TW201504265A - Energy-ray-curable resin composition and cured product of same - Google Patents

Abstract

A resin composition containing a (meth)acrylate compound (A) having an aromatic hydrocarbon backbone, a cyclic (meth)acrylate compound (B), and a polymerization initiator (C), the compound (B) being at least one type of (meth)acrylate compound selected from the group consisting of a (meth)acrylate compound having an aromatic hydrocarbon backbone other than the compound (A), a (meth)acrylate compound having an alicyclic hydrocarbon backbone, and a (meth)acrylate compound having a heterocyclic backbone.

Description

Energy ray hardening resin composition and cured product thereof

The energy ray-curable resin is usually processed without a solvent, 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 technology in various industries including display peripheral materials. In recent years, regarding displays, thin displays called flat panel displays (FPDs), particularly plasma displays (PDPs) and liquid crystal displays (LCDs) have been put on the market and widely used. Further, as a next-generation self-luminous thin film display, an organic EL display (OLED) is expected, and some products have been put into practical use. The organic EL element of the organic EL display has a structure in which an element portion body composed of a thin film layered 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 the element portion is likely to be deteriorated by moisture or oxygen, and the brightness is lowered or the life is shortened due to deterioration, and discoloration occurs. Therefore, the organic EL element is sealed in such a manner as to block penetration of moisture or impurities from the outside. In order to realize high-quality and high-reliability organic EL elements, it is desired to have a sealing material of higher performance, and various sealing techniques have been studied from the past.

As a typical sealing method of the organic EL element, there has been studied a method of fixing a sealing plate made of metal or glass which is previously filled with a desiccant to a substrate of an organic EL element by using a sealing adhesive (Patent Document 1). This method applies an adhesive to an organic EL device. A sealing cover is provided on the outer peripheral portion of the substrate, and then the adhesive is cured, whereby the substrate and the sealing cover are fixed to seal the organic EL element. In this method, sealing with a glass sealing cap has become mainstream. However, since the sealing cap made of glass is produced by etching a flat glass substrate to be filled with a desiccant, there is a tendency for the cost to become high. Further, since the seal is sealed by the seal cap and the desiccant is placed inside the seal cap, light cannot be extracted from the seal cap side. That is, the light emitted from the light source is extracted from the substrate side of the element, thereby being limited to the element of the bottom emission type. In the case of the element of the bottom emission type, there is a problem that the aperture ratio is lowered by the driver circuit portion formed on the substrate, and the light is blocked by the driver circuit portion, and the extraction efficiency is lowered. Therefore, it is desired to develop a sealing method which can be applied to a top emission type element which extracts light from the opposite side of a substrate of an organic EL element.

As a representative sealing method applicable to the top emission type element, there are a film sealing method and a solid sealing method. The film sealing method is a method in which a film composed of an inorganic or organic material is laminated on an organic EL element to form a passivation film (Patent Document 2). In order to impart sufficient moisture resistance to the element by this method, it is necessary to sequentially laminate a plurality of layers of the film on the element. Therefore, the film sealing method has a tendency that the film forming step is long and the cost is high, and the initial investment is increased due to the introduction of a large vacuum system necessary for film formation.

On the other hand, the solid sealing method is a method in which a passivation film is provided so as to cover the entire element portion of the organic EL element, and a sealing transparent substrate is provided thereon with a sealing material interposed therebetween (see Patent Document 3). Usually, the passivation film is formed by vapor deposition or sputtering of an inorganic material, but it is often an incomplete film having pinholes or a film having weak mechanical strength. Therefore, in the solid sealing method, after the passivation film is provided on the element, a sealing transparent substrate such as a glass substrate is provided via the sealing adhesive, thereby improving the reliability of the sealing. Such a solid sealing method has been attracting attention as a method which is simple and low-cost and can perform sealing of a top-emission type element.

In the sealing of the organic EL element by the solid sealing method, a thermal or photocurable resin can be used as the sealing adhesive, but these characteristics may be attributed to the performance and sealing of the element. It is very important that the productivity of the industry has a significant impact. For example, if the water vapor permeability of the adhesive for sealing is insufficient, moisture may penetrate into the element portion from the pinhole of the passivation film, which may cause deterioration of the element. Moreover, if the hardening reaction of the sealing material is slow, there is a possibility that the hardening step takes time and the productivity of the sealing operation is lowered.

In addition to the high transmittance required in the visible light region, it is required to withstand the light resistance of light emission, stable formability, or low hardenability and shrinkage for suppressing residual stress, and the like. The low water vapor permeability and the like for protecting the light-emitting element from moisture penetration. It is possible to use a known sealing agent as a sealing agent for an organic EL element, and to perform sealing by a solid sealing method. However, it is difficult to obtain satisfactory results in terms of reliability, productivity, and water vapor transmission rate, and it is desired to develop. A sealing adhesive which can be preferably used in a solid sealing method.

Prior 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. 4651172

Patent Document 5: Japanese Laid-Open Patent Publication No. 2001-81182

Patent Document 6: Japanese Laid-Open Patent Publication No. 2000-169552

An object of the present invention is to provide a resin composition suitable for a sealing material for an organic EL element, which is excellent in hardenability, and has visible light transmittance, hardening shrinkage ratio, and water vapor permeability. Low hardened material.

In order to solve the above problems, the present inventors have made an effort to solve the above problems, and have found that an energy ray-curable resin composition having a specific composition and a cured product thereof solve the above problems, and have completed the present invention.

That is, the present invention relates to the following (1) to (13).

(1) A resin composition containing a (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton, a cyclic (meth) acrylate compound (B), and a polymerization initiator (C),

The compound (B) is a (meth) acrylate compound having an aromatic hydrocarbon skeleton other than the compound (A), a (meth) acrylate compound having an alicyclic hydrocarbon skeleton, and a methyl group having a heterocyclic skeleton. At least one (meth) acrylate compound in the group consisting of acrylate compounds.

(2) The resin composition of (1), wherein the compound (A) is a (meth) acrylate compound having two or more aromatic hydrocarbon skeletons in one molecule.

(3) The resin composition of (1) or (2), wherein the aromatic hydrocarbon skeleton of the compound (A) has a skeleton represented by the following formula (1).

(wherein, X represents a direct bond or an alkyl group having 1 to 3 carbon atoms).

(4) The resin composition according to any one of (1) to (3), wherein the compound (A) is a compound represented by the following formula (2).

(wherein X represents a direct bond or an alkylene group having 1 to 3 carbon atoms, Y represents a hydrogen atom or a methyl group, and R ₁ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom or a (meth) group) Acryl fluorenyl, R ₂ represents a direct bond or a (poly)alkyleneoxy group having a carbon number of 1 to 10.

(5) The resin composition of (2), wherein the (meth) acrylate compound having two or more aromatic hydrocarbon skeletons in one molecule is a (meth) group having an anthracene skeleton, a naphthalene skeleton or a biphenyl skeleton. Acrylate compound.

(6) The resin composition of any one of (1) to (5), wherein the compound (B) is a (meth) acrylate compound having an alicyclic hydrocarbon skeleton, and has two or more in one molecule. a (meth) acrylate compound of an alicyclic hydrocarbon skeleton.

(7) The resin composition of (6), wherein the (meth) acrylate compound having an alicyclic hydrocarbon skeleton contains a bicyclodecane structure, a tricyclodecane ring or an adamantane ring as an alicyclic hydrocarbon skeleton .

(8) The resin composition of (6), wherein the (meth) acrylate compound having an alicyclic hydrocarbon skeleton is a (meth) acrylate compound represented by the following formula (3).

(In the formula, R ₃ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom or the following formula (4), and at least one of R ₃ is represented by the following formula (4)).

(wherein R ₂ represents a direct bond or a (poly)alkyloxy group having 1 to 10 carbon atoms, Y represents a hydrogen atom or a methyl group, and * is bonded to a cyclic skeleton).

(9) The resin composition of (6), wherein the alicyclic hydrocarbon skeleton is a (meth) acrylate compound represented by the following formula (5).

(wherein R ₆ and R ₇ each independently represent a direct bond or an alkylene group having 1 to 6 carbon atoms or a (poly)alkyleneoxy group).

The resin composition of any one of (1) to (5), wherein the compound (B) is a (meth) acrylate compound having a heterocyclic skeleton, and is represented by the following formula (6). (Meth) acrylate compound.

(wherein R ₈ represents a direct bond, a C 1 to 6 alkyl or an alkyloxy group. R ₉ represents hydrogen or a C 1 to 4 alkyl group. Z represents a carbon atom, an oxygen atom or Nitrogen atom).

(11) The resin composition (1), wherein the compound (A) represented by the following formula (2): the compound (B) represented by the following formula (3) has a weight ratio of 9:1 to 1:9. .

(wherein X represents a direct bond or an alkylene group having 1 to 3 carbon atoms, Y represents a hydrogen atom or a methyl group, and R ₁ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom or a (meth) group) Acryl fluorenyl, R ₂ represents a direct bond or a (poly)alkyleneoxy group having a carbon number of 1 to 10.

(In the formula, R ₃ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom or the following formula (4), and at least one of R ₃ is represented by the following formula (4)).

(wherein R ₂ represents a direct bond or a (poly)alkyloxy group having 1 to 10 carbon atoms, Y represents a hydrogen atom or a methyl group, and * is bonded to a cyclic skeleton).

(12) A low moisture permeability barrier film obtained by hardening the resin composition of any one of (1) to (11).

(13) A resin composition according to any one of (1) to (11) which is useful for OLED use.

The resin composition and the cured product of the present invention are particularly suitable for a sealing material for an organic EL device because they are excellent in visible light transmittance and have low curing shrinkage ratio and water vapor permeability.

The resin composition of the present invention contains a (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton, a cyclic (meth) acrylate compound (B), and a polymerization initiator (C).

According to the above configuration, the (meth) acrylate compounds of the two different skeletons are introduced into the curing system at the time of curing, and a low shrinkage ratio can be achieved, and a compound having only one type of cyclic skeleton can be obtained, which is impossible to achieve. Excellent low water vapor transmission rate.

The (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton contained in the resin composition of the present invention may be any one of the publicly known ones as long as it has at least one aromatic ring in the molecule. . In such a compound having an aromatic ring, by providing an aromatic ring, the resin composition can be made water-repellent, and the water vapor transmission rate can be lowered. Further, this effect can be sufficiently exhibited as long as it is a (meth) acrylate compound having one or more aromatic rings in the molecule. Further, since the effect is more excellent by having two or more aromatic rings in the molecule, it is preferable. Examples of the skeleton having two or more aromatic rings in such a molecule include a biphenyl skeleton or a bisphenol skeleton, and these skeletons have an effect of exhibiting excellent water vapor permeability.

Furthermore, the aromatic hydrocarbon skeleton may have a substituent or may have no substituent. In the case of having a substituent, the substituent is preferably an alkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms. An oxy group and an alkenyl group having 1 to 6 carbon atoms.

Specific examples of the (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton include the following monofunctional (meth) acrylate compounds or two or more functional groups. (Meth) acrylate compound.

Examples of the monofunctional (meth) acrylate compound include benzyl (meth) acrylate, ethoxy modified cresol (meth) acrylate, and propoxy modified cresol (meth) acrylate. Ester, neopentyl glycol benzoic acid (meth) acrylate, o-phenylphenol (meth) acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenyl phenol polyethoxy ( Methyl) acrylate, p-phenylphenol (meth) acrylate, p-phenylphenol monoethoxy (meth) acrylate, p-phenyl phenol polyethoxy (meth) acrylate, o-phenyl a monocyclic (meth) acrylate compound, carbazole (poly) ethoxy (meth) acrylate, carbazole (poly) propoxy group (such as benzyl acrylate or p-phenyl phenyl acrylate) (meth) acrylate compound, naphthyl (meth) acrylate, naphthyl (poly) ethoxylate, etc., such as acrylate, (poly)caprolactone modified carbazole (meth) acrylate (meth) acrylate, naphthyl (poly) propoxy (meth) acrylate, (poly) caprolactone modified naphthyl (meth) acrylate, binaphthol (meth) acrylate, Binaphthol (poly) Oxy (meth) acrylate, binaphthol (poly) propoxy (meth) acrylate, (poly) caprolactone modified binaphthol (meth) acrylate, naphthol (meth) acrylate Ester, naphthol (poly) ethoxy (meth) acrylate, naphthol (poly) propoxy (meth) acrylate, (poly) caprolactone modified naphthol (meth) acrylate, etc. A (meth) acrylate compound of a condensed ring.

Examples of the bifunctional or higher (meth) acrylate compound include (poly)ethoxylated bisphenol A di(meth)acrylate and (poly)propoxy modified bisphenol A di(methyl). Acrylate, (poly)ethoxy modified bisphenol F di(meth)acrylate, (poly)propoxy modified bisphenol F di(meth)acrylate, (poly)ethoxy modification Bisphenol S di(meth)acrylate, (poly)propoxy modified bisphenol S di(meth)acrylate, hexahydrophthalic acid di(meth)acrylate, bisphenoxy (poly) a (meth) acrylate compound having a heterocyclic ring such as a monocyclic (meth) acrylate compound or a biphenyl dimethanol di(meth) acrylate, such as ethoxylated oxime, or naphthol di(meth) acrylate , binaphthol (poly)ethoxy di(meth)acrylate, binaphthyl a (meth) acrylate compound having a condensed ring such as phenol (poly) propoxy di(meth) acrylate or (poly) caprolactone modified dinaphthol di(meth) acrylate, bisphenol quinone (Meth) acrylate, bisphenoxymethanol bis(meth) acrylate, bisphenoxyethanol hydrazine di(meth) acrylate, bisphenoxycaprolactone 茀 di(meth) acrylate A (meth) acrylate compound or the like having a polycyclic aromatic group.

As the (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton, In addition to the above (meth) acrylate monomer, an epoxy (meth) acrylate compound may also be mentioned.

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

In particular, as the (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton, for example, a (meth) acrylate compound having a partial skeleton of the following formula (1) can be preferably used.

(wherein, X represents a direct bond or an alkyl group having 1 to 3 carbon atoms).

It is considered that by having the above-mentioned partial skeleton, the water repellency imparted to the aromatic ring can be more effectively exhibited.

Specifically, among the (meth) acrylate compounds, the (meth) acrylate compound having a bisphenol skeleton such as a bisphenol A skeleton or a bisphenol F skeleton or a biphenyl skeleton conforms to the above formula (1). It can be preferably used.

Further, it is preferred that the (meth)acryl fluorenyl group is bonded to the aromatic hydrocarbon skeleton. Specifically, the (meth) acrylonitrile group is preferably bonded to the aromatic hydrocarbon skeleton directly or via a hydrocarbon group, and examples of the hydrocarbon group in the case of being bonded via a hydrocarbon group include an alkylene group having 1 to 10 carbon atoms or The ether bond has a carbon number of 1 to 10 alkyl groups.

Further, as the (meth) group having an aromatic hydrocarbon skeleton used in the present invention The acrylate compound (A) is preferably a (meth) acrylate compound represented by the following formula (2).

(wherein X represents a direct bond or an alkylene group having 1 to 3 carbon atoms, Y represents a hydrogen atom or a methyl group, and R ₁ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom or the following formula ( 4), R ₂ represents a direct bond or a (poly)alkyleneoxy group having a carbon number of 1 to 10.

(wherein R ₂ represents a direct bond or a (poly)alkyloxy group having 1 to 10 carbon atoms, Y represents a hydrogen atom or a methyl group, and * is bonded to a benzene skeleton).

Specific examples of such a (meth) acrylate compound include o-phenylphenol (meth) acrylate, o-phenylphenol monoethoxy (meth) acrylate, and o-phenyl phenol polyethylene. Oxy (meth) acrylate, p-phenylphenol (meth) acrylate, p-phenylphenol monoethoxy (meth) acrylate, p-phenyl phenol polyethoxy (meth) acrylate, Benzyl phenyl phenyl acrylate, benzyl p-phenyl acrylate, (poly) propoxy modified bisphenol A di(meth) acrylate, (poly) ethoxy modified bisphenol F bis (methyl) ) acrylate, (poly) propoxy modified bisphenol F di(meth) acrylate, and the like.

Regarding the (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton The content in the resin composition is usually preferably from 5 to 95 parts by weight, more preferably from 10 to 80 parts by weight, even more preferably from 20 to 70 parts by weight, per 100 parts by weight of the resin composition.

As the cyclic (meth) acrylate compound (B) used in the present invention, The (meth) acrylate having an aromatic hydrocarbon skeleton, the (meth) acrylate having an alicyclic hydrocarbon skeleton, and the (meth) acrylate having a heterocyclic skeleton can be used.

When a (meth) acrylate compound having an aromatic hydrocarbon skeleton is used as the cyclic (meth) acrylate compound (B), the resin composition contains two kinds of "having an aromatic structure" a (meth) acrylate compound of a hydrocarbon skeleton. That is, the (meth) acrylate having an aromatic hydrocarbon skeleton which can be used as the cyclic (meth) acrylate compound is the same as those enumerated above, but the same (meth) as the compound (A) cannot be used. Acrylate compound.

When a (meth) acrylate compound having an aromatic hydrocarbon skeleton as described above is used in a resin composition, it has an effect of preventing water vapor penetration as compared with other skeletons such as a chain structure. When it is disposed in the curing system together with the (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton, the penetration of water vapor can be remarkably prevented by the synergistic effect.

As the (meth) propylene having an alicyclic hydrocarbon skeleton which can be used in the present invention The acid ester compound can be used without any particular limitation, and the alicyclic hydrocarbon skeleton is preferably a saturated hydrocarbon skeleton. Such a ring skeleton has an effect of preventing water vapor penetration as compared with other skeletons such as a chain structure, and is disposed together with a (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton. The synergy effect can be used to significantly prevent the penetration of water vapor.

Examples of the cyclic hydrocarbon skeleton which may be specifically used include a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a bicyclodecane structure, a tricyclodecane ring, an adamantane ring, and an isodecyl group. Ring and so on.

Among them, a (meth) acrylate compound having a bridged cyclic hydrocarbon skeleton such as a tricyclodecane ring or an adamantane ring is preferred. Since such a compound is bridged to the alicyclic hydrocarbon skeleton, it has a three-dimensional structure and carbon atoms are disposed in the space of the cyclic structure, so that the penetration of water vapor can be more effectively prevented. Further, the above synergistic effect is made higher by mixing with such a (meth) acrylate compound having a bridged cyclic hydrocarbon skeleton.

Further, it is preferred that the (meth)acryl fluorenyl group is bonded to the cyclic hydrocarbon skeleton. Specifically, the (meth) acrylonitrile group is preferably bonded to the cyclic hydrocarbon skeleton directly or via a hydrocarbon group, and the hydrocarbon group in the case of being bonded via a hydrocarbon group may, for example, be an alkylene group having 1 to 10 carbon atoms or have The ether bond has a carbon number of 1 to 10 alkyl groups.

As such a (meth) acrylate compound having an alicyclic hydrocarbon skeleton As the embodiment, there are the following monofunctional (meth) acrylate compounds or bifunctional or higher (meth) acrylate compounds.

Examples of the monofunctional (meth) acrylate compound include isodecyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and (methyl). Alicyclic (meth) acrylate such as dicyclopentene oxyethyl acrylate or cyclohexyl (meth) acrylate, 1,3-adamantanediol di(meth) acrylate, 1,3-adamantane Dimethanol di(meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, (meth)acrylic acid 3 - hydroxy-1-adamantyl ester, 1-adamantyl (meth)acrylate, and the like.

Examples of the bifunctional or higher polyfunctional (meth) acrylate compound include alicyclic (meth) acrylates such as tricyclodecane dimethanol (meth) acrylate.

As such a (meth) acrylate compound having a cyclic hydrocarbon skeleton, A (meth) acrylate compound having a structure represented by the following formula (3) is preferably used.

(In the formula, R ₃ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom or the following formula (4), and at least one of R ₃ is represented by the following formula (4)).

(wherein R ₂ represents a direct bond or a (poly)alkyloxy group having 1 to 10 carbon atoms, Y represents a hydrogen atom or a methyl group, and * is bonded to a cyclic skeleton).

Specific examples of the (meth) acrylate compound of the above formula (3) include alicyclic (meth) acrylates such as tricyclodecane dimethanol (meth) acrylate.

The content of the (meth) acrylate compound having an alicyclic hydrocarbon skeleton in the resin composition is usually preferably from 5 to 95 parts by weight, more preferably from 10 to 80 parts by weight, per 100 parts by weight of the resin composition. , especially preferably 20 to 70 parts by weight.

The (meth) acrylate compound having a heterocyclic skeleton which can be used as a cyclic (meth) acrylate compound in the present invention will be described below.

Such a heterocyclic skeleton has a effect of preventing water vapor penetration as compared with other skeletons such as a chain structure. Further, by being disposed in the curing system together with the (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton, the penetration of water vapor can be remarkably prevented by the synergistic effect.

Regarding the heterocyclic skeleton, as a specific usable skeleton, there are mentioned: Alkane structure, three Alkane structure, isocyanurate structure, and the like.

Further, it is preferred that the (meth)acryl fluorenyl group is bonded to the heterocyclic skeleton. Specifically, the (meth) acrylonitrile group is preferably bonded to the heterocyclic skeleton directly or via a hydrocarbon group, and examples of the hydrocarbon group in the case of linking via a hydrocarbon group include an alkylene group having 1 to 10 carbon atoms or an ether group. The bond has a carbon number of 1 to 10 alkyl groups.

Specific to such a (meth) acrylate compound having a heterocyclic skeleton For example, there are the following (meth) acrylate compounds.

That is, (meth)acrylic acid tetrahydrofurfuryl ester, alkoxylated tetrahydrofurfuryl acrylate, caprolactone modified (meth)acrylic acid tetrahydrofurfuryl ester, and wortolin (meth) acrylate, Ecene cyanide EEO modified diacrylate (M-215), ε-caprolactone modified isocyanuric acid tris(propylene methoxyethyl) ester (M-327), isomeric cyanuric acid EO modified Di- and triacrylate (M-313 or M-315), hydroxytrimethylacetaldehyde modified trimethylolpropane diacrylate (R-604), pentamethylpiperidyl methacrylate (FA -711), tetramethylpiperidyl methacrylate (FA-712HM), cyclic trimethylolpropane formal acrylate (SR531).

Examples of the (meth) acrylate compound having a heterocyclic skeleton include, for example, a phenylephrine skeleton and a tetrahydrofuran skeleton. Alkane skeleton, two Alkane skeleton, three As the skeleton, the carbazole skeleton, the pyrrolidine skeleton, the piperidine skeleton, and the isocyanurate structure, a (meth) acrylate compound having a structure represented by the following formula (7) can be preferably used.

(wherein R ₈ represents a direct bond, an alkylene group having a carbon number of 1 to 6 or an alkylene group; R ₉ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkenyl group, and X represents a nitrogen atom; An oxygen atom or a methylene group, Y represents a methylene group or a carbonyl group, and m represents an integer of 1 to 4. Among them, no case where all X is a methylene group).

Here, it is preferred to use a compound represented by the following formula (6).

(wherein R ₈ represents a direct bond or a stretched alkyl group or a stretched alkyloxy group having 1 to 6 carbon atoms. R ₉ represents a hydrogen atom and an alkylene group having 1 to 4 carbon atoms. Z represents a carbon atom or an oxygen atom. Or nitrogen atom).

About a (meth) acrylate compound having a heterocyclic skeleton in a resin composition The content thereof is usually preferably from 5 to 95 parts by weight, more preferably from 10 to 80 parts by weight, even more preferably from 20 to 70 parts by weight, per 100 parts by weight of the resin composition.

Regarding the resin composition of the present invention, (meth) propylene in the resin composition In the acid ester component, it is preferred that the (meth) acrylate compound having the structure represented by the following partial structural formula (A) (hereinafter referred to as a poly-EO modified (meth) acrylate compound) has a small total weight. The total weight of the (meth) acrylate compound other than the poly-EO modified (meth) acrylate compound is more preferably 1/2 or less.

(wherein t represents an integer of 2 or more).

The reason for this is that the polyEO modified (meth) acrylate compound has a poor water vapor transmission rate, and if the content of the poly EO modified (meth) acrylate compound is large, it is dominant in the resin composition. There is a flaw in water vapor transmission rate.

Further, the total weight of the poly-EO modified (meth) acrylate compound in the resin composition is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, and even more preferably 2 parts by weight based on 100 parts by weight of the resin composition. Parts by weight or less.

In the present invention, it is a cyclic (meth) acrylate compound and is modified by poly EO. The cyclic polyEO modified (meth) acrylate compound of the (meth) acrylate compound is preferably not used as the (meth) acrylate compound (A) or cyclic group having an aromatic hydrocarbon skeleton of the present invention ( The methyl acrylate compound (B) is preferably 20 parts by weight or less, and particularly preferably 10 parts by weight or less based on 100 parts by weight of the resin composition, even if it is used.

In the present invention, the resin composition contains an aromatic hydrocarbon skeleton (A) The ratio of the acrylate compound (A) to the cyclic (meth) acrylate compound (B) is preferably from 1:9 to 9:1, more preferably from 7:3 to 9:1 by weight. It is 5:5~9:1.

By setting it as the above preferable range, the resin composition which is excellent in water vapor permeability is obtained.

As the polymerization initiator (C) used in the present invention, photopolymerization initiation can be used. Various polymerization initiators such as a catalyst and a thermal radical polymerization initiator.

Further, specific examples of the photopolymerization initiator include 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-phenylpropane-1- Ketone, diethoxyacetophenone, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-ifolinylpropan-1-one , oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone] and other acetophenones; 2-ethyl hydrazine, 2-tributyl butyl Anthraquinones such as hydrazine, 2-chloroindole and 2-pentylhydrazine; 2,4-diethyl 9-oxosulfur 2-isopropyl 9-oxosulfur 2-chloro 9-oxosulfur 9-oxosulfur a ketal such as acetophenone dimethyl ketal or benzoin dimethyl ketal; benzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 4,4' - benzophenones such as bis-methylaminobenzophenone; 2,4,6-trimethylbenzhydryldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene) a phosphine oxide such as phenylphosphine oxide or diphenyl-(2,4,6-trimethylbenzylidene)phosphine oxide. Preferred are acetophenones, and more preferred are 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl-phenyl ketone. Further, in the resin composition of the present invention, the photopolymerization initiator may be used singly or in combination of several kinds.

In addition, the thermal radical polymerization initiator is not particularly limited as long as it is a compound which generates a radical by heating and starts a chain polymerization reaction, and examples thereof include an organic peroxide, an azo compound, a benzoin compound, and a benzoin. Ether compound, acetophenone compound, benzene Alcohol, etc., preferably using benzene alcohol. For example, as an organic peroxide, Kayamek (trademark) A, M, R, L, LH, SP-30C, Perkadox (trademark) CH-50L, BC-FF, Cadox (trademark) B-40ES, Perkadox 14, Trigonox ( Trademarks) 22-70E, 23-C70, 121, 121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kayaester (trademark) P-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl (trademark) B, Perkadox 16, Kayacarbon (trademark) BIC-75, AIC-75 (manufactured by Kayaku Akzo Co., Ltd.), PERMECK (trademark) N, H, S, F, D, G, PERHEXA (trademark) H, HC, TMH, C, V, 22, MC, PERCURE (trademark) AH, AL, HB, PERBUTYL (trademark) H, C, ND, L, PERCUMYL (trademark) H, D, PEROYL (trademark) IB, IPP, PEROCTA (trademark) ND, manufactured by Nippon Oil Co., Ltd., etc., can be obtained as a commercial item. Further, as an azo compound, VA-044, V-070, VPE-0201, VSP-1001, etc. (manufactured by Wako Pure Chemical Industries, Ltd.) and the like can be obtained as commercially available products.

As the above thermal radical polymerization initiator, benzene is preferred Alcohol-based thermal radical polymerization initiator (including benzene) Alcohol is chemically modified). Specifically, exemplified by: benzene Alcohol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diethoxy-1,1,2,2-tetraphenylethane, 1, 2-Diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetrakis(4-methylphenyl)ethane, 1,2-Diphenoxy-1,1,2,2-tetrakis(4-methoxyphenyl)ethane, 1,2-bis(trimethyldecyloxy)-1,1,2, 2-tetraphenylethane, 1,2-bis(triethyldecyloxy)-1,1,2,2-tetraphenylethane, 1,2-bistributylbutyldimethyloxane -1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethyldecyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2- Triethyl decyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tributyl dimethyl decyloxy-1,1,2,2-tetraphenyl An alkane or the like, preferably 1-hydroxy-2-trimethyldecyloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethyldecyloxy-1,1, 2,2-tetraphenylethane, 1-hydroxy-2-tributyl dimethyl decyloxy-1,1,2,2-tetraphenylethane, 1,2-bis(trimethyl)矽 alkoxy)-1,1,2,2-tetraphenylethane, further preferably 1-hydroxy-2-trimethyldecyloxy-1,1,2,2-tetraphenylethane, 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenyl , Particularly preferably 1,2-bis (trimethyl silane-yloxy) 1,1,2,2-tetraphenyl ethane.

Benzene The alcohol is commercially available from Tokyo Chemical Industry Co., Ltd., and Wako Pure Chemical Industries Co., Ltd. Also, about making benzene The hydroxyl group of the alcohol is etherified and can be easily synthesized by a known method. Also, about making benzene The hydroxy thiol etherification of the alcohol can be achieved by the corresponding benzene The alcohol is obtained by synthesizing various deuteration agents by heating under an alkaline catalyst such as pyridine. As the oximation agent, trimethylchlorodecane (TMCS), hexamethyldioxane (HMDS), and N,O-bis(trimethyldecyl)trifluoride, which are generally known as trimethyl oximation agents, may be mentioned. Ethylamine (BSTFA) or triethylchlorodecane (TECS) as a triethyl sulfonating agent, tertiary butylmethyl decane (TBMS) as a tertiary dimethyl dimethyl oximation agent, and the like. Such reagents are readily available from the market of hydrazine derivative manufacturers and the like. The reaction amount of the oximation agent is preferably 1.0 to 5.0 times moles per mole of the hydroxyl group of the target compound. Further preferably, it is 1.5 to 3.0 times Mo. If it is less than 1.0 times mole, the reaction efficiency is inferior and the reaction time becomes long, so that the thermal decomposition is promoted. If it is more than 5.0 times the molar amount, the separation may be deteriorated at the time of recovery, or the purification may become difficult.

Regarding the content of the polymerization initiator (C) of the present invention, relative to the resin composition The total amount is 100 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass. Further, in the resin composition of the present invention, the polymerization initiator (C) may be used singly or in combination of two or more.

Further, in the resin composition of the present invention, the obtained resin group of the present invention is considered. As the viscosity, refractive index, adhesion, and the like of the product, a (meth) acrylate compound other than the compound (A) or the compound (B) can also be used. Specifically, a (meth) acrylate monomer is used, and as the (meth) acrylate monomer, a monofunctional (meth) acrylate or a bifunctional (meth) acrylate can be used, and the molecule has a molecule. Three or more (meth)acrylonitrile-based polyfunctional (meth)acrylates, (meth)acrylic polyesters, epoxy (meth)acrylates, and the like.

As the monofunctional (meth) acrylate, for example, there is a quinone ring Structure of quinone imine (meth) acrylate, butane diol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylate a (meth) acrylate having a hydroxyl group, a dimethylaminoethyl (meth) acrylate such as 2-hydroxybutyl ester, 4-hydroxybutyl (meth)acrylate or a dipropylene glycol (meth) acrylate, Butyloxyethyl methacrylate, caprolactone (meth)acrylate, isobutyl (meth)acrylate, butyl (meth)acrylate, octafluoropentyl (meth)acrylate, (A) (meth) octyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylate a (meth) acrylate having an alkyl group, an ethoxy diethylene glycol (such as a lipoester, isostearyl (meth) acrylate, isomyristyl (meth) acrylate, or lauryl (meth) acrylate ( Methyl) acrylate, 2-ethylhexyl carbitol (meth) acrylate, A (meth) acrylate of a polyhydric alcohol such as polyethylene glycol (meth) acrylate or polypropylene glycol (meth) acrylate.

As the (meth) acrylate monomer having two functional groups, there are mentioned: Acetyl hydrazide, 1,4-butanediol di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, 1,9, such as acryloylated isocyanurate - (meth) acrylate having a linear methylene structure, such as decanediol di(meth) acrylate or polybutane diol di(meth) acrylate, ethylene glycol di(meth) acrylate And 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.

As the polyfunctional (meth) acrylate monomer, there are mentioned: isocyanuric acid tris (propylene) Ethyloxyethyl)ester, (poly)caprolactone modified poly(meth) acrylate having isocyanurate ring, such as tris(propylene methoxyethyl) isocyanurate, neopentyl Tetraol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, (poly)ethoxy modified neopentaerythritol tetra(meth)acrylate, (poly)propoxy modification Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta (meth) acrylate, (poly)caprolactone modified dipentaerythritol penta (meth) acrylate, (poly) B Oxygen-modified dipentaerythritol penta(meth)acrylate, (poly)propoxy-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate (poly)caprolactone modified dipentaerythritol hexa(meth) acrylate, (poly) ethoxylated dipentaerythritol hexa (meth) acrylate, (poly) propoxy Dipentaerythritol hexa(meth) acrylate, polypentaerythritol poly(meth) acrylate, trimethylolpropane tri(meth) acrylate, (poly) ethoxylated trimer Methylpropane tri(meth)acrylate, (poly)propoxy modified trimethylolpropane tri(meth)acrylate Polyfunctional (meth) acrylates such as di-trimethylolpropane tetra(meth)acrylate or tris(meth)acrylate, polyfunctional (meth) acrylates such as tris(meth)acrylate, etc. Aromatic polyfunctional (meth) acrylate such as (meth) acrylate or trimethylolpropane benzoic acid (meth) acrylate, 2,2,2-tripropenyloxymethyl group A polyfunctional (meth) acrylate having a polyfluorene skeleton such as a polyfunctional (meth) acrylate or a polydecyl hexa (meth) acrylate which is acid-modified such as succinic acid.

Such a compound (A), a compound (B) other than a (meth) acrylate single The content in the resin composition is usually preferably from 5 to 95 parts by weight, more preferably from 10 to 80 parts by weight, even more preferably from 20 to 70 parts by weight, per 100 parts by weight of the resin composition.

In the present invention, (meth) urethane can be used to the extent that the properties are not impaired.

Examples of the (meth)acrylic acid amine ester include a diol compound (for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, Neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1,5 - pentanediol, 2,4-diethyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, polyethylene a diol, a polypropylene glycol, a bisphenol A polyethoxy diol, a bisphenol A polypropoxy diol, or the like) or as a diol compound and a dibasic acid or an anhydride thereof (for example, succinic acid, adipic acid, a polyester diol of a reactant of azelaic acid, a dimer acid, an isophthalic acid, a terephthalic acid, a phthalic acid or an anhydride thereof, and an organic polyisocyanate (for example, tetramethylene diisocyanate, Chain-like saturated hydrocarbon isocyanate such as hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate or 2,4,4-trimethylhexamethylene diisocyanate, isophorone II Isocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylene double (iso Cyclic saturated hydrocarbon isocyanate such as 4-cyclohexyl acid ester, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, 2,4-toluene diisocyanate, 1,3-benzenedimethyl diisocyanate , aromatic phenyl diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate, 1,5-naphthalene diisocyanate, etc. The reaction is carried out by reacting a polyisocyanate with a hydroxyl group-containing (meth) acrylate.

The content of the (meth) acrylate compound in the resin composition relative to the resin composition 100 parts by weight, usually preferably 5 to 95 parts by weight, more preferably 10 to 80 parts by weight, particularly preferably 20 to 70 parts by weight.

In the present invention, fine particles may be appropriately contained in the resin composition. As a particle, Listed: organic particles, inorganic particles. Further, the fine particles may be used alone or in combination of several kinds depending on the necessary light transmittance, hardness, scratch resistance, hardening shrinkage ratio, and refractive index.

Further, from the viewpoint of improving the transmittance (especially the transmittance at 380 nm to 780 nm), it is preferred that the particles are not contained.

As the organic fine particles usable in the present invention, polystyrene resin particles can be cited. Organic polymer particles such as particles, acrylic resin particles, amine ester resin particles, and polycarbonate resin particles, porous polystyrene resin particles, porous acrylic resin particles, porous amine ester resin particles, and porous polycarbonate Porous organic polymer particles such as resin particles, resin powder of benzoquinone-formalin condensate, resin powder of benzoquinone-melamine-formalin condensate, resin powder of urea-formalin condensate, and aspartate derivative Powder of powder, powder of zinc stearate, powder of decylamine stearate, epoxy resin powder, polyethylene powder, etc., preferably crosslinked polymethyl methacrylate resin particles or crosslinked polymethyl methacrylate Ester-styrene resin particles and the like. These organic fine particles can be easily obtained by means of a commercially available product, and can also be prepared by referring to a known document.

As the inorganic fine particles usable in the present invention, there can be mentioned: conductive metal oxidation Materials, transparent metal oxides, other inorganic fillers, and the like.

As the conductive metal oxide which can be used in the present invention, zinc citrate, Tin oxide doped indium oxide (ITO), antimony-doped tin oxide (ATO), antimony pentoxide, tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, fluorine-doped tin oxide, and the like.

As the transparent metal oxide which can be used in the present invention, there can be mentioned: oxidation Bismuth, titanium oxide, zirconium oxide, hafnium oxide, zinc oxide, iron oxide, titanium oxide/zirconia/tin oxide/pentadium oxide complex, zirconia/tin oxide/pentadium oxide complex, titanium oxide/zirconia/ Tin oxide complexes, etc.

As other inorganic fillers which can be used in the present invention, calcium oxide and chlorination are mentioned. Calcium, zeolite, silicone, etc.

As the fine particles which can be used in the present invention, it is preferably excellent in hardness and scratch resistance. For high-magnification particles, titanium oxide, zirconium oxide, hafnium oxide, zinc oxide, iron oxide, titanium oxide/zirconia/tin oxide/pentadium oxide complex, zirconia/tin oxide/niobium pentoxide can be preferably used. Composite, titanium oxide / zirconia / tin oxide composite. Further, the optical sheet used in the display is required to have a high light transmittance, and therefore the primary particle diameter of the fine particles is preferably 100 nm or less. The blending ratio of the compound is preferably from 1 to 30 parts by mass, more preferably from 5 to 20 parts by mass, per 100 parts by mass of the total of the compound (A) + the compound (B).

Further, a polycarboxylic acid-based dispersant, a decane coupling agent, or a titanate system may be used in combination. A polyanthracene dispersing agent such as a decane coupling agent or a modified polyoxygenated oil or a dispersing agent of an organic copolymer is used as a dispersing agent for fine particles. The blending ratio of the resin composition is about 0 to 30% by mass, preferably about 0.05 to 5% by mass, based on the total mass of the resin composition of the present invention.

Furthermore, the term "primary particle size" means that the particle has a collapse when the agglutination collapses. Minimum particle size. That is, in the case of an elliptical particle, the short diameter is defined as the primary particle diameter. The primary particle diameter can be measured by dynamic light scattering or electron microscope observation. Specifically, the primary particle diameter can be measured under an acceleration voltage of 30 kV using a JSM-7700F field emission scanning electron microscope manufactured by Nippon Denshi Co., Ltd.

In the present invention, the primary particle diameter is preferably 100 nm or less. Further, particles of 5 to 100 nm can be preferably used. By being 100 nm or less, it is possible to provide a cured product which imparts scratch resistance and a high transmittance.

The microparticles can be dispersed and used in a solvent. Especially inorganic particles are dispersed in water. In the form of an organic solvent, a commercially available product can be easily obtained. Examples of the organic solvent to be used include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene, and hexane, octane, and decane. An aliphatic hydrocarbon solvent, and petroleum ether, white gasoline as a mixture of the same Gasoline), solvent 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; Ether acetate, diethylene glycol 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, dialkyl glutarate, succinic acid Examples of the polybasic alkyl esters such as a dialkyl ester and a dialkyl adipate, and examples of the ether solvent include alkyl ethers such as diethyl ether and ethyl butyl ether, and ethylene glycol dimethyl ether. a glycol ether such as ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether or triethylene glycol diethyl ether, or a cyclic ether such as tetrahydrofuran. Examples thereof include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

When the particles are used in the present invention, the content of the particles is relative to the resin composition. The amount of the compound is usually 0.001 to 20 parts by weight, more preferably 0.001 to 10 parts by weight, still more preferably 0.001 to 5 parts by weight.

In the resin composition of the present invention, in addition to the above components, in order to improve the work In terms of convenience, etc., a release agent, an antifoaming agent, a leveling agent, a light stabilizer, an antioxidant, a polymerization inhibitor, a plasticizer, an antistatic agent, and the like may be contained and used in combination.

Moreover, in order to obtain durability or flexibility, there are many examples of using a plasticizer. As The materials used are selected according to the desired viscosity, durability, transparency or flexibility. Specific examples thereof include olefin-based polymers such as polyethylene and polypropylene; dimethyl phthalate, diethyl phthalate, dibutyl phthalate, and bis(2-phthalic acid). Ethylhexyl)ester, diisononyl phthalate, butyl benzyl phthalate, diisononyl phthalate, dicyclohexyl phthalate, ethyl phthalate Phthalate esters such as ethyl glycolate, butyl phthalate, butyl phthalate; benzotricarboxylic acid esters such as tris(2-ethylhexyl) benzoate; dibutyl adipate Ester, diisobutyl adipate, bis(2-ethylhexyl) adipate, diisononyl adipate, diisononyl adipate, di(2-(2-butyl) adipate Oxy ethoxy) Aliphatic acid esters such as esters, bis(2-ethylhexyl) sebacate, dibutyl sebacate, bis(2-ethylhexyl) sebacate, diethyl succinate, etc. Trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris(2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, tris(xylylene) phosphate, cresyl phosphate a normal phosphate such as phenyl ester or 2-ethylhexyl diphenyl phosphate; ricinoleate such as methyl acetoacetate; poly(1,3-butanediol adipate) and the like; Acetate such as glycerin acetate; sulfonamide such as N-butylbenzenesulfonamide; polyethylene glycol benzoate, polyethylene glycol dibenzoate, polypropylene glycol benzoate, polypropylene glycol Polyalkyl ether (di)benzoate such as benzoate, polybutanediol benzoate, polybutanediol dibenzoate; polypropylene glycol, polyethylene glycol, polybutanediol Polyether; polyethoxylated bisphenol A, polypropoxy modified bisphenol A and other polyalkoxy modified bisphenol A; polyethoxy modified bisphenol F, polypropoxy modified bisphenol Polyalkoxy modified bisphenol F such as F; polycyclic aromatic such as naphthalene, phenanthrene and anthracene; Phenol, (poly)ethoxy modified (cyano) naphthol, (poly)propoxy modified (linked) naphthol, (poly) butanediol modified (linked) naphthol, (poly) Ester-modified naphthol derivatives such as naphthol; diphenyl sulfide, diphenyl polysulfide, benzothiazole disulfide, diphenyl thiourea, phenylephrine dithiobenzothiazole, cyclohexyl benzo Thiazol-2-sulfenylamine, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetrakis(2-ethylhexyl)thiuram disulfide, monosulfide Sulfur-containing compounds such as tetramethylthiuram, di-pentamethylene thiuram tetrasulfide. Preferred are (poly)ethylene glycol dibenzoate, (poly)propylene glycol dibenzoate, binaphthol, (poly)ethoxy modified binaphthol, (poly)propoxy modified linker Naphthol, diphenyl sulfide.

Further, a polymer such as an acrylic polymer, a polyester elastomer, an amine ester polymer, or a nitrile rubber may be added as needed.

The organic compound component having no reactive group preferably has a weight average molecular weight of 10,000 g/mol or less, and more preferably 5,000 g/mol or less in terms of compatibility. In the present invention, the content of the organic compound having no reactive group in the resin composition is preferably 1.5% by weight or less, more preferably 1.0% by weight or less, and particularly preferably 0.5% by weight based on the resin composition. The amount is below %. When it is 1.5% by weight or less, it is possible to prevent the components having no reactive group from being incompatible, and to remain as an insoluble component such as a solid or a gel. Therefore, it is possible to prevent transparency and heat resistance as cured properties. Therefore, it is better. Further, in order to lower the water vapor permeability, an organometallic compound such as an aluminum alkyl may be added. Although a solvent may be added, it is preferred to add no solvent.

In the resin composition of the present invention, an excellent property is also desired regarding the transmittance. Specifically, the light transmittance of each wavelength of the wavelength of 380 to 780 nm is preferably 90% or more. The light transmittance can be measured by a measuring machine such as a spectrophotometer U-3900H manufactured by Hitachi High-Technologies Co., Ltd.

Further, in the resin composition of the present invention, the glass transition temperature is preferably 70 ° C or higher, and more preferably 100 ° C or higher.

The resin composition of the present invention can be obtained by mixing and dissolving the components according to a conventional method. Preparation was carried out. For example, it can be obtained by adding each component to a round bottom flask equipped with a stirring device and a thermometer, and stirring at 20 to 80 ° C, preferably 40 to 80 ° C for 0.5 to 6 hours.

Regarding the viscosity of the resin composition of the present invention, as a viscosity suitable for workability, It is preferable to use a composition having a viscosity of not less than 1000 mPa·s at 25 ° C as measured by an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.), and the viscosity is preferably 500 mPa·s or less.

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

The resin composition of the present invention is irradiated with the above energy ray according to a conventional method, whereby The cured product of the present invention is obtained. The liquid refractive index of the resin composition of the present invention is usually from 1.45 to 1.55, preferably from 1.48 to 1.52. The refractive index can be measured by an Abbe refractometer (Model: DR-M2, manufactured by Atago).

In the resin composition of the present invention, the water vapor transmission rate at a thickness of 100 μm at 60 ° C is preferably 200 g/m ² ‧ days or less, more preferably 100 g/m ² ‧ days or less, and particularly preferably 60 g/m ² Below ‧day By being in this range, damage to the element due to penetration of moisture can be effectively prevented.

Solid sealing method of organic EL element using the resin composition of the present invention Preferably, the method comprises the steps of: forming a passivation film on the organic EL element formed on the substrate; applying a sealing adhesive to the passivation film; providing a transparent substrate for sealing; and curing the sealing adhesive Further, the curable resin composition of the present invention described above can be used as an adhesive for sealing.

The sealed organic EL element is, for example, a substrate, and includes a lower electrode, at least The organic EL layer containing the light-emitting layer and the element body of the upper electrode are formed. The substrate may be a glass substrate, a transparent organic material composed of cycloolefin, polycarbonate, polymethyl methacrylate or the like, or an organic/inorganic hybrid transparent which is made of glass fiber or the like to increase the rigidity of the transparent organic material. A flat substrate made of an electrically insulating substance such as a substrate. Moreover, as a representative structure of the element part main body, the following are mentioned.

(1) Lower electrode / luminescent layer / upper electrode

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

(3) Lower electrode / luminescent layer / hole transmission layer / upper electrode

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

For example, the organic EL device having the layer structure of the above (4) can be produced by forming a lower portion composed of an Al-Li alloy or the like on one surface of the substrate by a resistance heating vapor deposition method or a sputtering method. Electrode (cathode), and then, by a film formation method such as resistance heating vapor deposition or ion beam sputtering, sequential lamination is performed as an organic EL layer An electron transport layer composed of an oxadiazole derivative or a triazole derivative, a light-emitting layer, a hole transport layer composed of TPD or the like, and an upper electrode (anode). In addition, 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 resin composition of the present invention can be applied to an organic EL element of any configuration.

The passivation film is formed in such a manner as to cover the organic EL element. Passivation film can be An inorganic material such as tantalum nitride or ruthenium oxide is formed by a method such as vapor deposition or sputtering. The passivation film is provided to prevent penetration of moisture, ionic impurities, or the like into the organic EL element. The thickness of the passivation 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 depends on the film formation method, but usually there are incomplete pinholes. Membrane, or a film with weak mechanical strength. Therefore, in the solid sealing method using the resin composition of the present invention, the adhesive can be bonded by using a transparent substrate for sealing by applying an adhesive to the passivation film, thereby curing the adhesive to improve the reliability of the sealing.

Example

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

The resin composition and cured product of the present invention having an ultraviolet curing type were obtained in the composition shown in the following examples. Moreover, the evaluation method and evaluation criteria of the resin composition and the cured film are as follows. Further, in the examples containing the organic solvent, the organic solvent was sufficiently volatilized by an evaporator and then evaluated.

(1) Moisture permeability: The resin composition was sandwiched between glass substrates having a thickness of 5 mm, the film thickness was adjusted using a spacer of 100 μm, and the resin composition was cured at 3000 mJ/cm ² by a high pressure mercury lamp (120 W/cm, no ozone). And make a test piece. For the obtained test piece, the moisture permeability was measured at 60 ° C × 90% RH using a Lyssy water vapor permeability meter L80-5000 (manufactured by Systech IIIinois Co., Ltd.). The results are shown in Table 1.

(2) Tg (glass transition point): The Tg point of the cured resin composition was measured by a viscoelasticity measuring system EXSTAR DMS-6000 (manufactured by SII NanoTechnology) in a tensile mode at a frequency of 1 Hz. The results are shown in Table 1.

(3) Hardening shrinkage ratio: a resin composition is applied onto a substrate, and a high-pressure mercury lamp (120 W/cm, no ozone) is used to irradiate 3000 mJ/cm ² to cure the resin composition to prepare a film for specific gravity measurement. Things.

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

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

(4) Brittleness: The resin composition was applied to a PET (A4300 100 μm thickness: manufactured by Toyobo Co., Ltd.) at a thickness of 20 μm using a Meyer bar coater, using a high-pressure mercury lamp (120 W/cm, none). Ozone) Irradiation of 3000 mJ/cm ^{2 was} carried out to cure the above resin composition to obtain a test piece. Thereafter, the test piece was evaluated by bending the test piece by 180°.

(5) Transmittance: The resin composition was sandwiched between glass substrates, and the film thickness was adjusted using a 60 μm spacer, and the resin composition was hardened by a high-pressure mercury lamp (120 W/cm, no ozone) at 3000 mJ/cm ² . Audition. The obtained test piece was measured by a spectrophotometer U-3900 (manufactured by Hitachi High-Technologies Co., Ltd.) in a measurement range of 780 to 380 nm, a light source: C, and a viewing angle of 2°, and a penetration of 400 nm was recorded. rate.

In Comparative Example 1, since the high pressure mercury lamp (120 W/cm, no ozone) was not completely cured at 2000 mJ/cm ² , only items that can be measured were described.

R-604: Hydroxytrimethylacetaldehyde modified trimethylolpropane diacrylate, manufactured by Nippon Kayaku Co., Ltd.

R-684: Tricyclodecane dihydroxymethacrylate, manufactured by Nippon Kayaku Co., Ltd.

OPP-1: Ethyl phenylphenoxy acrylate, manufactured by Nippon Kayaku Co., Ltd.

PHE: Ethyl phenoxy acrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

FA-320A: Ethylene oxide 2 molar modified bisphenol A diacrylate, manufactured by Hitachi Chemical Co., Ltd.

Nicanor Y-50: a reaction of m-xylene with formaldehyde (quantitative molecular weight 250), manufactured by Fudow Co., Ltd.

ADAMANTATE M-104: 1-adamantyl methacrylate, manufactured by Idemitsu Kosan Co., Ltd.

MH-002: 1,2-bis(trimethyldecyloxy)-1,1,2,2-tetraphenylethane, manufactured by Wako Pure Chemical Industries Co., Ltd.

Irgacure 184D: 1-hydroxycyclohexyl phenyl ketone, manufactured by BASF

From the evaluation results of Examples 1 to 8 and Comparative Example 1 of Table 1, it is clear that the resin composition of the present invention having a specific composition has a high Tg and a low curing shrinkage ratio and a low moisture permeability. Therefore, it is suitable, for example, for various sealing materials, particularly sealing materials for organic EL elements. Further, in the examples, the curing shrinkage ratio was all 2% or less, and no crack was observed even in the brittleness test. The penetration rate is all above 90%.

The present invention has been described in detail with reference to the preferred embodiments of the invention.

Furthermore, the present application is based on Japanese Patent Application (2013-071027) filed on March 29, 2013, which is incorporated herein by reference. Also, all reference systems cited herein It is invoked in a holistic manner.

[Industrial availability]

The resin composition and the cured product of the present invention are excellent in visible light transmittance, high in Tg, and low in curing shrinkage ratio, moisture permeability, and brittleness, and therefore are suitable for various sealing materials, particularly those of organic EL elements.

Claims (13)

A resin composition containing a (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton, a cyclic (meth) acrylate compound (B), and a polymerization initiator (C), and a compound (B) A (meth) acrylate compound having an aromatic hydrocarbon skeleton other than the compound (A), a (meth) acrylate compound having an alicyclic hydrocarbon skeleton, and a (meth) acrylate compound having a heterocyclic skeleton are selected. At least one (meth) acrylate compound in the group. The resin composition of the first aspect of the invention, wherein the compound (A) is a (meth) acrylate compound having two or more aromatic hydrocarbon skeletons in one molecule. The resin composition of the first or second aspect of the invention, wherein the aromatic hydrocarbon skeleton of the compound (A) has a skeleton represented by the following formula (1), (wherein, X represents a direct bond or an alkyl group having 1 to 3 carbon atoms). The resin composition according to any one of claims 1 to 3, wherein the compound (A) is a compound represented by the following formula (2), (wherein X represents a direct bond or an alkylene group having 1 to 3 carbon atoms, Y represents a hydrogen atom or a methyl group, and R ₁ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom or a (meth) group) Acryl fluorenyl, R ₂ represents a direct bond or a (poly)alkyleneoxy group having a carbon number of 1 to 10. The resin composition of claim 2, wherein the (meth) acrylate compound having two or more aromatic hydrocarbon skeletons in one molecule is (meth)acrylic acid having an anthracene skeleton, a naphthalene skeleton or a biphenyl skeleton. Ester compound. The resin composition according to any one of claims 1 to 5, wherein the compound (B) is a (meth) acrylate compound having an alicyclic hydrocarbon skeleton and has two or more lipids in one molecule. A (meth) acrylate compound of a cyclic hydrocarbon skeleton. The resin composition of claim 6, wherein the (meth) acrylate compound having an alicyclic hydrocarbon skeleton contains a bicyclononane structure, a tricyclodecane ring or an adamantane ring as an alicyclic hydrocarbon skeleton . The resin composition of the sixth aspect of the invention, wherein the (meth) acrylate compound having an alicyclic hydrocarbon skeleton is a (meth) acrylate compound represented by the following formula (3), (wherein R ₃ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom or the following formula (4), and at least one of R ₃ is represented by the following formula (4)); (wherein R ₂ represents a direct bond or a (poly)alkyloxy group having 1 to 10 carbon atoms, Y represents a hydrogen atom or a methyl group, and * is bonded to a cyclic skeleton). The resin composition of the sixth aspect of the invention, wherein the alicyclic hydrocarbon skeleton is a (meth) acrylate compound represented by the following formula (5), (wherein R ₆ and R ₇ each independently represent a direct bond or an alkylene group having 1 to 6 carbon atoms or a (poly)alkyleneoxy group). The resin composition according to any one of claims 1 to 5, wherein the compound (B) is a (meth) acrylate compound having a heterocyclic skeleton and is represented by the following formula (6) (A) Acrylate compound, (wherein R ₈ represents a direct bond, a C 1 to 6 alkyl or an alkyloxy group, R ₉ represents hydrogen or a C 1 to 4 alkyl group, and Z represents a carbon atom, an oxygen atom or Nitrogen atom). The resin composition represented by the following formula (2), wherein the weight ratio of the compound (B) represented by the following formula (3) is from 9:1 to 1:9. , (wherein X represents a direct bond or an alkylene group having 1 to 3 carbon atoms, Y represents a hydrogen atom or a methyl group, and R ₁ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom or a (meth) group) Acryl fluorenyl, R ₂ represents a direct bond or a (poly)alkyleneoxy group having a carbon number of 1 to 10, (wherein R ₃ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom or the following formula (4), and at least one of R ₃ is represented by the following formula (4)); (wherein R ₂ represents a direct bond or a (poly)alkyloxy group having 1 to 10 carbon atoms, Y represents a hydrogen atom or a methyl group, and * is bonded to a cyclic skeleton). A low moisture-permeable barrier film which is obtained by hardening a resin composition according to any one of claims 1 to 11. The resin composition of any one of claims 1 to 11, which can be used for OLED applications.