KR20160030077A - Resin composition for sealing organic el element, and cured product thereof - Google Patents

Abstract

(Meth) acrylate compound having an aromatic hydrocarbon skeleton, a monofunctional (meth) acrylate compound having an alicyclic hydrocarbon skeleton and a monofunctional (meth) acrylate compound having a heterocyclic skeleton, Monofunctional cyclic (meth) acrylate compound (A); (Meth) acrylate compounds having two or more functional groups having an aromatic hydrocarbon skeleton, (meth) acrylate compounds having two or more functional groups having an alicyclic hydrocarbon skeleton, and (meth) acrylate compounds having two or more functional groups having a heterocyclic skeleton. (B) a cyclic (meth) acrylate compound having at least one functional group selected from the group consisting of (meth) acrylate compounds; And a polymerization initiator (C).

Description

TECHNICAL FIELD The present invention relates to a resin composition for sealing an organic EL device and a cured product thereof,

The present invention relates to a curable resin composition and a cured product thereof which can be suitably used as various barrier materials, particularly as a film sealing material for an organic EL device.

In recent years, displays are becoming widespread due to the introduction of thin type displays, especially plasma displays (PDP) and liquid crystal displays (LCD), which are called flat panel displays (FPD). In addition, an organic EL display (OLED) is expected as a next-generation self-emission type thin film display, and has already been put to practical use in some products. The organic EL display has attracted attention as a flat panel display in place of a CRT or a liquid crystal display due to many advantages such as low power consumption, high response speed, and high viewing angle. The organic EL element of the organic EL display has a structure in which an element body made of a thin film stacked body including a light emitting layer sandwiched between a cathode and an anode is formed on a substrate such as glass on which a driving circuit such as a TFT is formed. The light emitting layer or the electrode layer of the element portion is easily deteriorated by moisture or oxygen, and deterioration in brightness, lifetime, and discoloration occurs due to deterioration. Therefore, the organic EL element is sealed so as to block intrusion of moisture or impurities from the outside. A higher-performance sealing method and sealing material are required for realizing a high-quality and highly reliable organic EL device, and various techniques have been studied from the past.

As a representative sealing method of the organic EL element, a method of fixing a metallic or glass sealing cap into which a desiccant is previously inserted is fixed to a substrate of the organic EL element by using a sealing adhesive (Patent Document 1). In this method, an adhesive is applied to the outer peripheral portion of the substrate of the organic EL element, a sealing cap is provided thereon, and then the adhesive is solidified to fix the substrate and the sealing cap to seal the organic EL element. In this method, the sealing by the glass sealing cap is the mainstream. However, since the glass sealing cap is manufactured by processing a concave portion for inserting a desiccant into a flat glass substrate, the glass sealing cap tends to be expensive. In addition, sealing with the sealing cap can not draw light from the sealing cap side because the desiccant is inserted into the inside of the sealing cap. That is, the light emitted from the light source is drawn out from the substrate side of the element, and is limited to the bottom-emitter type element. In the case of the bottom emission type device, there is a problem that the aperture ratio is reduced by the driving circuit portion formed on the substrate and that the drawing efficiency is lowered due to the partial blocking of light by the driving circuit portion. Therefore, development of a sealing method applicable to a mission type device in a tower for drawing light from the opposite side of the substrate of the organic EL element is required.

As a typical sealing method applicable to a top-mounted type device, there is a thin-film sealing method. In the thin film sealing method, a thin film made of an inorganic or organic material is laminated on an organic EL element to form a passivation film (Patent Document 2). Silicon nitride is used as an inorganic material in a typical sealing film, and is often used by being laminated with an organic material such as (meth) acrylate resin or epoxy resin. The formation of this film is to form a laminated film by plasma CVD (chemical vapor deposition), which usually has a relatively high formation rate. Although the film formed by plasma CVD using silicon nitride is generally formed to a thickness of several hundreds nm, the film is peeled off. However, even if the film is formed to about 1 탆 by forming the organic material layer as the buffer layer, peeling in the bending test or tape peeling test is eliminated, Is also not seen. In order to impart sufficient moisture-proofing property to the device by this method, it is necessary to sequentially laminate several layers of thin films on the device. When the film is formed, the organic layer is damaged, so that particles (particles) are generated, resulting in defects such as pinholes and cracks. Further, there is a problem that an organic gas is generated by the damage of the organic layer. Therefore, development of an organic material with less damage at the time of film formation is required.

Japanese Patent No. 4876609 Japanese Patent Application Publication No. 2012-059553 Japanese Patent Application Laid-Open No. 2009-270134 Japanese Patent No. 4759971

An object of the present invention is a resin composition suitable for a process for forming a resin layer on a sheet or continuous running substrate. In particular, it is a resin composition suitable for an organic film for protection of an organic EL device, which is excellent in hardenability and processability, and has a high plasma damage resistance.

DISCLOSURE OF THE INVENTION As a result of intensive studies for solving the above problems, the present inventors have found that an ultraviolet ray curable resin composition having a specific composition and a cured product thereof solve the above problems and accomplished the present invention.

That is, the present invention relates to the following (1) to (19).

(1) a monomer selected from the group consisting of a monofunctional (meth) acrylate compound having an aromatic hydrocarbon skeleton, a monofunctional (meth) acrylate compound having an alicyclic hydrocarbon skeleton and a monofunctional (meth) acrylate compound having a heterocyclic skeleton At least one monofunctional cyclic (meth) acrylate compound (A);

(Meth) acrylate compounds having two or more functional groups having an aromatic hydrocarbon skeleton, (meth) acrylate compounds having two or more functional groups having an alicyclic hydrocarbon skeleton, and (meth) acrylate compounds having two or more functional groups having a heterocyclic skeleton. (B) a cyclic (meth) acrylate compound having at least one functional group selected from the group consisting of (meth) acrylate compounds; And

A resin composition for sealing an organic EL device, which comprises a polymerization initiator (C).

(2) The resin composition for sealing an organic EL device according to (1), wherein the liquid resin composition is vaporized and deposited on a substrate.

(3) The resin composition for sealing an organic EL device according to (2), wherein the resin composition deposited on a substrate is cured by heat or light.

(4) The resin composition for sealing an organic EL device according to (2) or (3), which is used in a process of further depositing an inorganic material to laminate an organic layer and an inorganic layer.

(5) The resin composition for sealing an organic EL device according to (3) or (4), wherein the resin composition is cured by an energy ray.

(6) The resin composition for sealing an organic EL device according to (5), wherein the light source of the energy ray is an LED (light emitting diode).

(7) The resin composition for sealing an organic EL device according to (6), wherein an emission wavelength of the LED is in a range of 365 to 425 nm.

(8) The positive resist composition according to any one of (1) to (7), wherein the monofunctional (meth) acrylate compound (A) is a monofunctional (meth) acrylate compound having an aromatic hydrocarbon skeleton having a skeleton represented by the following formula ) Acrylate compound represented by the following formula (1).

Wherein X represents an oxygen atom, an alkylene group having 1 to 3 carbon atoms or an alkyleneoxy group having 1 to 3 carbon atoms. The dotted line may be present or absent, and * may be bonded to an organic group having a (meth) acryloyl group.

(9) The positive resist composition according to any one of (1) to (8), wherein the monofunctional (meth) acrylate compound (A) is a monofunctional (meth) acrylate having an aromatic hydrocarbon skeleton represented by the following formula Wherein the organic compound is a compound.

X is an oxygen atom, an alkylene group having 1 to 3 carbon atoms or a (poly) alkyleneoxy group having 1 to 3 carbon atoms, R ₁ is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 3 carbon atoms Y represents a hydrogen atom, a phenyl group of a direct bond, or an alkyl group of 1 to 4 carbon atoms, and R < 3 > represents a hydrogen atom,

(10) The positive resist composition according to any one of (1) to (7), wherein the monofunctional (meth) acrylate compound (A) is a (meth) acrylate compound having two or more alicyclic hydrocarbon skeletons in one molecule Wherein the resin composition for sealing an organic EL device is a resin composition for sealing an organic EL device.

(11) The positive resist composition according to (10), wherein the monofunctional (meth) acrylate compound having an alicyclic hydrocarbon skeleton includes any one of dicyclodecane ring, tricyclodecane ring, isobornyl ring and adamantane ring By weight based on the total weight of the resin composition.

(12) The positive resist composition according to any one of (1) to (7), wherein the monofunctional cyclic (meth) acrylate compound (A) has an alicyclic hydrocarbon skeleton represented by any one of the following formulas (3) to (Meth) acrylate compound as a main component.

[Wherein, R ₃ are each independently a hydrogen atom, a C 1 -C 3 alkyl group, a halogen atom, a carboxyl group, a represents a hydroxyl group or the following formula (7), either one is the following formula (7) In the R ₃ ]

[Wherein R ₂ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom, a carboxyl group or a hydroxyl group, and * bonds to a cyclic skeleton]

(13) The organic EL device described in any one of (1) to (12), wherein the (meth) acrylate compound (B) having two or more functional groups has a skeleton represented by the following formula Resin composition for device sealing.

Wherein X represents a direct bond, a methylene group, a dimethylmethylene group, a sulfonyl group, a sulfur atom or an oxygen atom. The dotted line may or may not be present, and * is bonded to an organic group having a (meth) acryloyl group.

(14) The organic EL device described in any one of (1) to (13), wherein the (meth) acrylate compound (B) having two or more functional groups has a skeleton represented by the following formula Resin composition for device sealing.

X represents a direct bond, a methylene group, a dimethylmethylene group, a sulfonyl group, a sulfur atom or an oxygen atom, n is a repetition number, and represents an integer of 1 to 50,

(15) The organic EL device described in any one of (1) to (12), wherein the (meth) acrylate compound (B) having two or more functional groups has a skeleton represented by the following formula Resin composition for device sealing.

[Wherein R ₆ and R ₇ each independently represent a direct bond, an alkylene group having 1 to 6 carbon atoms or an alkyleneoxy group]

(16) The positive resist composition according to any one of (1) to (12), wherein the (meth) acrylate compound (B) having two or more functional groups is a compound having two or more functional groups having a hetero ring skeleton represented by the following formula Is a (meth) acrylate compound having at least one functional group in the molecule.

Wherein each R ₈ independently represents a direct bond, an alkylene group having 1 to 6 carbon atoms or an alkyleneoxy group. R ₉ each independently represent hydrogen, an alkylene group having 1 to 4 carbon atoms or a hydroxyl group. Z each independently represents carbon, oxygen or nitrogen;

(17) The positive resist composition according to any one of (1) to (16), wherein the monofunctional (meth) acrylate compound (A): the cyclic (meth) acrylate compound (B) having two or more functional groups has a mass ratio of 9: 1 to 1: 9. The resin composition for sealing an organic EL device according to claim 1,

(18) A low moisture permeability barrier film characterized by curing the resin composition for sealing an organic EL device according to any one of (1) to (17).

(19) An organic EL display on which an optical material obtained by curing the resin composition for sealing an organic EL device according to any one of (1) to (17) is mounted.

(Effects of the Invention)

INDUSTRIAL APPLICABILITY The resin composition of the present invention and its cured product are excellent in curability, processability, visible light transmittance, and small in plasma damage. Therefore, it is useful as a vapor deposition resin composition, and is particularly suitable for a film sealing material of an organic EL device.

The resin composition of the present invention is characterized by containing a monofunctional cyclic (meth) acrylate compound (A), a cyclic (meth) acrylate compound (B) having two or more functional groups and a polymerization initiator (C).

With the above-described structure, the use of the (meth) acrylate compound of two kinds of cyclic structures makes it possible to achieve both low plasma damability and excellent substrate adhesion while maintaining processability such as deposition.

As the monofunctional cyclic (meth) acrylate compound (A) contained in the resin composition of the present invention, any known compound having an aromatic ring, alicyclic or heterocyclic ring may be used. The compound having such a cyclic structure has a ring structure, so that the plasma damage in the subsequent step can be suppressed to a low level. This is strongly related to the cyclic structure, particularly the compound having an aromatic ring or alicyclic ring, having a high dry etching resistance. The above effect can be sufficiently exerted if the compound is a (meth) acrylate compound having at least one cyclic structure in the molecule. Further, it is preferable to select (meth) acrylate having at least one aromatic ring or alicyclic ring in the molecule because the above effect is more excellent. Examples of the skeleton having at least one aromatic ring or alicyclic ring in the molecule include a phenyl skeleton, a biphenyl skeleton, a bisphenol skeleton, a cumyl skeleton, a naphthalene skeleton, a binaphthalene skeleton, a cyclohexane skeleton, a cyclopentane skeleton, a cyclobutane skeleton, , A norbornene skeleton, an isobornyl skeleton, a dicyclodecane skeleton, a tricyclodecane skeleton, and an adamantane skeleton, and these skeletons can exhibit excellent low plasma damage resistance. The same applies to the ring structure in the cyclic (meth) acrylate compound having two or more functional groups described later.

The skeleton described in the present invention may or may not have a substituent. When the substituent is present, the substituent is preferably an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.

Specific examples of the monofunctional (meth) acrylate compound (A) having such an aromatic hydrocarbon skeleton are as follows.

(Meth) acrylate, o-phenylphenol (meth) acrylate, o-caprolactone (meth) acrylate, neopentyl glycol benzoate Phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-phenylphenol (meth) acrylate, p- (Meth) acrylate compounds having aromatic cyclic rings such as phenol polyethoxy (meth) acrylate, o-phenylbenzyl acrylate and p-phenylbenzyl acrylate, carbazole (poly) ethoxy (meth) (Meth) acrylate having a heterocyclic ring such as carbazole (poly) propoxy (meth) acrylate and (poly) caprolactone modified carbazole (meth) acrylate, naphthyl (meth) acrylate, naphthyl ) Ethoxy (meth) acrylate, naphth (Meth) acrylates such as (poly) propoxy (meth) acrylate, (poly) caprolactone modified naphthyl (meth) acrylate, binaphthol (meth) acrylate, binaphthol (Meth) acrylate, naphthol (meth) acrylate, naphthol (poly) ethoxy (meth) acrylate, naphthol (poly) Acrylate, (poly) caprolactone-modified naphthol (meth) acrylate, and the like.

Among them, as the monofunctional (meth) acrylate compound having an aromatic hydrocarbon skeleton, for example, a (meth) acrylate compound having a partial skeleton represented by the following formula (1) can be suitably used.

Wherein X represents an oxygen atom, an alkylene group having 1 to 3 carbon atoms or an alkyleneoxy group having 1 to 3 carbon atoms. The dotted line may be present or absent, and * may be bonded to an organic group having a (meth) acryloyl group.

By having the above-mentioned partial skeleton, it is considered that it is possible to more effectively exhibit the low plasma damage property which can be imparted by the aromatic ring.

Specifically, among the above (meth) acrylate compounds, the (meth) acrylate compound having a phenyl skeleton, a biphenyl skeleton, a bisphenol skeleton, a naphthalene skeleton, or a naphthalene skeleton corresponds to Formula (1) .

Herein, in the present specification, the alkyleneoxy group means an alkylene group having an ether bond, and examples thereof include (poly) oxyethylene group, (poly) oxypropylene group, -O- (CH ₂ ) ₂ -O- group and the like , And so on.

As the monofunctional (meth) acrylate compound having an aromatic hydrocarbon skeleton used in the present invention, a (meth) acrylate compound represented by the following formula (2) is preferable.

Wherein X represents an oxygen atom, an alkylene group having 1 to 3 carbon atoms or an alkyleneoxy group having 1 to 3 carbon atoms, and R ₁ represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkyleneoxy group having 1 to 3 carbon atoms, Y represents a hydrogen atom, a phenyl group of a direct bond, or an alkyl group of 1 to 4 carbon atoms], a halogen atom, a (meth) acryloyl group, a phenyl group or an oxyphenyl group,

Specific examples of such (meth) acrylate compounds include benzyl (meth) acrylate, phenol monoethoxy (meth) acrylate, phenol polyethoxy (meth) acrylate, phenol monopropoxy (Meth) acrylate, o-phenylphenol (meth) acrylate, o-phenylphenol monoethoxy (meth) acrylate, (Meth) acrylate, p-phenylphenol monoethoxy (meth) acrylate, p-phenylphenol polyethoxy (meth) acrylate, (Meth) acrylate, p-phenylphenol monopropyl methacrylate, p-phenylphenol polypropoxy (meth) acrylate, o-phenylbenzyl And the like. These compounds are low in plasma damability and low in viscosity, and thus have excellent vapor deposition processability. Of these, benzyl acrylate, phenol monoethoxy acrylate, o-phenylphenol (poly) ethoxy acrylate and o-phenyl benzyl acrylate are preferable, and benzyl acrylate is particularly preferable.

The content of the monofunctional (meth) acrylate compound having an aromatic hydrocarbon skeleton in the resin composition is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, still more preferably 30 to 70 parts by mass, desirable.

As the monofunctional (meth) acrylate compound having an alicyclic hydrocarbon skeleton which can be used in the present invention, known ones can be used without particular limitation, and the alicyclic hydrocarbon skeleton is preferably a saturated hydrocarbon skeleton. In such a cyclic skeleton, it has an effect of preventing permeation of water vapor as compared with other skeletons such as a chain structure, and is arranged in a curing system together with a (meth) acrylate compound having an aromatic hydrocarbon skeleton, It becomes possible to prevent transmission. Since the organic EL element is easily deteriorated by the attack of organic gas or water vapor, it can be said that the water vapor transmission rate is low, that is, the low moisture permeability is an important property.

Specific examples of the skeleton which can be used as the cyclic hydrocarbon skeleton include a cyclopropane skeleton, a cyclobutane skeleton, a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a dicyclodecane ring, a tricyclodecane ring, an adamantane ring, an isobornyl ring, Borane ring, and the like.

Among them, a (meth) acrylate compound having a crosslinked cyclic hydrocarbon skeleton such as a tricyclodecane ring, an isobornyl ring, an adamantane ring and the like is preferable. Such a compound is considered to exhibit an effect of suppressing plasma damage due to its excellent dry etching resistance. Further, such a compound has a high Tg (glass transition point) as compared with other skeletons such as a chain structure, but tends to have a low curing shrinkage ratio. Therefore, the hardness under the use environment can be maintained, and the residual stress at the interface at the time of curing on the substrate is small. From this point, it is also a material excellent in adhesion to a substrate. The synergistic effect is further enhanced by the mixing of the (meth) acrylate compound having a crosslinked cyclic hydrocarbon skeleton and the (meth) acrylate compound having an aromatic cyclic hydrocarbon skeleton. The same applies to the alicyclic hydrocarbon skeleton in the cyclic (meth) acrylate compound having two or more functional groups described later.

Specific examples of the monofunctional (meth) acrylate compound having an alicyclic hydrocarbon skeleton include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl (Meth) acrylate, cyclohexyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, 1,3-adamantanediol (Meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl . Of these, cyclohexyl acrylate is preferred.

As the monofunctional (meth) acrylate compound having an alicyclic hydrocarbon skeleton, a (meth) acrylate compound having a structure represented by the following formulas (3) to (6) can be preferably used.

[Wherein, R ₃ are each independently a hydrogen atom, a C 1 -C 3 alkyl group, a halogen atom, a carboxyl group, a represents a hydroxyl group or the following formula (7), either one is the following formula (7) In the R ₃ ]

[Wherein R ₂ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom, a carboxyl group or a hydroxyl group, and * bonds to a cyclic skeleton]

The content of the monofunctional (meth) acrylate compound having an alicyclic hydrocarbon skeleton in the resin composition is preferably from 10 to 90 parts by mass, more preferably from 20 to 80 parts by mass, still more preferably from 30 to 70 parts by mass, per 100 parts by mass of the resin composition Particularly preferred.

The (meth) acrylate compound having a hetero ring skeleton usable as the monofunctional cyclic (meth) acrylate compound in the present invention is described below.

The heterocyclic skeleton has an effect of preventing plasma damage as compared with other skeletons such as a chain structure, and is arranged in a curing system together with a (meth) acrylate compound having an aromatic hydrocarbon skeleton or alicyclic hydrocarbon skeleton, It becomes possible to prevent the plasma damage remarkably.

Specific examples of the hetero ring skeleton include dioxane skeleton, trioxane skeleton, tetrahydrofuran skeleton, pyrrolidine skeleton, piperidine skeleton, spiroglycol skeleton, morpholine skeleton, triazine skeleton, isocyanurate A skeleton, a carbazole skeleton, an imidazole skeleton, and the like.

Specific examples of the (meth) acrylate compound having such a heterocyclic skeleton include the following (meth) acrylate compounds.

(Meth) acrylate, morpholine (meth) acrylate, isocyanuric acid EO (meth) acrylate, isophorone diisocyanate, (Meth) acrylate,--caprolactone modified ((meth) acryloxyethyl) isocyanurate, hydroxypivaline aldehyde modified trimethylolpropane (meth) acrylate, pentamethylpiperidinyl , Tetramethylpiperidinyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, spiroglycol (meth) acrylate, imide (meth) acrylate and the like.

The content of the monofunctional (meth) acrylate compound having a hetero ring skeleton in the resin composition is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, still more preferably 30 to 70 parts by mass, desirable.

With respect to the resin composition of the present invention, a (meth) acrylate compound having a structure represented by the following partial structural formula (PE) (hereinafter referred to as a poly EO-modified (meth) acrylate compound ) Is preferably smaller than the total mass of the (meth) acrylate compound other than the poly EO-modified (meth) acrylate compound, more preferably 1/2 or less.

[Wherein t represents an integer of 2 or more]

This is because the poly EO-modified (meth) acrylate compound tends to be subjected to plasma damage, and if the content of the poly EO-modified (meth) acrylate compound is large and becomes dominant in the resin composition, the plasma damability to be.

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

In the present invention, the cyclic poly (EO) modified (meth) acrylate compound which is a cyclic (meth) acrylate compound and is a poly EO modified (meth) acrylate compound may be a (meth) acrylate compound having an aromatic hydrocarbon skeleton of the present invention or a cyclic (Meth) acrylate compound, it is preferably 50 parts by mass or less, more preferably 20 parts by mass or less, based on 100 parts by mass of the resin composition, even if it is used.

As the cyclic (meth) acrylate compound (B) having two or more functional groups used in the present invention, any compound having an aromatic ring, alicyclic or heterocyclic ring may be used.

As the (meth) acrylate compound (B) having two or more functional groups having an aromatic hydrocarbon skeleton, the skeleton suitable as an aromatic ring or an alicyclic group is as described above. Specifically, a (poly) ethoxy-modified bisphenol A di (Meth) acrylate, (poly) propoxy modified bisphenol A di (meth) acrylate, (poly) ethoxy (poly) propoxy modified bisphenol A di (Meth) acrylate, (poly) propoxy modified bisphenol F di (meth) acrylate, (poly) ethoxy (poly) propoxy modified bisphenol F di (Poly) propoxy-modified bisphenol S di (meth) acrylate, hexahydrophthalic acid di (meth) acrylate, bis (meth) acrylate, (Meth) acrylate, biphenyl dimethanol di (meth) acrylate, biphenol (poly) ethoxydi (meth) acrylate, biphenol (poly) pro (Meth) acrylate having a heterocyclic ring such as a phenoxyethyl (meth) acrylate and a phthalic acid modified pentaerythritol tri (meth) acrylate, dihydroxynaphthalene di (meth) acrylate, dihydroxynaphthalene (Meth) acrylate, dihydroxynaphthalene (poly) propoxydi (meth) acrylate, binaphthol di (meth) acrylate, binaphthol (Meth) acrylate having a condensed ring such as bis (meth) acrylate, bis (meth) acrylate and (poly) caprolactone modified binaphthol di (meth) acrylate, bisphenol fluorene di Ondi (meta) arc (Meth) acrylate having a polycyclic aromatic group such as bisphenol A (meth) acrylate, bisphenoxyethanol fluorene di (meth) acrylate and bisphenoxy (poly) caprolactone fluorene di A reaction product of a kly epoxy resin and acrylic acid (and, if necessary, a reaction product with a polybasic acid anhydride), and the like. Among them, compounds having a naphthalene skeleton are preferable, and binaphthol (poly) ethoxydi (meth) acrylate is particularly preferable.

Among them, (meth) acrylate having a partial structure represented by the following formula (A) is preferable.

Wherein X represents a direct bond, a methylene group, a dimethylmethylene group, a sulfonyl group, a sulfur atom or an oxygen atom. The dotted line may or may not be present and * is bonded to an organic group having a (meth) acryloyl group.

Further, (meth) acrylate represented by the following formula (B) is particularly preferable.

(Wherein X represents a direct bond, a methylene group, a dimethylmethylene group, a sulfonyl group, a sulfur atom or an oxygen atom, m and n are repeated numbers and represent an integer of 1 to 50)

In the formula (B), m + n is preferably 2 to 30, and particularly preferably m + n is 4 to 10.

Specific examples of the polybasic acid anhydrides which can be used in the reaction with the biphenyl-type phenol aralkyl epoxy resin, acrylic acid and polybasic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, Dibasic acid anhydride such as phthalic anhydride phthalic acid, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride and anhydrous chlorendic acid, anhydrous trimellitic acid, anhydrous pyromellitic acid, benzophenonetetracarboxylic acid anhydride, biphenyltetracarboxylic acid Acid anhydrides and the like. Of these, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferable from the viewpoint of excellent heat resistance and hydrolytic resistance.

Examples of the (meth) acrylate compound (B) having two or more functional groups having an alicyclic hydrocarbon skeleton include tricyclodecane dimethanol di (meth) acrylate, cyclohexanedimethanol di (meth) (Meth) acrylate, hydrogenated bisphenol A (poly) ethoxydi (meth) acrylate, hydrogenated bisphenol A (poly) propoxydi (meth) acrylate, hydrogenated bisphenol F (Meth) acrylate, hydrogenated bisphenol F (poly) propoxydi (meth) acrylate, hydrogenated bisphenol S (poly) ethoxydi (meth) acrylate and hydrogenated bisphenol S (poly) propoxydi (Meth) acrylate, and the like.

As the (meth) acrylate compound having two or more functional groups having an alicyclic hydrocarbon skeleton, a (meth) acrylate compound having a structure represented by the following formula (3) can be preferably used.

[Wherein R ₃ represents the following formula (7)

[Wherein R ₂ is as defined above and * bonds to a cyclic skeleton]

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

The content of the (meth) acrylate compound having two or more functional groups having an alicyclic hydrocarbon skeleton in the resin composition is preferably from 10 to 90 parts by mass, more preferably from 20 to 80 parts by mass, more preferably from 30 to 30 parts by mass, To 70 parts by mass is particularly preferable.

Examples of the (meth) acrylate compound (B) having two or more functional groups having a hetero ring skeleton include isocyanuric acid EO-modified di (meth) acrylate, epsilon -caprolactone modified tris ((meth) acryloxyethyl) iso (Meth) acrylate, isobutyric acid, isobutyrate, isobutyrate, isobutyrate, isobutyrate, isobutyrate and isobutyrate.

Examples of the (meth) acrylate compound having such a heterocyclic skeleton include a morpholine skeleton, a tetrahydrofuran skeleton, an oxane skeleton, a dioxane skeleton, a triazine skeleton, a carbazole skeleton, a pyrrolidine skeleton, A piperazine skeleton, and a spiroglycol skeleton, and preferably a (meth) acrylate compound having a structure represented by the following formula (10) can be used.

Wherein R ₁₀ is a direct bond, an alkylene group having 1 to 6 carbon atoms or an alkyleneoxy group, R ₁₁ is a hydrogen atom or an alkylene group having 1 to 4 carbon atoms, X is a nitrogen atom, oxygen Y represents a methylene group or a carbonyl group, and m represents an integer of 1 to 4. Provided that X does not all become a methylene group]

Here, preferably, a compound represented by the following formula (9) can be used.

Wherein each R ₈ independently represents a direct bond, an alkylene group having 1 to 6 carbon atoms or an alkyleneoxy group. And each R ₉ independently represents a hydrogen atom or an alkylene group having 1 to 4 carbon atoms. Z represents a methylene group, an oxygen atom or a nitrogen atom]

The content of the (meth) acrylate compound having two or more functional groups having a hetero ring skeleton in the resin composition is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, still more preferably 30 to 80 parts by mass, Particularly preferably 70 parts by mass.

In the present invention, the molecular weight of the (meth) acrylate monomer that can be used for film formation is preferably 100 to 1000. More preferably 120 to 700, and particularly preferably 150 to 400. This is because it is difficult to vaporize monomers having a large molecular weight. If the ease of vaporization between the constituting resins is significantly different, there is a possibility that the resin composition ratio in the evaporator is changed. Further, in the case of a material which is difficult to vaporize, the productivity tends to deteriorate, and as a result, the tact time tends to be long, which may increase the cost.

As the polymerization initiator (C) used in the present invention, the following polymerization initiators can be used.

Specific examples of the polymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; Acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy- 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, oligo [2-hydroxy- Hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone]; Anthraquinones such as 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, 2-chloro anthraquinone, and 2-amylanthraquinone; Thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenylsulfide and 4,4'-bismethylaminobenzophenone; (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, and the like Pin oxides and the like. Preferably acetophenones, more preferably 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl-phenylketone. There is also a case where an LED lamp is used as a light source for performing photo-curing for the purpose of minimizing damage to other materials. Generally, LED lamps are said to have lower irradiation energy than high-pressure mercury lamps or metal halide lamps. When the curing by the LED lamp is performed, the light emitting wavelength is 365 nm, 385 nm, 390 nm, 395 nm, 405 nm, or the like, which is a commercial product. However, since any of the lamps is near to visible light, a photopolymerization initiator having a relatively long wavelength side There is a need. In that case, a photopolymerization initiator of phosphine oxides is preferable, and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is particularly preferable. A photopolymerization initiator based on acylphosphine oxide is particularly preferable.

The content of the component (C) of the present invention is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total amount of the resin composition. In the resin composition of the present invention, the polymerization initiator (C) may be used singly or in combination of plural kinds.

In the resin composition of the present invention, a (meth) acrylate compound other than the component (A) and the component (B) may be used in consideration of the viscosity, refractive index and adhesion of the resin composition of the present invention. Examples of the (meth) acrylate monomer include monofunctional (meth) acrylates, bifunctional (meth) acrylates, polyfunctional (meth) acrylates having three or more (meth) acryloyl groups in the molecule, urethane (Meth) acrylate, polyester (meth) acrylate, and the like can be used.

Examples of the monofunctional (meth) acrylate include butanediol (meth) acrylate, hexanediol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (Meth) acrylate having a hydroxyl group such as hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and dipropylene glycol (meth) acrylate, dimethylaminoethyl (Meth) acrylate, octyl (meth) acrylate, isobutyl (meth) acrylate, octyl (meth) acrylate, (Meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl Late, Isomi (Meth) acrylate, 2-ethylhexylcarbitol (meth) acrylate, polyethylene glycol (meth) acrylate having an alkyl group such as methyl (meth) acrylate, (Meth) acrylate of a polyhydric alcohol such as poly (meth) acrylate, polypropylene glycol (meth) acrylate and the like.

Examples of the (meth) acrylate monomer having two functional groups include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, (Meth) acrylate, (poly) ethylene glycol di (meth) acrylate having a linear methylene structure such as 1,10-decanediol di (meth) acrylate and polytetramethylene glycol di (meth) Di (meth) acrylate of polyhydric alcohols such as poly (propylene glycol) di (meth) acrylate.

Examples of the polyfunctional (meth) acrylate monomer include pentaerythritol tri (meth) acrylate, pentaerythritol (poly) ethoxy tri (meth) acrylate, pentaerythritol (poly) propoxy tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, pentaerythritol (poly) ethoxytetra (meth) acrylate, pentaerythritol (poly) propoxytetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol (poly) ethoxypenta (meth) acrylate, dipentaerythritol But are not limited to, erythritol (poly) caprolactone hexa (meth) acrylate, dipentaerythritol (poly) ethoxyhexa (meth) acrylate, dipentaerythritol (Meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol propane (poly) ethoxy tri (meth) acrylate, trimethylol propane Polyfunctional (meth) acrylates of polyhydric alcohols such as poly (meth) acrylate, poly (meth) acrylate, poly (meth) acrylate, (Meth) acrylate having a silicon skeleton such as an acid-modified polyfunctional (meth) acrylate such as a polyfunctional (meth) acrylate and 2,2,2-trisacryloxymethylsuccinic acid, ) Acrylate, and the like.

Examples of the urethane (meth) acrylate include diol compounds such as 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, Butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A polyethoxydiol, bisphenol A polypro Or a polyester diol which is a reaction product of these diol compounds with a dibasic acid or an anhydride thereof (for example, succinic acid, adipic acid, azelaic acid, dimeric acid, isophthalic acid, terephthalic acid, phthalic acid or an anhydride thereof) Organic polyisocyanates (e.g., tetramethylene diisocyanate, hexamethylene diisocyanate Chain saturated hydrocarbon isocyanates such as isocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, Cyclic saturated hydrocarbon isocyanates such as methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate and hydrogenated toluene diisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, aromatic polyisocyanates such as p-phenylenediisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-isopropyl-1,3-phenyldiisocyanate and 1,5-naphthalene diisocyanate) , And a reaction product in which a hydroxyl group-containing (meth) acrylate is added.

Examples of the epoxy (meth) acrylate include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, terminal glycidyl ether of propylene oxide adduct of bisphenol A, fluorene epoxy resin, bisphenol S type epoxy resin And reaction products of (meth) acrylic acid and the like.

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

The content of the (meth) acrylate monomer other than the component (A) and the component (B) in the resin composition is preferably 5 to 95 parts by mass, more preferably 10 to 80 parts by mass, To 70 parts by mass is particularly preferable.

The resin composition of the present invention may contain a compound having an oxetane ring.

The compound having an oxetane ring can be used without any particular limitation, and examples thereof include 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [2- Ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyloxethenyl) butyl] ether, Methoxy] benzene, 1,2-bis [(3-ethyloxetan-3-yl) methoxy] benzene, 1,3- , 3,4'-bis [(3-ethyloxetan-3-yl) methoxy] biphenyl, 2,2'-bis [ , 3 ', 5,5'-tetramethyl [4,4'-bis (3-ethyloxetan-3- yl) methoxy] biphenyl, 2,7- 3-yl) methoxy] -2,2,3,3,4,4,5,5-octafluorohexane, 3 (meth) Bis [(2- (1-ethyl-3-oxetanyl) methoxymethyl] -tricyclo [5.2.1.2.6] decane, Ethyl-3-oxetanyl) methoxy] ethylthio} ethane, 4,4'-bis [ 3-oxetanyl) methyl] thiodibenzenethio ether, 2,3-bis [(3-ethyloxetan-3- yl) methoxymethyl] Ethyl-3-oxetanyl) methyl] -propane-1,3-diol, 2,2-dimethyl- Ethyl-1,3-O-bis [(3-ethyloxetan-3-yl) methyl] Methyl-propane-1,3-diol, 1,4-O-bis [(3-ethyloxetan- 4,6-O-tris [(3-ethyloxetan-3-yl) methyl] cyanuric acid and the like. These are preferably two or more kinds, and at least one of them is preferably an oxetane compound having an alkyleneoxy group.

The content of the oxetane compound in the resin composition is preferably 5 to 95 parts by mass, more preferably 10 to 80 parts by mass, and particularly preferably 20 to 70 parts by mass, relative to 100 parts by mass of the resin composition.

The resin composition of the present invention may suitably contain a compound having an epoxy group. Examples of the compound having an epoxy group include a monofunctional epoxy compound, a polyfunctional epoxy compound and an alicyclic epoxy.

Examples of the monofunctional epoxy compound include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, -Butylene oxide, 1,3-butadiene monoxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexenesoxide, 3-methacryloyloxy Methylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, and the like.

Examples of polyfunctional epoxy compounds include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl Ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexyl Methyl-3 ', 4'-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane- Epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinyl epoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4- Cyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylene bis ( (3,4-epoxycyclohexanecarboxylate), ethylenebis (3,4-epoxycyclohexanecarboxylate), epoxyhexahydroxane (3,4-epoxycyclohexanecarboxylate), dicyclopentadiene diepoxide, Dihexyl phthalate, dihexyl phthalate di-2-ethylhexyl, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl Ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,1,3-tetradecadienedioxide, limonene dioxide, 1,2,7,8-diepoxy octane, 1, 2,5,6-diepoxycyclooctane, and the like.

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

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

Among these epoxy compounds, aromatic epoxy compounds and alicyclic epoxy compounds are preferred from the viewpoint of better curing speed, and alicyclic epoxy compounds are particularly preferred. Among the alicyclic epoxy compounds, bifunctional alicyclic epoxy is preferable, and 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate is particularly preferable. These may be used alone, or two or more of them may be used. The content of the component (B) of the present invention is preferably from 0 to 70 parts by mass, more preferably from 20 to 70 parts by mass, particularly preferably from 0 to 70 parts by mass, relative to 100 parts by mass of the total amount of the component (A) Is 25 to 50 parts by mass. The epoxy equivalent is preferably 50 to 500 g / eq, more preferably 100 to 300 g / eq.

In order to cure the oxetane resin and the epoxy resin, it is necessary to blend a polymerization initiator (C) such as a photocationic polymerization initiator. As the Gwangyang ionic initiator, for example, aromatic iodonium complex salt or aromatic sulfonium complex salt can be given.

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

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

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

Given the environmental and human health hazards and regulations of various countries, it has been found that diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate, tris [4- 4-acetylphenylsulfanyl) phenyl] sulfoniumtris [(trifluoromethyl) sulfonyl] methanide is most preferably used. The content of the photocationic polymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the total amount of the oxetane resin and the epoxy resin component. The photocationic polymerization initiator may be used singly or in combination of plural kinds.

The resin composition of the present invention may contain a release agent, a defoaming agent, a leveling agent, a light stabilizer, an antioxidant, a polymerization inhibitor, a plasticizer, an antistatic agent, etc., have.

Further, there are many examples in which a plasticizer is used to obtain durability and flexibility. The material to be used is selected according to desired viscosity, durability, transparency, flexibility and the like. Specific examples thereof include olefin-based polymers such as polyethylene and polypropylene, aliphatic polymers such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, dicyclohexyl Phthalate esters such as phthalate, ethyl phthalyl ethyl glycolate and butyl phthalyl butyl glycolate, trimellitic acid esters such as tris (2-ethylhexyl) trimellitate, dibutyl adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, bis (2- (2-butoxyethoxy) ethyl) adipate, bis Aliphatic dibasic acid esters such as bis (2-ethylhexyl) sebacate and diethyl succinate, trimethyl phosphate, triethyl phosphate, tributyl phosphate (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, and 2-ethylhexyldiphenyl phosphate, and methyl acetyl ricinoleate And poly (1,3-butanediol adipate), acetates such as glyceryl triacetate, sulfonamides such as N-butylbenzenesulfonamide, , Polyalkylene oxide (dibenzoate) such as polypropylene glycol benzoate, polypropylene glycol dibenzoate, polytetramethylene glycol benzoate and polytetramethylene glycol benzoate, polypropylene glycol, polyethylene glycol, polytetramethylene glycol , Polyethoxy-modified bisphenol A, poly Polyalkoxy-modified bisphenol F such as polyoxy-modified bisphenol F, polypropoxy-modified bisphenol F and the like, polycyclic aromatics such as naphthalene, phenanthrene and anthracene, (non-naphthol) Naphthol derivatives such as (poly) ethoxy-modified (non) naphthol, (poly) propoxy-modified (non) naphthol, (poly) tetramethylene glycol- But are not limited to, sulfide, diphenylsulfide, benzothiazolyl disulfide, diphenyl thiourea, morpholinodithiobenzothiazole, cyclohexylbenzothiazole-2-sulfenamines, tetramethylthioranedisulfide, tetraethylthiouram A sulfhydryl compound such as disulfide, tetrabutyl thioram disulfide, tetrakis (2-ethylhexyl) thiorandom disulfide, tetramethylthiothiam monosulfide, dipentamethylenethiothiomer tetrasulfide and the like. Preferred are (poly) ethylene glycol dibenzoate, (poly) propylene glycol dibenzoate, binaphthol, (poly) ethoxy-modified binaphthol, (poly) propoxy-modified binaphthol, diphenylsulfide.

From the viewpoint of compatibility, the weight average molecular weight of the organic compound component having no reactive group is preferably 10,000 g / mol or less, and particularly preferably 5,000 g / mol or less. In the present invention, the content of the organic compound having no reactive group in the resin composition is preferably 1.5% by mass or less, more preferably 1.0% by mass or less, and particularly preferably 0.5% by mass or less based on the resin composition. When the content is 1.5% by mass or less, it is easy to prevent the component having no reactive group from being miscible and remaining as an insoluble component such as solid or gel, which makes it easy to prevent transparency and heat resistance from being inferior in curing properties desirable. Further, an organic metal compound such as alkyl aluminum may be added to lower the water vapor permeability. A solvent may be added, but it is preferable not to add a solvent because it causes a decrease in the degree of vacuum.

The substrate to which the resin layer is to be formed in the present invention is not particularly limited and examples thereof include PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PEN (polyethylene naphthalate), TAC (triacetyl cellulose) A gas barrier film, an optical film, a protective film, or the like may be used as long as it is capable of forming a monomer layer such as various resin films such as polyimide, PI (polyimide) and PMMA (polymethyl methacrylate) Various base films used for various functional films of the present invention can be used. A glass substrate is often used in organic EL display applications. In order to produce a flexible organic EL display, substrates must be flexible, and high dimensional stability and heat resistance are required, so that a thin film glass substrate, PEN, PI, or a composite material thereof is often used.

Examples of a method for depositing the resin composition of the present invention on a substrate include an ink jet method, a roll coat method, a spin coat method, a die coat method, and a vapor deposition method, but in the present invention, a vapor deposition method is preferable.

The vapor deposition apparatus used in the vapor deposition system includes a step of supplying at least a liquid resin composition to the evaporator, a step of vaporizing the resin composition with the evaporator to discharge the vaporized resin composition, And a step of performing a step of curing the deposited resin composition.

The means for performing the supplying step may be a method capable of supplying the resin composition to a certain amount of the evaporator, but it is preferable to control the amount of supply with a dispenser or an ink jet. Particularly preferably, it is a supply by an inkjet method. In the inkjet head, there is a thermal type having a heating actuator and a piezo type having a piezo element and vibrating by applying a voltage. In the present invention, piezo type is preferable. This is because the durability of the head and the controllability of the supplied resin are excellent.

It is preferable that the means for performing the vaporizing step is capable of adjusting the internal pressure of the evaporator, and the internal pressure is preferably 0.01 Torr to 10 Torr. More preferably 0.1 Torr to 1 Torr. Further, it is preferable that the evaporator can adjust the internal temperature, and the internal temperature is preferably 100 to 300 ° C. More preferably 200 to 250 ° C.

The step of discharging and the step of depositing step may be carried out by discharging a certain amount of the vaporized resin composition from the evaporator and vapor-depositing the resin on a sheet or continuously running substrate to obtain a uniform resin layer. The resin layer is usually 0.1 mu m to 10 mu m, more preferably 1 mu m to 5 mu m. By setting the thickness to a desired value, the strength of the inorganic layer can be ensured and the crack resistance is improved.

In the means for performing the step of curing the deposited resin composition, the light source to be cured is an energy ray, and the energy ray may be an electron beam such as ultraviolet rays, visible rays, infrared rays, X rays, gamma rays, laser beams, And the like. In the present invention, ultraviolet rays, laser beams, visible rays or electron beams are preferred among these. Particularly preferably, it is ultraviolet or visible light. Examples of the light source include high-pressure mercury lamps, metal halide lamps, and LED lamps. When it is necessary to conserve electric power or damage to an organic material, an LED lamp which generates less heat is preferable.

In the resin composition of the present invention, excellent characteristics are preferred with respect to the transmittance. Concretely, it is preferable that the light transmittance of each wavelength at a wavelength of 380 to 780 nm is 90% or more. The light transmittance can be measured by a measuring instrument such as a spectrophotometer U-3900H manufactured by Hitachi High-Technologies Corporation.

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

The viscosity of the resin composition of the present invention is not particularly limited, but a nozzle using a piezo element may be used to supply the resin into the vacuum chamber, so that a low viscosity is sometimes required. In this case, a composition having a viscosity of 200 mPa · s or less measured at 25 ° C using an E-type viscometer (TV-200, manufactured by Toki Sangyo Co., Ltd.) is preferable. More preferably 50 mPa · sec or less, and particularly preferably 20 mPa · sec.

The cured product of the present invention can be obtained by irradiating the resin composition of the present invention with the energy ray according to the conventional method. The liquid refractive index of the resin composition of the present invention is usually from 1.45 to 1.55, and more preferably from 1.47 to 1.54. The refractive index can be measured by Abbe's refractometer (model: DR-M2, manufactured by Atago Co., Ltd.).

Example

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

The ultraviolet ray curable resin composition and the cured product of the present invention were obtained in the composition shown in Table 1 below. Evaluation methods and evaluation criteria for the physical properties of the resin composition and the cured film shown in Table 1 are as follows.

Synthesis Example 1 and Synthesis Example 2 in Table 1 were synthesized by the following methods. The physical properties in the synthetic examples were measured by the following methods.

[Epoxy equivalent] The epoxy equivalent was measured by the method described in JIS K7236: 2001.

Synthesis Example 1: Synthesis of epoxycarboxylate (poly) carboxylic acid compound

144 g of biphenyl-type phenol aralkyl epoxy resin NC-3000H (288 g / eq of epoxy, n = 2.1) manufactured by Nippon Kayaku Co., Ltd. as the epoxy resin, 144 g of acrylic acid AA, molecular weight: 72), 1.5 g of triphenylphosphine as a catalyst, and 100 g of propylene glycol monomethyl ether monoacetate as a solvent were added and reacted at 100 DEG C for 24 hours to obtain an epoxycarboxylate compound.

To the obtained epoxy carboxylate compound, 4 g (set acid value 7) of tetrahydrophthalic anhydride as a polybasic acid anhydride was added, and propylene glycol monomethyl ether monoacetate as a solvent was added thereto so as to have a solid content of 70% by mass and heated at 100 DEG C for 10 hours To obtain a (poly) carboxylic acid compound (actual solid component acid value: 11).

Synthesis Example 2: Synthesis of binaphthol polyethoxydiacrylate

286.3 g (1.0 mole) of 1,1'-bi-2-naphthol, 264.2 g (3.0 mole) of ethylene carbonate, 41.5 g (0.3 mole) of potassium carbonate, 2000 ml of toluene was introduced and reacted at 110 ° C for 12 hours.

After the reaction, the obtained reaction solution was washed with water and 1% NaOH aqueous solution, and then washed with water until the washing water became neutral. The solvent after washing with water was distilled off under reduced pressure using a rotary evaporator to obtain 300.0 g of a reaction product of 2 mol of ethylene oxide of 1,1'-bi-2-naphthol.

Subsequently, 187.2 g (0.5 mole) of the ethylene oxide 2 mole reactant of 1,1'-bi-2-naphthol, 86.5 g (2.4 mole) of acrylic acid, 0.95 g of toluene sulfonic acid, 0.87 g of hydroquinone, 917.4 g of toluene, and 393.2 g of cyclohexane were injected into the reaction vessel and reacted at a reaction temperature of 95 to 105 ° C while distilling off the product with a solvent. After the reaction, the reaction solution was neutralized with a 25% NaOH aqueous solution and then washed three times with 200 g of 15% by mass of saline. The solvent was distilled off under reduced pressure to obtain binaphthol polyethoxydiacrylate.

[Evaluation method and evaluation standard]

(1) Viscosity: Measured at 25 캜 using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.).

(2) Cure shrinkage ratio: An ultraviolet curable resin layer was applied on a substrate, and irradiated with a high-pressure mercury lamp (80 W / cm, ozone) at 3000 mJ / cm 2 to cure the cured product.

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 DEG C, and the curing shrinkage percentage was calculated by the following equation. The measurement result is expressed by an average value of four measurement results.

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

(3) Liquid Refractive Index (25 캜): The refractive index (25 캜) of the combined energy ray curable resin was measured by Abbe's refractive index meter (DR-M2: manufactured by Atago Co., Ltd.).

(4) Tg (glass transition point): The Tg point of the cured ultraviolet curable resin layer was measured with a viscoelasticity measurement system EXSTAR DMS-6100 (Hitachi High-Tech Science Corporation), a tensile mode, and a frequency of 1 Hz.

(5) Plasma Damage: The ultraviolet curable resin composition was applied on a glass substrate to a film thickness of 3 占 퐉, and the sample was cut into 1 cm 占 1 cm and measured for TDS (temperature elevation desorption gas analyzer) before and after UV treatment.

The detection strength of M / Z = 28 before and after the UV treatment

2.0 x 10 ^-11 or less A

The detection strength of any one of M / Z = 28 before and after the UV treatment is

2.0 × 10 ^-11 or more · · · D

Respectively.

The UV treatment conditions were a wavelength of 170 nm, an illumination of 2.3 mW / cm 2, and an irradiation time of 5 minutes.

The TDS measurement conditions were a heating rate of 10 占 폚 / min, 60 占 폚 to 300 占 폚 using WA1000S manufactured by ESCO, Ltd., and heating was performed by IR.

FANCRYL (trade name) FA-BZA: benzyl acrylate, manufactured by Hitachi Chemical Co., Ltd.

NEWFRONTIER (trade name) PHE: phenol monoethoxy acrylate, DKS Co. Made by

ARONIX (trade name) M117: nonylphenol polypropoxyacrylate, manufactured by Toagosei Co., Ltd.

VISCOAT (trade name) # 150: tetrahydrofurfuryl acrylate, manufactured by Osaka Organic Chemical Industry Ltd.

VISCOAT (trade name) # 155: cyclohexyl acrylate, manufactured by Osaka Organic Chemical Industry Ltd.

KAYARAD (trade name) OPP-1: o-phenylphenol monoethoxyacrylate, manufactured by Nippon Kayaku Co., Ltd.

KAYARAD R-604: hydroxypivalic aldehyde-modified trimethylol propane diacrylate, manufactured by Nippon Kayaku Co., Ltd.

KAYARAD R-684: tricyclodecane dimethylol diacrylate, manufactured by Nippon Kayaku Co., Ltd.

NEWFRONTIER BPE-4A: bisphenol A tetraethoxydiacrylate, DKS Co. Made by

IRGACURE (trade name) 819: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, manufactured by BASF Japan, Ltd.

IRGACURE TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF Japan, Ltd.

IRGACURE 369: 2-Benzyl-2-dimethylamino- 1- (4-morpholinophenyl) -butanone-1, manufactured by BASF Japan, Ltd.

IRGACURE 184: 1-hydroxycyclohexyl-phenyl ketone, manufactured by BASF Japan, Ltd.

HDDA: 1,6-hexanediol diacrylate, manufactured by Daicel-Cytec Co., Ltd.

BLEMMER (trade name) AE-400: polyethylene glycol acrylate, manufactured by NOF Corporation

KAYARAD DPHA: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.

KAYARAD TMPTA: trimethylolpropane triacrylate, manufactured by Nippon Kayaku Co., Ltd.

LIGHTACRYLATE L-A: Lauryl acrylate, manufactured by Kyoeisha Chemical Co., Ltd.

As is evident from the evaluation results of Examples 1 to 8 and Comparative Examples 1 to 3, the resin composition of the present invention having a specific composition is excellent in workability, has a low hardening shrinkage percentage, and low in plasma damage. Therefore, it is suitable, for example, for an organic film for various barrier substrates, particularly a resin composition for film sealing of an organic EL device.

Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

The present application is based on Japanese Patent Application (2013-108477) filed on May 23, 2013, which is incorporated by reference in its entirety. Also, all references cited herein are incorporated by reference in their entirety.

INDUSTRIAL APPLICABILITY The resin composition of the present invention and its cured product are excellent in visible light transmittance and workability, and have a low hardening shrinkage ratio, so that the substrate adhesion is good. In addition, it is suitable for various barrier materials, in particular, a film sealing material of an organic EL element, from the point that the plasma damage is small.

Claims (19)

(Meth) acrylate compound having an aromatic hydrocarbon skeleton, a monofunctional (meth) acrylate compound having an alicyclic hydrocarbon skeleton and a monofunctional (meth) acrylate compound having a heterocyclic skeleton, Monofunctional cyclic (meth) acrylate compound (A);
(Meth) acrylate compounds having two or more functional groups having an aromatic hydrocarbon skeleton, (meth) acrylate compounds having two or more functional groups having an alicyclic hydrocarbon skeleton, and (meth) acrylate compounds having two or more functional groups having a heterocyclic skeleton. (B) a cyclic (meth) acrylate compound having at least one functional group selected from the group consisting of (meth) acrylate compounds; And
A resin composition for sealing an organic EL device, which comprises a polymerization initiator (C). The method according to claim 1,
A resin composition for sealing an organic EL device, characterized in that the liquid resin composition is vaporized and deposited on a substrate. 3. The method of claim 2,
A resin composition for sealing an organic EL device, characterized in that the resin composition deposited on a substrate is cured by heat or light. The method according to claim 2 or 3,
A resin composition for sealing an organic EL device, characterized in that it is used in a process of further depositing an inorganic material to laminate an organic layer and an inorganic layer. The method according to claim 3 or 4,
Wherein the resin composition is cured by an energy ray. 6. The method of claim 5,
Wherein the light source of the energy ray is an LED (light emitting diode). The method according to claim 6,
Wherein the light emitting wavelength of the LED is in a range of 365 to 425 nm. 8. The method according to any one of claims 1 to 7,
Wherein the monofunctional (meth) acrylate compound (A) is a monofunctional (meth) acrylate compound having an aromatic hydrocarbon skeleton having a skeleton represented by the following formula (1) .

Wherein X represents an oxygen atom, an alkylene group having 1 to 3 carbon atoms or an alkyleneoxy group having 1 to 3 carbon atoms. The dotted line may be present or absent, and * may be bonded to an organic group having a (meth) acryloyl group. 9. The method according to any one of claims 1 to 8,
Wherein the monofunctional cyclic (meth) acrylate compound (A) is a monofunctional (meth) acrylate compound having an aromatic hydrocarbon skeleton represented by the following formula (2).

X is an oxygen atom, an alkylene group having 1 to 3 carbon atoms or a (poly) alkyleneoxy group having 1 to 3 carbon atoms, R ₁ is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 3 carbon atoms Y represents a hydrogen atom, a phenyl group of a direct bond, or an alkyl group of 1 to 4 carbon atoms, and R < 3 > represents a hydrogen atom, 8. The method according to any one of claims 1 to 7,
Wherein the monofunctional cyclic (meth) acrylate compound (A) is a (meth) acrylate compound having two or more alicyclic hydrocarbon skeletons in one molecule. 11. The method of claim 10,
A resin composition for sealing an organic EL device, wherein the monofunctional (meth) acrylate compound having an alicyclic hydrocarbon skeleton includes any one of a dicyclo decane ring, a tricyclodecane ring, an isobornyl ring, and an adamantane ring. 8. The method according to any one of claims 1 to 7,
Wherein the monofunctional (meth) acrylate compound (A) is a monofunctional (meth) acrylate compound having an alicyclic hydrocarbon skeleton represented by any one of the following formulas (3) to (6) Resin composition for sealing.

[Wherein, R ₃ are each independently a hydrogen atom, a C 1 -C 3 alkyl group, a halogen atom, a carboxyl group, a represents a hydroxyl group or the following formula (7), either one is the following formula (7) In the R ₃ ]

[Wherein R ₂ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom, a carboxyl group or a hydroxyl group, and * bonds to a cyclic skeleton] 13. The method according to any one of claims 1 to 12,
Wherein the (meth) acrylate compound (B) having two or more functional groups has a skeleton represented by the following formula (A).

Wherein X represents a direct bond, a methylene group, a dimethylmethylene group, a sulfonyl group, a sulfur atom or an oxygen atom. The dotted line may or may not be present, and * is bonded to an organic group having a (meth) acryloyl group. 14. The method according to any one of claims 1 to 13,
Wherein the (meth) acrylate compound (B) having two or more functional groups has a skeleton represented by the following formula (B).

X represents a direct bond, a methylene group, a dimethylmethylene group, a sulfonyl group, a sulfur atom or an oxygen atom, n is a repetition number, and represents an integer of 1 to 50, 13. The method according to any one of claims 1 to 12,
Wherein the (meth) acrylate compound (B) having two or more functional groups has a skeleton represented by the following formula (8).

[Wherein R ₆ and R ₇ each independently represent a direct bond, an alkylene group having 1 to 6 carbon atoms or an alkyleneoxy group] 13. The method according to any one of claims 1 to 12,
Wherein the (meth) acrylate compound (B) having two or more functional groups is a (meth) acrylate compound having two or more functional groups having a hetero ring skeleton represented by the following formula (9) Resin composition for sealing.

Wherein each R ₈ independently represents a direct bond, an alkylene group having 1 to 6 carbon atoms or an alkyleneoxy group. R ₉ each independently represent hydrogen, an alkylene group having 1 to 4 carbon atoms or a hydroxyl group. Z each independently represents carbon, oxygen or nitrogen; 17. The method according to any one of claims 1 to 16,
Characterized in that the mass ratio of the monofunctional (meth) acrylate compound (A): the cyclic (meth) acrylate compound (B) having two or more functional groups is from 9: 1 to 1: 9 Composition. A low moisture permeability barrier film which is obtained by curing the resin composition for sealing an organic EL device according to any one of claims 1 to 17. An organic EL display comprising an optical material obtained by curing the resin composition for sealing an organic EL device according to any one of claims 1 to 17.