., Ltd. -3',4'-epoxycyclohexenecarboxylate

GSID 26-1: manufactured by BASF Japan Co., Ltd. (Ref. [4-(4-Ethylphenylthio)phenyl]indole [(trifluoromethyl)sulfonyl]methyl

SZR-K: MEK dispersed zirconia made by 堺Chemical Industry Co., Ltd. (solid concentration 30% primary particle size 4nm)

OXT-101: 3-Ethyl-3-hydroxymethyloxetane manufactured by East Asia Synthetic Co., Ltd.

As is apparent from the evaluation results of Examples 1-3 and Comparative Examples 1 to 4, the resin composition of the present invention having a specific composition has a small hardening shrinkage ratio, and has a high Tg and a low water vapor permeability. For this reason, it is suitable as a sealing material of an organic electroluminescent element especially as various sealing materials, for example, and can be used as an adhesive for the sealing of the transparent transparent substrate of the organic EL element.

(industrial availability)

The resin composition of the present invention has a small curing shrinkage ratio, and the cured product is excellent in visible light transmittance and light resistance, high in Tg, and low in water vapor permeability. Therefore, it is suitable as various sealing materials, and is particularly suitable as a sealing for organic EL elements. As the material, an adhesive for the subsequent sealing of the transparent substrate which is a solid seal of the organic EL element can be used.

Claims (23)

An energy ray-curable resin composition for an organic EL element sealing material, which contains two or more kinds of compounds (A) having two or more oxetane rings in a molecule. The energy ray-curable resin composition for an organic EL device sealing material according to the first aspect of the invention, wherein the energy ray-curable resin composition does not contain a reactive group having a weight average molecular weight of 10,000 g/mol or more. When the organic compound component is contained or contained, the content thereof is less than 1.5% by weight based on the total amount of the resin composition. The energy ray-curable resin composition for an organic EL device sealing material according to the first or second aspect of the invention, wherein the compound (A) having two or more oxetane rings in the molecule has at least a compound of the following oxetane ring represented by the following formula (1) or the following formula (2); (wherein R ₁ each independently represents a direct bond or a linear or branched chain hydrocarbon group having 1 to 6 carbon atoms, and R ₂ represents a linear or branched chain hydrocarbon group having 1 to 15 carbon atoms, 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 linear or branched chain hydrocarbon group having 1 to 6 carbon atoms, and n is an average value, representing an integer of 1 to 5) (2) (wherein R ₄ each independently represents a linear or branched chain hydrocarbon group having 1 to 6 carbon atoms, and R ₅ each independently represents a linear or branched chain hydrocarbon group having 1 to 6 carbon atoms). The energy ray-curable resin composition for an organic EL device sealing material according to any one of claims 1 to 3, wherein the compound having two or more oxetane rings in the molecule (A) Is a compound having at least an alicyclic or aromatic ring in the molecule. The energy ray-curable resin composition for an organic EL device sealing material according to any one of claims 1 to 4, wherein the compound of the above formula (1) and the compound of the above formula (2) are contained as a molecule A compound (A) having two or more oxetane rings therein. The energy ray-curable resin composition for an organic EL device sealing material according to claim 5, wherein the compound of the formula (2) has a content ratio of 0.6 to 1 part by mass of the compound of the formula (1). A range of 1.5 parts by mass. The energy ray-curable resin composition for an organic EL device sealing material according to any one of the first aspect of the present invention, wherein two or more types of oxetane rings are contained in the molecule. The compound (A), which is a total organic compound component contained in the resin composition, is composed of a component having a weight average molecular weight of 10,000 g/mol or less and mutually soluble from 20 ° C to 80 ° C. The organic EL element seal according to any one of claims 1 to 6 An energy ray-curable resin composition for a material, which does not contain a (meth) acrylate compound, or a content of less than 15 parts by mass based on 100 parts by mass of the total amount of the resin composition for removing the solvent. Share. The energy ray-curable resin composition for an organic EL device sealing material according to any one of claims 1 to 8, further comprising an epoxy compound (B) and a photocationic polymerization initiator (C) Either or both of them are contained in an amount of 0.1 to 70 parts by mass based on 100 parts by mass of the total of the solvent-removing resin composition; and the above compound (A) is based on the total content thereof, relative to the solvent-removing resin composition. The total amount of the substance is 100 parts by mass, and is contained in an amount of 30 to 99.9 parts by mass. The energy ray-curable resin composition for an organic EL device sealing material according to any one of the first aspect of the invention, further comprising an epoxy compound (B). The energy ray-curable resin composition for an organic EL device sealing material according to the invention of claim 9, wherein the epoxy compound (B) is an alicyclic epoxy compound. The energy ray-curable resin composition for an organic EL device sealing material according to any one of the invention, wherein the epoxy compound (B) has two or more epoxy groups in the molecule. compound of. The energy ray-curable resin composition for an organic EL device sealing material according to any one of claims 10 to 12, wherein the total amount of the compound (A) and the epoxy compound (B) is 100. The parts by mass contain 20 to 70 parts by mass of the epoxy compound (B). The energy ray-curable resin composition for an organic EL device sealing material according to any one of claims 10 to 13, wherein the compound having two or more oxetane rings in the molecule (A) And the total amount of epoxy compound (B) 100 The parts by mass contain 30 to 90 parts by mass of the compound (A). The energy ray-curable resin composition for an organic EL device sealing material according to any one of claims 1 to 14, further comprising a photocationic polymerization initiator (C). The energy ray-curable resin composition for an organic EL device sealing material according to claim 15, wherein the photocationic polymerization initiator (C) is a cerium salt, an iodonium salt, a cerium salt or an ammonium salt. And at least one selected from the group consisting of citrate. The energy ray-curable resin composition for an organic EL element sealing material according to any one of the first aspect of the invention, which further contains fine particles (D). The energy ray-curable resin composition for an organic EL device sealing material according to claim 17, wherein the primary particle diameter 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 any one of claims 1 to 18, wherein the viscosity at 25 ° C is 10 mPa as measured by an E-type viscosity meter. s above. The energy ray-curable resin composition for an organic EL device sealing material according to any one of the first aspect of the invention, wherein the curing shrinkage ratio of the resin composition when the resin composition is cured is 5.5% or less. A cured product obtained by curing an energy ray-curable resin composition of an organic EL device sealing material according to any one of claims 1 to 20. The hardened material according to claim 21, wherein the water vapor permeability at a thickness of 100 μm is 200 g/m ² . Daily / 60 ° C or less. An organic EL display having the cured product described in claim 21 or 22.