TW201428026A - Resin composition and cured product thereof (2) - Google Patents

Abstract

This invention relates to a resin composition for surface sealing of an organic EL element, containing an alicyclic compound (A) having an oxetanyl group or an epoxy group, and a cyclic compound (B) having an oxetanyl group or an epoxy group and meeting the following conditions (the conditions of the cyclic compound (B): the ring of the cyclic compound (B) is an aliphatic ring or a heterocyclic ring, when the ring is an aliphatic ring, the cyclic compound is a compound having a structure different from the compound used as the alicyclic compound (A).) The resin composition for surface sealing of organic EL element of this invention has an excellent liquid refractive index, and enables the resin composition to be cured by energy rays or heat such as light, and is capable of obtaining a cured product with excellent visible light transmittance and light resistance, a high Tg, low curing shrinkage and water vapor permeability, and thus it is particularly suitable for use as a surface sealing material for organic EL elements.

Description

Resin composition and hardened material (2)

The present invention relates to a resin composition and a cured product thereof.

Recently, low moisture permeability materials are important materials in various industries. In particular, in electrical and electronic and display peripheral materials, in order to maintain quality, it is an indispensable material, and a low-permeability material with higher performance is desired.

In recent years, displays, which are referred to as flat panel displays (FPDs), have been widely used, such as plasma display (PDP) and liquid crystal display (LCD), which have been put on the market. Further, an organic EL (Electrically Excited Light) display (OLED) is expected as a next-generation self-luminous thin film display, and has been put into practical use in some products. The organic EL device of the organic EL display has a structure in which an element portion main body including a thin film laminate including a light-emitting layer held by a cathode and an anode is formed on a substrate on which a driving circuit such as a TFT is formed. The layer of the element portion such as the light-emitting layer or the electrode is likely to be deteriorated by moisture or oxygen, and the brightness, the life, and the discoloration are caused by the deterioration. Therefore, the organic EL element is packaged to block infiltration of moisture or impurities from the outside. In order to realize high-quality and high-reliability organic EL elements, and to expect higher-performance packaging materials, various packaging technologies have been studied from the past.

In a typical packaging method of an organic EL device, a metal or glass sealing cap to which a desiccant is inserted in advance is fixed by using an adhesive for packaging. A method of a substrate of an organic EL element has been studied (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 cover is placed thereon, and then the substrate is fixed to the sealing cover by curing the adhesive to close the organic EL element. In such a method, packaging with a glass sealing cover is becoming mainstream. However, the sealing cap made of glass is produced by excavation for inserting a desiccant into a flat glass substrate, and the cost tends to be high. Further, the sealing is performed by the sealing cover, and since the desiccant is inserted into the inside of the sealing cover, light cannot be extracted from the sealing cover side. That is, the light emitted from the light source is taken out from the substrate side of the element, and is limited to the bottom emission type element. In the case of a bottom-emission type element, there is a problem in that the aperture ratio of the driver circuit portion formed on the substrate is lowered, and the extraction efficiency of the portion of the light is blocked by the driver circuit portion. Therefore, it has been desired to develop a packaging method suitable for a top emission type element which extracts light from the opposite side of a substrate of an organic EL element.

As a typical packaging method applicable to the top emission type element, there are a film encapsulation method and a solid encapsulation method. The thin film encapsulation method is a method of forming a passivation film by laminating a plurality of thin films made of an inorganic or organic material on an organic EL element (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, in the thin film encapsulation method, the film formation step is long and the cost is high, and the initial investment tends to be high by the introduction of the large-scale vacuum system equipment required for film formation.

On the other hand, the solid encapsulation method is a method in which a protective film is provided to cover all of the element portions of the organic EL element, and a transparent substrate for encapsulation is provided thereon via a package material. Generally, the protective film is formed by vapor deposition or sputtering of an inorganic material, but it is usually an incomplete film having pinholes or a film having weak mechanical strength. Therefore, in the solid encapsulation method, after the protective film is provided on the device, the adhesive for encapsulation is used. The reliability of the package is improved by providing a transparent substrate for packaging such as a glass substrate. Further, a method of filling the air gap with a heat or light-curing resin to improve the reliability of the package has been studied. Such a solid encapsulation method is attracting attention by a method of embedding a top emission type element in a simple and low cost.

The package is encapsulated by an organic EL device, and a thermal or photocurable resin can be used as an adhesive for encapsulation or an adhesive for surface encapsulation. However, the properties of the device and the productivity of packaging operations may be due to such characteristics. It is very important, so it is very important. For example, if the water vapor permeability of the adhesive for encapsulation is not very low, it may permeate from the pinhole of the protective film to the element portion, possibly causing deterioration of the element. Moreover, if the hardening reaction of the encapsulating material is slow, the hardening step takes time, and the productivity of the packaging operation may be lowered.

The adhesive for encapsulation can be used in addition to high transmittance in the visible light region, and is required to withstand light resistance, stable formability, or low hardenability and shrinkage for suppressing residual stress. The light-emitting element is protected from low water vapor permeability of moisture and the like. A conventional adhesive can be used as a solid encapsulation method for encapsulating an organic EL element, but it is difficult to obtain a result that satisfies both reliability and productivity, and it is desired to develop a solid package suitable for use. Adhesive for packaging.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4876609

[Patent Document 2] Japanese Laid-Open Patent Publication No. 2012-059553

[Patent Document 3] Japanese Patent No. 4557172

[Patent Document 4] Japanese Laid-Open Patent Publication No. 2001-81182

[Patent Document 5] Japanese Laid-Open Patent Publication No. 2011-225773

[Patent Document 6] Japanese Patent No. 4850231

An object of the present invention is to provide an encapsulating material for an organic EL device, particularly a resin composition suitable for surface encapsulation, and excellent in visible light transmittance, light resistance, hardenability, high Tg, hardening shrinkage, and low water vapor permeability. Hardened matter.

The inventors of the present invention have found that a resin composition having a specific composition and a cured product thereof can solve the aforementioned problems in order to solve the aforementioned problems, and the present invention has been completed.

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

(1) A resin composition for surface encapsulation of an organic EL device, which comprises an alicyclic compound (A) having an oxetanyl group or an epoxy group, and an oxetane group Or a cyclic compound (B) which satisfies the following conditions; the condition of the cyclic compound (B): the ring of the cyclic compound (B) is an aliphatic ring or a heterocyclic ring, and the ring is an aliphatic group In the case of a ring, the cyclic compound is a compound having a structure different from that of the compound used as the alicyclic compound (A).

(2) The resin composition of the above (1), wherein the alicyclic compound (A) is a skeleton having a group selected from the group consisting of the following (A-1); A-1: tricyclodecane, isodecyl, Adamantane, cyclopentane, cyclohexane, hydrogenated bisphenol A, hydrogenated bisphenol F, and hydrogenated bisphenol S.

(3) The resin composition of the above (1) or (2), wherein the alicyclic compound (A) has a group selected from the group consisting of tricyclodecane, adamantane, cyclohexane, and hydrogenated bisphenol A. The skeleton serves as an oxetane compound or an epoxy compound of an aliphatic ring.

(4) The resin composition according to any one of the above (1) to (3) wherein the cyclic compound (B) has a skeleton selected from the group consisting of the following (B-1); B-1: tricyclic fluorene Alkane, isodecyl, adamantane, cyclopentane, cyclohexane, hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S.

(5) The resin composition of the above (4), wherein the cyclic compound (B) is a skeleton having a group selected from the group consisting of tricyclodecane, adamantane, cyclohexane, and hydrogenated bisphenol A as an aliphatic ring An oxetane compound or an epoxy compound.

(6) The resin composition according to any one of the above (1) to (3) wherein the cyclic compound (B) has a skeleton selected from the group consisting of the following (B-3); B-3: morpholine, Tetrahydrofuran, Alkane, two Alkane, three (triazine), carbazole, pyrrolidine, and piperididine.

(7) The resin composition of the above (6), wherein the cyclic compound (B) is selected from the group consisting of Alkane, two Alkane and three The group of skeletons serves as a heterocyclic oxetane compound or an epoxy compound.

(8) The resin composition according to any one of (1) to (7) above which further contains a hardener (C).

(9) The resin composition of the above (8), wherein the hardener (C) is a photocationic polymerization initiator.

(10) The energy ray-curable resin composition according to the above (9), wherein the photocationic polymerization initiator is a compound selected from the group consisting of the following (C-1); C-1: phosphonium salt, cerium salt, cerium Salt, ammonium salt and citrate.

(11) The thermosetting resin composition of the above (8), wherein the hardener (C) is heat The hardener and the resin composition are thermosetting resin compositions.

(12) The thermosetting resin composition according to the above (11), wherein the thermosetting agent is a compound selected from the group consisting of the following (C-2); and C-2: an amine compound, an acid anhydride compound, and a guanamine system A compound, a phenolic compound, a carboxylic acid compound, an imidazole compound, an isocyanuric acid addition product, a metal compound, a phosphonium salt, an ammonium salt, a cerium salt, a phosphonium salt, and a microcapsule-type curing agent.

The resin composition of any one of the above-mentioned (1) to (12), wherein the resin composition contains 20 to 100 parts by mass based on the total amount of the alicyclic compound (A) and the cyclic compound (B). 80 parts by mass of the alicyclic compound (A).

The resin composition according to any one of the above-mentioned (1), wherein the resin composition is contained in an amount of 20 parts by mass based on 100 parts by mass of the total of the alicyclic compound (A) and the cyclic compound (B). To 80 parts by mass of the cyclic compound (B).

The resin composition according to any one of the above-mentioned (1), wherein the total amount of the alicyclic compound (A) and the cyclic compound (B) is 100 parts by mass. 0.1 to 5 parts by mass of the hardener (C).

(16) The resin composition according to any one of the above (1), wherein the viscosity measured at 25 ° C is 15 Pa. s below.

(17) An organic EL display obtained by surface-sealing a cured product obtained by curing the resin composition according to any one of the above (1) to (16).

(18) A film for surface encapsulation of an organic EL display, which has a barrier property in which the resin composition according to any one of the above (1) to (16) is applied onto a substrate and cured.

(19) Use of a surface package of an organic EL display of the resin composition according to any one of the above (1) to (16).

The resin composition for surface encapsulation of the organic EL device of the present invention (hereinafter, simply referred to as "resin composition for surface encapsulation" or "resin composition") is low in viscosity, and the cured product is visible light. It is excellent in transmittance and light resistance, high in Tg, low in curing shrinkage and water vapor permeability, and therefore is particularly suitable for a surface encapsulating material for organic EL elements.

An alicyclic compound (A) having an oxetane group or an epoxy group contained in the resin composition of the present invention (also referred to as "alicyclic compound (A)" or "in the present specification" The component (A)") can be used as long as it is a compound having at least one aliphatic ring in the molecule and having at least one oxetanyl group or an epoxy group. The alicyclic compound (A) is, for example, an oxetane compound having an aliphatic ring or an epoxy compound having an aliphatic ring exemplified below.

In the alicyclic compound (A) contained in the resin composition of the present invention, an alicyclic hydrocarbon skeleton or a cyclic alkyl skeleton having a crosslinked structure (having no crosslinked structure), and having a cyclic compound of an oxetane group or an epoxy group; or an alicyclic epoxy compound having at least one alicyclic epoxy group in the molecule. Examples of such specific configurations are described in detail below.

The alicyclic hydrocarbon skeleton or the cycloalkylene skeleton having a crosslinked structure may have a substituent or may have no substituent. When the alicyclic hydrocarbon skeleton or the cycloalkylene skeleton has a substituent, the substituent may, for example, be an alkyl group, an alkoxy group or an alkenyl group, and any of these groups may have a carbon number of 1 to 4 Preferably.

Such a compound is combined with the above cyclic compound (B) having an oxetane group or an epoxy group (also referred to as "cyclic compound (B)" or "component (B)" in the present specification). A cured product having an excellent moisture resistance effect can be obtained. The above skeleton has a sufficient barrier to moisture, so that moisture permeability can be prevented.

The above-mentioned alicyclic hydrocarbon group having a crosslinked structure means a polycyclic skeleton formed by a crosslinked structure in an aliphatic ring, specifically, for example, an adamantane skeleton or a tricyclodecane skeleton (also referred to as a The cyclopentadienyl skeleton) and the isodecyl skeleton are suitable. As described above, the groups may have a substituent selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkenyl group having 1 to 4 carbon atoms. As the above alicyclic hydrocarbon group having a crosslinked structure, a tricyclodecane skeleton is particularly preferable.

The cycloalkyl group skeleton is preferably, for example, a C 4 to 7 carbon group, more preferably a C 5 or 6 ring alkyl group skeleton, and preferred examples thereof include a cyclopentane skeleton and cyclohexane. Skeleton and cycloheptane skeleton. As the above cycloalkyl skeleton, a cyclohexane skeleton is particularly preferable.

The cycloalkyl group is bonded directly or via a linking group to bond two cyclohexane skeletons, which may be represented by the following formula (AA) (In the above formula, Y represents a direct bond, a sulfur atom or an alkylene group having 1 to 10 carbon atoms, an alkylene group having an ether bond or an alkylene group having an ester bond, and R ₃ independently represents a hydrogen atom or An alkyl group having 1 to 4 carbon atoms, and t represents an integer of 1 to 4. The skeleton shown.

The skeleton represented by the above formula (A-A) is preferably a direct bond or a carbon number of 1 to For the alkyl group of 10, Y is preferably a direct bond, a methylene or a propane-2,2-diyl group, and Y is particularly preferably a direct bond.

The alicyclic hydrocarbon skeleton having a crosslinked structure, the cycloalkylene skeleton (including the above formula (AA) skeleton), the oxetanyl group or the epoxy group, or a link containing a hydrocarbon group directly or The base connection is preferred.

When the above-mentioned skeleton is bonded to the oxetane group or the epoxy group by the above-mentioned linking group containing a hydrocarbon group, the linking group may, for example, also contain an ether bond or an ester-bonded hydrocarbon group, preferably, for example, a carbon number. An alkylene group of 1 to 10, an alkylene group having 1 to 10 carbon atoms having an ether bond, or an alkylene group having 1 to 10 carbon atoms having an ester bond.

In the above-mentioned linking group, specific examples of the hydrocarbon group containing an ether bond, for example, C1 to C4 are alkyl-oxy-C1 to C4 alkyl, more preferably C1 to C3 alkyl-oxy-C1 to C3. The carbon atom of the alkyl group or the like contains an ether-bonded carbon number of 2 to 10, more preferably a carbon number of 2 to 6 alkyl group; and the -oxymethyl group has an ether bond at the terminal of the alkylene group. C1 to C4 alkyl ((oxy-C1 to C4 alkyl), more preferably -oxy-C1 to C3 alkyl and the like. When the alkylene group has an ether bond at the terminal, the oxy group is generally bonded to the aliphatic ring, and the alkyl group is bonded to the oxetane ring or the epoxy ring.

In the above-mentioned linking group, as a specific example of the hydrocarbon group containing an ester bond, for example, a C1 to C6 alkyl group having an ester bond at one end (ester bond - C1 to C6 alkyl group), more preferably an ester bond a knot-C1 to C3 alkyl group; an ester bond-C1 to C6 alkylene group (more preferably a C2 to C5 alkylene group)-ester bond is equivalent to a C1 to C6 alkylene group having an ester bond at both ends; C1 to C4 alkyl-ester bond-C1 to C4 alkyl group, and C1 to C3 alkyl group-ester bond-C1 to C6 alkyl group-ester bond-C1 to C3 alkyl group is equal to carbon atom An alkylene group having an ester bond and having a carbon number of 2 to 10 (more preferably 2 to 8 carbon atoms). When the hydrocarbon group containing an ester bond has an ester bond at a terminal, it is generally an ester bond, and is a carbonyl group. The bond is bonded to an aliphatic ring, and the ether group is bonded to an alkyl group.

More preferably, the above-mentioned linking group is, for example, a C1 to C3 alkyl-oxy-C1 to C3 alkyl group, an oxy-C1 to C3 alkyl group, and an ester bond-C1 to C3 alkyl group.

The alicyclic epoxy compound is a compound having an aliphatic ring formed with an alicyclic epoxy group, and can be used as the alicyclic compound (A) in the present invention. The alicyclic epoxy group means an epoxy group which is directly bonded to an aliphatic ring by bonding one oxygen atom to two carbon atoms constituting the aliphatic ring. The aliphatic ring in which an alicyclic epoxy group is formed in the alicyclic epoxy compound is, for example, the aforementioned cycloalkyl group skeleton or an alicyclic hydrocarbon skeleton having a crosslinked structure, more specifically, for example, a cyclopentane skeleton. And a cycloalkyl group having a carbon number of 5 to 7 such as a cyclohexane skeleton, an adamantane skeleton, a tricyclodecane skeleton, and an isodecyl skeleton.

The alicyclic epoxy compound is preferably a compound having two or more alicyclic epoxy groups and having two or more aliphatic rings each having one alicyclic epoxy group. In this case, it is preferred that two or more of the aliphatic rings in which the alicyclic epoxy group is formed are directly or through a linking group containing the hydrocarbon group.

The alicyclic epoxy compound may have an oxetanyl group or an epoxy group in addition to the alicyclic epoxy group, or may be an aliphatic ring and an oxo group having an alicyclic epoxy group. The butylene group or the epoxy group is a compound which is directly or through a linking group containing the above hydrocarbon group.

A compound which is suitable as the above alicyclic epoxy compound is, for example, a compound having a skeleton selected from the group consisting of a cyclopentane skeleton, a cyclohexane skeleton and a tricyclodecane skeleton, and having an alicyclic epoxy group formed on the skeleton. More preferably, it is a compound having a cyclohexane skeleton having an alicyclic epoxy group formed, more preferably two 1,2-epoxycyclohexane skeletons directly or by a carbon number of 1 having an ester bond A compound obtained by linking alkyl groups.

The aliphatic ring (including those having an alicyclic epoxy group) of the alicyclic compound (A) of the present invention is preferably a skeleton selected from the group (A-1) below: A-1: a tricyclodecane skeleton, an isodecyl skeleton, an adamantane skeleton, a cyclopentane skeleton, a cyclohexane skeleton, a hydrogenated bisphenol A skeleton, a hydrogenated bisphenol F skeleton, and a hydrogenated bisphenol S skeleton are selected from the following (A- 2) The skeleton of the group is better: A-2: a tricyclodecane skeleton, an adamantane skeleton, a cyclohexane skeleton, and a hydrogenated bisphenol A skeleton.

Among the alicyclic compound (A), preferred examples of the oxetane compound having an aliphatic ring are, for example, 3(4),8(9)-bis[(1-ethyl-3). -oxetanyl)methoxymethyl]-tricyclo[5.2.1.2.6]decane, and the like.

Among the alicyclic compound (A), preferred examples of the epoxy compound having an aliphatic ring are, for example, groups (a-1a), (a-1b) and (a-1c) which will be described later. An alicyclic epoxy compound; a hydrogenated bisphenol A epoxy compound such as hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether; hydrogenated bisphenol F epoxide a bisphenol F type epoxy compound such as propyl ether or hydrogenated bisphenol F diglycidyl ether; hydrogenated bisphenol S diglycidyl ether, hydrogen bromide bisphenol S diglycidyl ether, etc. Hydrogenated bisphenol S type epoxy compound; epoxy compound having a tricyclodecane skeleton such as dicyclooxytricyclodecane, tricyclodecane dimethanol diglycidyl ether; adamantane epoxide ether An epoxy compound or the like having an adamantane skeleton.

Formula (a-1a):

(n is an average and represents a positive number from 1 to 5.)

The alicyclic compound (A) contained in the resin composition of the present invention is preferably an alicyclic epoxy compound or has a hydrogenated bisphenol A skeleton and a tricyclodecane skeleton. An oxetane compound or an epoxy compound of the skeleton of the group.

The alicyclic compound (A) of the present invention is preferably a compound having two or more functional groups of an oxetanyl group or an epoxy group, and a compound having two functional groups is more preferable.

The content of the component (A) of the present invention is preferably 20 to 80 parts by mass, preferably 30 to 70 parts by mass, per 100 parts by mass of the total of the component (A) and the component (B) of the reactive compound. . In order to achieve low moisture permeability of the cured product obtained from the resin composition of the present invention, the functional group equivalent of the component (A) is preferably from 10 to 500 g/eq, more preferably from 50 to 250 g/eq.

a cyclic compound (B) having an oxetane group or an epoxy group contained in the resin composition of the present invention (also referred to as "ring combination" in the present specification The substance (B) or the "component (B)") satisfies the following conditions.

The condition of the cyclic compound (B): "The ring contained in the cyclic compound (B) has an aliphatic ring or a heterocyclic ring. Here, when the ring is an aliphatic ring, the cyclic compound (B) is a cyclic compound (B). A compound having a structure different from that used as the compound of the above alicyclic compound (A) is used.

That is, when the cyclic compound (B) having a ring of an aliphatic ring is used, the resin composition of the present invention contains an oxetane compound having two different aliphatic rings or has an aliphatic ring. Made of epoxy compounds.

Among the cyclic compounds (B), examples of the compound in which the ring is an aliphatic ring can be exemplified as the compound of the above alicyclic compound (A). Among the cyclic compounds (B), preferred examples of the compound in which the ring is an aliphatic ring are, for example, compounds which are preferred in the description of the alicyclic compound (A). The same is true for better compounds and the like. In the resin composition of the present invention, when a compound having a ring of an aliphatic ring is used as the cyclic compound (B), it is more preferable to use a compound different from the skeleton used as the alicyclic compound (A).

In the cyclic compound (B), the aliphatic ring (including those having an alicyclic epoxy group) when the ring is an aliphatic ring is preferably a skeleton selected from the group (B-1) below: B-1: a tricyclodecane skeleton, an isodecyl skeleton, an adamantane skeleton, a cyclopentane skeleton, a cyclohexane skeleton, a hydrogenated bisphenol A skeleton, a hydrogenated bisphenol F skeleton, and a hydrogenated bisphenol S skeleton, selected from the group consisting of The skeleton of the group (B-2) is more preferable: B-2: a tricyclodecane skeleton, an adamantane skeleton, a cyclohexane skeleton, and a hydrogenated bisphenol A skeleton.

Hereinafter, specific examples of the compound in which the ring is an aliphatic ring among the cyclic compounds (B) will be described.

Among the cyclic compounds (B), preferred examples of the oxetane compound having an aliphatic ring are, for example, 3(4),8(9)-bis[(1-ethyl-3-) Oxetane)methoxymethyl]-tricyclo[5.2.1.2.6]decane, etc.

Among the cyclic compounds (B), preferred examples of the epoxy compound having an aliphatic ring are shown in the group of (b-1a), (b-1b) and (b-1c) which will be described later. An alicyclic epoxy compound; a hydrogenated bisphenol A epoxy compound such as hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether; hydrogenated bisphenol F diglycidyl Hydrogenated bisphenol F type epoxy compound such as hydrogenated bisphenol F diglycidyl ether; hydrogenated bisphenol S diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, etc. Hydrogenated bisphenol S type epoxy compound; epoxy compound having a tricyclodecane skeleton such as dicyclooxytricyclodecane, tricyclodecane dimethanol diglycidyl ether; adamantane epoxide ether An epoxy compound or the like having an adamantane skeleton.

Formula (b-1a):

(n is an average value and represents a positive number from 1 to 5.)

In the cyclic compound (B) of the present invention, the oxetane compound or the epoxy compound in which the ring is an aliphatic ring is a compound different from the alicyclic compound (A) in the above compound, wherein the above-mentioned fat A ring-shaped epoxy compound or an epoxy compound having a skeleton selected from the group consisting of the above-mentioned tricyclodecane skeleton, the adamantane skeleton, and the hydrogenated bisphenol A skeleton is preferred.

Among the cyclic compounds (B), the oxetane compound or the epoxy compound in which the ring is an aliphatic ring is excellent in viscosity, moisture permeability, and light transmittance, and the alicyclic epoxy is used. The compound and the epoxy compound having the aforementioned tricyclodecane skeleton or the aforementioned adamantane skeleton are particularly preferable.

Further, the cyclic compound (B) in which the ring is an aliphatic ring is preferably a compound having a bifunctional or higher oxetanyl group or an epoxy group, and more preferably a bifunctional compound.

In the cyclic compound (B) of the present invention, the cyclic compound in the case where the ring is an aliphatic ring (B) The content is preferably from 20 to 80 parts by mass, preferably from 30 to 70 parts by mass, per 100 parts by mass of the total of the component (A) and the component (B) of the reactive compound. In order to achieve low moisture permeability of the cured product obtained from the resin composition of the present invention, the functional group equivalent of the cyclic compound (B) when the ring is an aliphatic ring is preferably from 10 to 1000 g/eq, and is from 50 to 500 g. /eq is better.

Among the cyclic compounds (B), the compound having a ring as a hetero ring has at least one heterocyclic ring composed of a hetero atom other than a carbon atom and a carbon atom in the molecule, and has at least one oxetane. As the compound of the alkyl group or the epoxy group, any compound can be used. The above hetero atom may, for example, be a nitrogen atom, an oxygen atom or a sulfur atom.

Examples of the heterocyclic ring which the cyclic compound (B) having a hetero ring is a ring, for example, the skeleton of the following (B-3).

B-3: morpholine skeleton, tetrahydrofuran skeleton, Alkane skeleton, two Alkane skeleton, three Skeleton (containing an iso-cyanate ring), a carbazole skeleton, a pyrrolidine skeleton, and a piperidine skeleton.

The above heterocyclic ring system may have a substituent or may have no substituent. The substituent in the case where the above heterocyclic ring has a substituent is, for example, an alkyl group, an alkoxy group or an alkenyl group, and any of these groups is preferably one to four carbon atoms. Further, as the substituent present in the above heterocyclic ring, an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 1 to 3 carbon atoms is more preferable.

The cyclic compound (B) in which the ring is a hetero ring is preferably a skeleton selected from the group consisting of the following (B-4) and a compound having an oxetane group or an epoxy group. B-4: Alkane skeleton, two Alkane skeleton, three Skeleton (containing an iso-cyanate ring).

Further, as the cyclic compound (B) having a ring-heterocyclic ring, a compound having a bifunctional or higher oxetanyl group or an epoxy group is preferred, and a bifunctional compound is more preferred.

The above heterocyclic skeleton, with an oxetanyl group or an epoxy group, is generally straight It is preferably linked by a linking group containing a hydrocarbon group to be bonded by the linking group.

The linking group when the above-mentioned skeleton is bonded to the oxetane group or the epoxy group by the above-mentioned linking group containing a hydrocarbon group may be, for example, an ether-bonded hydrocarbon group, preferably a hydrocarbon having 1 to 10 carbon atoms. A group or an alkyl group having 1 to 10 carbon atoms having an ether bond. As the linking group, for example, a C1 to C4 alkyl group and a C1 to C4 alkyl group (-oxy-C1 to C4 alkyl group) having an ether bond at the terminal of the alkyl group are more preferable.

Among the cyclic compounds (B) having a heterocyclic ring, preferred examples of the oxetane compound having a hetero ring, such as isomeric cyanuric acid (CIC acid) and oxetane (oxetane) The reaction product of alcohol).

Among the cyclic compounds (B) having a heterocyclic ring, preferred examples of the epoxy compound having a hetero ring, such as 1,3,5-triepoxypropyl isocyanate and 1- a compound having an iso-cyanate skeleton such as allyl-3,5-dioxypropyl iso-isocyanate and two Alkanediol diepoxypropyl ether, etc. An epoxy compound such as a compound of an alkanediol skeleton.

When a heterocyclic oxetane compound or an epoxy compound is used as the cyclic compound (B) of the present invention, among the above compounds, an epoxy compound having an isomeric cyanate skeleton is preferred. Among them, a compound having the hetero-cyanate skeleton and two or three epoxy groups is particularly preferable.

In the cyclic compound (B) of the present invention, a preferred content of the cyclic compound (B) when the ring is a heterocyclic ring is 100 mass based on the total amount of the component (A) and the component (B) of the reactive compound. The portion is 20 to 80 parts by mass, preferably 30 to 70 parts by mass. For the cured product obtained from the resin composition of the present invention, in order to achieve low moisture permeability, the cyclic equivalent compound (B) of the ring is preferably a functional group equivalent of 10 to 1000 g/eq, more preferably 50 to 500 g/ Eq.

The present invention relates to a curable resin composition containing the above component (A) and the above component (B). The following is a description of a suitable combination of such ingredients.

In a preferred combination, for example, the component (A) or the component (B) has a weight average molecular weight of 2,000 or less, more preferably 1,000 or less, and particularly preferably 500 or less, as a curable resin composition. Preferably. When such a low molecular weight is used for any of the component (A) and the component (B), the low hygroscopicity of the cured product can be ensured, and the resin composition has a low viscosity, and is easily spread after coating, so that it can be obtained. An excellent composition for the manufacture of OLEDs. It is more preferable that both of the component (A) and the component (B) are the above-mentioned low molecular weight compounds.

Further, in particular, when the resin composition of the present invention is cured by heat hardening, either one of the component (A) and the component (B) is preferably an oxetane compound. When any of them is an oxetane compound, a low hygroscopic property can be ensured, and a resin composition excellent in curability in a short period of time can be obtained.

The appropriate ratio of the component (A) to the component (B) in the resin composition of the present invention is (A)/(B) in terms of mass ratio of 8/2 to 2/8, and 7/3 to 3/7. Better.

When the Tg (glass transition temperature) is to be increased from the cured resin composition of the present invention, the component (A) or the component (B) may be introduced into a dicyclopentadiene skeleton, an isodecyl skeleton or a diamond. a compound of an alkane skeleton.

In addition, when the alicyclic epoxy compound is used as the component (A) or the component (B), the alicyclic epoxy compound has a low viscosity, and thus a resin composition having excellent processability and excellent curing rate can be obtained. In this regard, in the resin composition of the present invention, it is preferred to use the alicyclic epoxy compound. Among the alicyclic epoxy compounds, more preferably a bifunctional alicyclic epoxy compound, 3,4-dicyclooxycyclohexenylmethyl-3',4'-epoxycyclohexene Carboxylic esters are particularly preferred.

In the present invention, the viscosity of the resin composition (the viscosity when measured by an E-type viscometer at 25 ° C, the same below) is generally 15 Pa. Below s, preferably 3500 mPa. Below s, more preferably 1000mPa. Below s, especially good for 500mPa. Below s, the best is 300mPa. In the following, the component (A) and the component (B) are selected, and the resin composition of the present invention is preferably prepared.

The curing agent (C) contained in the resin composition of the present invention has reactivity with the epoxy compound and the oxetane compound. As the hardener, a compound which initiates a hardening reaction by an energy ray such as heat or light can be used. In the present invention, any hardener may be used, and a hardener (C) which generally starts the hardening reaction with an energy ray is preferred.

The curing agent (C) which initiates the curing reaction by an energy line such as light can be used as long as it absorbs ultraviolet rays (having a wavelength of about 200 to 400 nm) to produce a cation, and is not particularly limited. The curing agent (C) which initiates a hardening reaction by an energy line such as light, for example, a cationic polymerization initiator (hereinafter also referred to as a photocationic polymerization initiator) which absorbs energy rays such as light to generate a cation, is exemplified. Such as strontium salt, strontium salt, strontium salt, ammonium salt, citrate.

The onium salt used as the photocationic polymerization initiator may, for example, be triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate or triphenylsulfonium (pentafluorophenyl)borate. 4,4'-bis[diphenylfluorene]diphenyl sulfide-bishexafluorophosphate, 4,4'-bis[bis(?-hydroxyethoxy)phenylhydrazine]diphenyl sulfide-double Hexafluoroantimonate, 7-[bis(p-tolyl)purine]-2-isopropylthioxanthone hexafluorophosphate, 7-[bis(p-tolyl)purine]-2-isopropyl Thiopoketone hexafluoroantimonate, 7-[bis(p-tolyl)indole]-2-isopropylindole (pentafluorophenyl)borate, phenylcarbonyl-4'-diphenylanthracene -diphenyl sulfide-hexafluorophosphate, phenylcarbonyl-4'-diphenylanthracene-diphenyl sulfide-hexafluoroantimonate, 4-third Phenylphenylcarbonyl-4'-diphenylphosphonium-diphenyl sulfide-hexafluorophosphate, 4-tert-butylphenylcarbonyl-4'-diphenylphosphonium-diphenyl sulfide-hexafluoroantimonic acid Salt, 4-tert-butylphenylcarbonyl-4'-diphenylanthracene-diphenyl sulfide-indole (pentafluorophenyl)borate, thiophenyldiphenylphosphonium hexafluoroantimonate, thiobenzene Diphenylphosphonium hexafluorophosphate, 4-{4-[2-chlorobenzylidene]phenylthio}phenylbis(4-fluorophenyl)phosphonium hexafluoroantimonate, thiophenyldiphenyl a hexafluoroantimonate halide, 4,4',4"-tris(β-hydroxyethoxyphenyl)phosphonium hexafluoroantimonate, 4,4'-bis[diphenylfluorene] II Phenyl sulfide-bis hexafluoroantimonate, diphenyl[4-(phenylthio)phenyl]phosphonium trifluoropentafluoroethyl phosphite and ginseng [4-(4-ethyl phenyl sulfonate) Mercapto)phenyl]indole [(trifluoromethyl)sulfonyl] methanide and the like.

The onium salt used as the photocationic polymerization initiator may, for example, be diphenylphosphonium (pentafluorophenyl) borate, diphenylphosphonium hexafluorophosphate or diphenylphosphonium hexafluoroantimonate. Bis(4-mercaptophenyl)phosphonium hexafluorophosphate and (triisopropylphenyl)phosphonium (pentafluorophenyl) borate.

The onium salt used as the photocationic polymerization initiator may, for example, be tri-n-butyl (2,5-dihydroxyphenyl)phosphonium bromide or cetyltributylphosphonium chloride.

The ammonium salt used as the photocationic polymerization initiator may, for example, be benzyltrimethylammonium chloride, phenyltributylammonium chloride or benzyltrimethylammonium bromide.

The ceric acid salt used as the photocationic polymerization initiator may, for example, be triphenylsulfonium hexafluoroantimonate, p-(phenylthio)phenyldiphenylphosphonium hexafluoroantimonate or 4-chloro Phenyldiphenylphosphonium hexafluoroantimonate, bis[4-(diphenylfluorene)phenyl] sulfide dihexafluoroantimonate, diallyl hexafluoroantimonate, and the like.

The hardener (C) which initiates a hardening reaction by an energy ray such as light, which is used in the present invention, is preferably the above-mentioned cerium salt and the above cerium salt, wherein high sensitivity and easy to be used from the city (triisopropylphenyl)phosphonium (pentafluorophenyl)borate, thiophenyldiphenylphosphonium hexafluoroantimonate, 4-{4-[2-chlorobenzhydryl]benzenesulfide Phenyl bis(4-fluorophenyl)phosphonium hexafluoroantimonate, diphenyl[4-(phenylthio)phenyl]phosphonium trifluoropentafluoroethyl phosphite and ginseng [4-( 4-Ethylphenylsulfonyl)phenyl]indole [(trifluoromethyl)sulfonyl] methanide or the like is preferred.

Furthermore, in view of the harmfulness to the environment and the human body and the laws of various countries, the hardening agent (C) which starts the hardening reaction with the above energy ray, uses (triisopropylphenyl) ruthenium (pentafluorofluoride) which does not contain lanthanum element. Phenyl)borate, diphenyl[4-(phenylthio)phenyl]indole trifluoromethylene pentafluoroethyl phosphite or gin[4-(4-ethylmercaptophenylsulfonyl)phenyl The ginseng [(trifluoromethyl)sulfonyl] methanide is the best.

In the resin composition of the present invention, the content of the photocationic polymerization initiator is preferably 0.05 to 5 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B). It is preferably 0.1 to 3 parts by mass. Further, in the resin composition of the present invention, the photocationic polymerization initiator may be used singly or in combination of plural kinds.

In the resin composition of the present invention, a thermal curing agent which initiates a hardening reaction with the epoxy compound and the oxetane compound by heat can be used. The thermosetting agent may, for example, be an amine compound, an acid anhydride compound, a guanamine compound, a phenol compound or a carboxylic acid compound.

Specific examples of the heat hardener which can be used include, for example, diaminodiphenylmethane, diethylidene triamine, triethylidenetetramine, diaminodiphenylphosphonium, isophoronediamine, Aminoamines such as dicyandiamide, a polyammonium resin synthesized from a dimer of linoleic acid and a diamine, an imidazole, a trifluoroborane-amine complex, and a guanidine derivative. Compounds and guanamine compounds; phthalic anhydride, trimellitic anhydride (trimellitic anhydride), pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, Nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane tetracarboxylic anhydride, bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, methyl bicyclic [2,2,1]heptane-2,3-dicarboxylic anhydride and an acid anhydride compound such as cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride; bisphenol A, bisphenol F, Bisphenol S, bismuth bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3',5,5'-tetramethyl-[1,1'-linked Benzene]-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, gins-(4-hydroxyphenyl)methane, 1,1,2,2-indole (4-hydroxyphenyl) Ethane, phenols (phenols, alkyl-substituted phenols, naphthols, alkyl-substituted naphthols, dihydroxybenzenes, dihydroxynaphthalenes, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzene Formaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4, 4'-double (A Polycondensates of oxymethyl)-1,1'-biphenyl, 1,4'-bis(chloromethyl)benzene or 1,4'-bis(methoxymethyl)benzene, etc. A phenolic compound such as a halogenated bisphenol such as a halogenated bisphenol such as tetrabromobisphenol A or a condensate of a terpene and a phenol, but is not limited thereto. These may be used alone or in combination of two or more.

Further, the encapsulating material, particularly the surface encapsulation of the organic EL, is preferably an acid anhydride excellent in transparency after curing, wherein methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, and six Hydrogen phthalic anhydride, methyl hexahydrophthalic anhydride, butane tetracarboxylic anhydride, bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2,2, 1] An acid anhydride having an alicyclic skeleton such as heptane-2,3-dicarboxylic anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is preferred. As the acid anhydride having an alicyclic skeleton, a commercially available product such as an H-TMA series from Mitsubishi Gas Chemical Co., Ltd., or the like, can be obtained as a solid or liquid product of an acid anhydride having the alicyclic skeleton (although it is described as a liquid Product, but at room temperature is semi-solid state, workability is very poor).

Further, when cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is used as the thermal curing agent, it is used alone, and the workability is extremely poor because of a solid state or a semi-solid state having a high viscosity. Therefore, it is desirable to use together with other hardeners, preferably anhydrides having an alicyclic skeleton. In this case, the hardener which can be used in combination is not particularly limited as long as it is liquid and has a low viscosity, and is, for example, a commercially available hardener, RIKACID HNA-100 containing methyl nadic anhydride and nadic anhydride. A sclerosing agent such as Nippon Physicochemical Co., Ltd., or RIKACID MH700 (manufactured by Nippon Chemical and Chemical Co., Ltd.) containing hexahydrophthalic anhydride and methylhexahydrophthalic anhydride. When cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and other hardeners are used together as a heat hardener, solid or semi-solid cyclohexane-1,3,4- may be previously prepared. The tricarboxylic acid-3,4-anhydride and the low-viscosity hardener are mixed to become uniform at room temperature or under heating to form a state in which workability is good. The heating conditions at this time are preferably 150 ° C or lower, more preferably 120 ° C, in order to prevent volatilization of the curing agent. Further, from the viewpoint of handling workability and depression of the encapsulating material after hardening, the use ratio of cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride in all hardeners is 20 to 90% by mass. More preferably, it is in the range of 30 to 80% by mass or less. When the mixing ratio exceeds 90% by mass, the workability of the hardener is extremely poor. Moreover, when it is less than 20% by mass, the effect of improvement is less likely to occur at the point of depression of the encapsulating material.

In the present invention, the proportion of the thermosetting agent in the case where the thermosetting agent is used as the curing agent is based on the functional group equivalent of the epoxy compound or the oxetane compound and the functional group of the curing agent. The equivalent of (for example, the carboxyl group of the carboxylic acid-based curing agent) is determined. It is preferably 1 equivalent to the epoxy group or oxetane group of the functional group of the component (A) and the component (B), and the functional group of the thermosetting agent such as a carboxyl group is 0.2 to 5 equivalents, more preferably 0.5. Up to 2 equivalents. Hardening reaction when it exceeds this range If it does not fully carry out, and the residual functional group remains, the toughness and heat resistance of a hardened material cannot fully exhibit.

In the resin composition of the present invention, the above-mentioned curing agent may be used together with a curing catalyst (also referred to as a curing accelerator), or a curing agent may be used alone without using the above-mentioned heat curing agent.

Specific examples of the hardening accelerator which can be used in the resin composition of the present invention, for example, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl 4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl -2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6(2'-methylimidazolium(1'))ethyl-s-three 2,4-Diamino-6(2'-undecylimidazolium (1'))ethyl-s-three 2,4-Diamino-6(2'-ethyl, 4-methylimidazolium (1'))ethyl-s-three 2,4-Diamino-6(2'-methylimidazolium(1'))ethyl-s-three . Isophthalic acid adduct, 2:3 adduct of 2-methylimidazoisocyanuric acid, 2-phenylimidazolium isocyanurate adduct, 2-phenyl-3,5- Various kinds of dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole Imidazoles; such imidazoles and polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, maleic acid, oxalic acid, etc. Salts; guanamines such as dicyanodiamine; diaza compounds such as 1,8-diaza-bicyclo(5.4.0) undecen-7, and tetraphenylborate and phenol thereof a salt such as a novolak, a salt of the above polyvalent carboxylic acid or a phosphonic acid; an ammonium salt such as tetrabutylammonium bromide, cetyltrimethylammonium bromide or trioctylmethylammonium bromide; a cationic initiator; a phosphine or bismuth compound-based thermal cationic initiator such as triphenylphosphine, tris-tolylphosphine, tetraphenylphosphonium bromide or tetraphenylphosphonium tetraphenylborate; 1-naphthalene Methylmethyl-p-hydroxyphenyl hexafluoroantimonate, benzylmethyl-p-hydroxyphenyl a cation-based thermal cation initiator such as hexafluoroantimonate or dimethyl-p-ethoxycarbonyl phenyl hexafluoroantimonate; 1-naphthylmethylmethyl-p-hydroxyphenyl hydrazine a cesium salt-based thermal cation initiator such as hexafluorophosphate, benzylmethyl-p-hydroxyphenyl sulfonium hexafluorophosphate or dimethyl-p-ethoxylated phenyl hexafluorophosphate; a metal compound such as a phenol such as 4,6-aminoaminomethylphenol, an amine adduct or tin octylate; and a microcapsule-type hardening accelerator which is microencapsulated by such a hardening accelerator.

Which of these hardening accelerators is used can be suitably selected according to the characteristics required for the transparent resin composition obtained by transparency, hardening speed, and operating conditions. As the thermal curing agent, a thermal cationic initiator is preferred, and a cerium salt-based thermal cationic initiator is particularly preferred. The content of the hardening accelerator such as a thermal cationic initiator is preferably in the range of 0.001 to 15 parts by mass, preferably 0.01 to 5, based on 100 parts by mass of the total of the component (A) and the component (B). Parts by mass.

The resin composition of the present invention is also effective in curing by a redox reaction using a cracking type photopolymerization initiator which is used in a radical polymerization system. When a cracking type photopolymerization initiator is used in combination, the ease of generation of an electron-moving reaction determines the reactivity. At this time, since the reactivity of the cerium salt having a low energy level of LUMO (the lowest empty rail region: the standard for easiness of the electron-moving reaction) is good, it is preferable to use a cerium salt as the curing agent (C). When a split type photopolymerization initiator is used in combination, any cracking type photopolymerization initiator is also used, and examples thereof include 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl-benzene. Ketone.

The thermal curing agent used in the resin composition of the present invention is preferably a thermal curing agent which is initially thermally hardened at 100 ° C or less, and a thermal cationic polymerization initiator is preferably used, in consideration of the reaction rate and the heat history of the constituent members. In the present invention, the point of the thermal history of the constituent members is considered, and the photocationic polymerization which does not require thermal energy is used. The use of the starting agent is preferred.

The resin composition of the present invention may contain other components than the component (A), the component (B), and the component (C) as needed. The other components may, for example, be fine particles, a dispersant, or a reactive compound other than the component (A) and the component (B) (for example, an oxetane compound or an epoxy compound having an aromatic ring, ( A photopolymerization initiator other than a photocationic polymerization initiator, such as a methyl acrylate or the like, and other additives.

The resin composition of the present invention may be used in combination with fine particles as needed. Examples of the fine particles include organic fine particles and inorganic fine particles. Further, the fine particles are used in consideration of the light transmittance, hardness, scratch resistance, hardening shrinkage ratio, and refractive index required for the cured product, and may be used singly or in combination.

Examples of the organic fine particles to be used in the present invention include organic polymer particles such as polystyrene resin particles, acrylic resin particles, polyurethane resin particles, and polycarbonate resin particles; porous polystyrene resin particles and porosity. Porous organic polymer particles such as acrylic resin particles, porous polyurethane resin particles, and porous polycarbonate resin particles; resin powder of benzoguanamine-formaldehyde condensate; benzoguanamine-melamine-formaldehyde condensate Resin powder, resin powder of urea-formaldehyde condensate, powder of aspartic acid ester derivative, zinc stearate powder, decyl stearate powder, epoxy resin powder, polyethylene powder, and the like. Among them, crosslinked polymethyl methacrylate resin particles or crosslinked polymethyl methacrylate/styrene resin particles are preferred. These organic fine particle systems can be easily obtained from commercially available products, and can also be prepared by referring to conventional literature.

Examples of the inorganic fine particles to be used in the present invention include conductive metal oxides, transparent metal oxides, and other inorganic fillers.

The conductive metal oxide which can be used in the present invention is, for example, 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, and fluorine doped tin oxide.

The transparent metal oxide which can be used in the present invention may, for example, be cerium oxide, titanium oxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, titanium oxide/zirconia/tin oxide/penta pentoxide composite, Zirconium oxide/tin oxide/penta pentoxide composite and titanium oxide/zirconia/tin oxide composite.

Other inorganic fillers which can be used in the present invention include, for example, calcium oxide, calcium chloride, zeolite, and cerium oxide gel.

The fine particles which can be used in the present invention are hardness and scratch resistance. Preferably, the particles having a high refractive index are preferably used, and titanium oxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, titanium oxide/zirconia/tin oxide/pentadium oxide complex, zirconia/tin oxide/five A cerium oxide composite and a titanium oxide/zirconia/tin oxide composite. Further, since the optical sheet used in the display is required to have a high light transmittance, the primary particle diameter of the fine particles is preferably 100 nm or less.

The proportion of the compounding agent in the resin composition of the present invention is preferably from 1 to 30 parts by mass, preferably from 5 to 20 parts by mass, per 100 parts by mass of the total of the component (A) and the component (B). .

When the fine particles are used in combination in the present invention, a dispersing agent for the fine particles may be used in combination with a polycarboxylic acid-based dispersing agent; a polydecane-oxygen system such as a decane coupling agent, a titanate coupling agent, or a modified polyoxygenated oil. a dispersing agent; or a dispersing agent of an organic copolymer system.

The blending ratio of the above-mentioned dispersing agent in the resin composition of the present invention is preferably from 0.001 to 30% by mass, preferably from 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 when agglomerating and disintegrating, the particles have The smallest particle size. That is, in the elliptical-shaped fine particles, the short diameter is the primary particle diameter. The primary particle size 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 electric field radiation type scanning electron microscope manufactured by Nippon Denshi Co., Ltd.

These fine particles can be used by being dispersed in a solvent. In particular, the inorganic fine particles are easily dispersed in water or an organic solvent, and a commercially available product can be easily obtained. Examples of the organic solvent to be used include a hydrocarbon solvent, an ester solvent, an ether solvent, and a ketone solvent.

Examples of hydrocarbon solvent-based aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene; aliphatic hydrocarbon solvents such as hexane, octane, and decane; and petroleum ether and unleaded gasoline of such mixtures Solvent oil (solvent naphtha) and the like.

Examples of the ester solvent include alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate; and cyclic esters such as γ-butyrolactone; ethylene glycol monomethyl ether acetate and diethylene glycol alone. Methyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, and Butanediol monomethyl ether monoacetate (mono or poly) alkanediol monoalkyl ether monoacetate; polycarboxylate such as dialkyl glutarate, dialkyl succinate and dialkyl adipate Acid alkyl esters and the like.

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

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

In the present invention, an oxetane compound having an aromatic ring or an epoxy compound can be used as the optional component.

An oxetane compound having an aromatic ring which can be used as an optional component, for example, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl }Benzene, 3-ethyl-3-phenoxymethyloxetane, 1,4-bis[(3-ethyloxetan-3-yl)methoxy]benzene, 1, 3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, 1,2-bis[(3-ethyloxetan-3-yl)methoxy] Benzene, 4,4'-bis[(3-ethyloxetan-3-yl)methoxy]biphenyl, 2,2'-bis[(3-ethyl-3-oxetan) Alkyl)methoxy]biphenyl, 3,3',5,5'-tetramethyl[4,4'-bis(3-ethyloxetan-3-yl)methoxy] Benzene, 2,7-bis[(3-ethyloxetan-3-yl)methoxy]naphthalene and 4,4'-bis[(1-ethyl-3-oxetanyl) ) methyl] thiodiphenyl sulfide or the like.

An epoxy compound having an aromatic ring which can be used as an optional component, and examples thereof include a phenyl skeleton such as styrene oxide, phenylepoxypropyl ether, and p-t-butylphenylepoxypropyl ether. Epoxy compound; biphenyl epoxypropyl ether, biphenyl diglycidyl ether, 3,3',5,5'-tetramethyl-4,4'-bis(glycidoxy) An epoxy compound having a biphenyl skeleton such as a 1,1,1'-biphenyl or a biphenyl aralkyl type epoxy compound; a novolac type such as a phenol novolak type epoxy compound and a cresol novolac type epoxy compound; Epoxy compound; bisphenol A diglycidyl ether and bisphenol A type epoxy compound such as brominated bisphenol A diglycidyl ether; bisphenol F diglycidyl ether and brominated bisphenol F Bisphenol F type epoxy compound such as diglycidyl ether; bisphenol S type epoxy compound such as bisphenol S diglycidyl ether and brominated bisphenol S diglycidyl ether; 1, 3 An epoxy having an adamantane group substituted with an aromatic ring such as bis(4'-glycidoxyphenyl)adamantane and 2,2-bis(4'-glycidoxyphenyl)adamantane Compound; bisphenylphosphonium diepoxypropyl ether and diphenyl Epoxy compound having an anthracene skeleton such as ethanol diepoxypropyl ether; glycidoxynaphthalene, 1,6-bis(2,3-epoxypropan-1-yloxy)naphthalene, binaphthyl ring Oxypropyl propyl ether, binaphthyl diepoxypropyl ether and binaphthol ethanol An epoxy compound having a naphthalene skeleton or the like such as a epoxidized propyl ether.

The above oxetane compound or epoxy compound having an aromatic ring preferably has an epoxy group selected from the group consisting of phenyl, biphenyl, bisphenol A, bisphenol F, bisphenol S and naphthalene. Compound. In the case where the viscosity of the resin composition is low, the moisture permeability of the cured product is low, and the light transmittance is excellent, an epoxy compound having a skeleton selected from the group consisting of biphenyl, bisphenol A, and naphthalene is particularly preferable. A preferred content when an oxetane compound or an epoxy compound having an aromatic ring is used in the resin composition of the present invention is 100 mass based on the total amount of the component (A) and the component (B) of the reactive compound. The portion is 20 to 80 parts by mass, preferably 30 to 70 parts by mass. In order to achieve low moisture permeability of the cured product, the functional group equivalent of the oxetane compound or the epoxy compound having an aromatic ring is preferably from 10 to 1000 g/eq, more preferably from 50 to 500 g/eq.

Further, in the resin composition of the present invention, in order to impart rigidity to the coating film, an oxetane compound or an epoxy compound having a condensed aromatic ring structure such as hydrazine or carbazole is preferably used. These oxetane compounds or epoxy compounds may be used singly or in combination of two or more.

Further, in the resin composition of the present invention, the viscosity, refractive index, and adhesion of the obtained resin composition of the present invention are considered, and the component (A), the component (B), and the above-mentioned oxygen heterocycle having an aromatic ring are considered. In addition to the butane compound or the epoxy compound, a reactive compound can also be used. Specific examples of the reactive compound include (meth) acrylate.

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

Examples of the monofunctional (meth) acrylate include isodecyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and (methyl). Alicyclic (meth) acrylate such as dicyclopentenyloxyethyl acrylate and cyclohexyl (meth) acrylate; tetrahydrofuran methyl (meth) acrylate, caprolactone modified (meth) acrylate Heterocyclic (meth) acrylate such as tetrahydrofuran methyl ester and morpholine (meth) acrylate; benzyl (meth) acrylate, ethoxy modified cresol (meth) acrylate, propoxy Modified cresol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, o-phenyl phenol (meth) acrylate, o-phenyl phenol monoethoxy (A) Acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-phenylphenol (meth) acrylate, p-phenyl phenol monoethoxy (meth) acrylate, pair (meth) acrylate having an aromatic ring such as phenylphenol polyethoxy (meth) acrylate, acrylic acid o-phenyl phenyl methyl ester and acrylic acid p-phenyl benzyl methyl ester; carbazole (poly) Ethoxy (meth) acrylate, (meth) acrylate having a heteroaromatic ring such as carbazole (poly) propoxy (meth) acrylate and (poly) caprolactone modified carbazole (meth) acrylate; naphthalene (meth) acrylate Ester, (poly)ethoxy naphthyl (meth) acrylate, (poly) propoxy (na) naphthyl (meth) acrylate, (poly) caprolactone modified naphthyl (meth) acrylate, binaphthol ( Methyl) acrylate, binaphthol (poly) ethoxy (meth) acrylate, binaphthol (poly) propoxy (meth) acrylate, (poly) caprolactone modified binaphthol ( Methyl) acrylate, naphthol (meth) acrylate, naphthol (poly) ethoxy (meth) acrylate, naphthol (poly) propoxy (meth) acrylate and (poly) Ester-modified naphthol (meth) acrylate (meth) acrylate having a condensed ring; quinone imine (meth) acrylate having a quinone ring structure; butane diol mono (meth) acrylate , 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and dipropylene (meth) acrylate having a hydroxyl group such as an alcohol (meth) acrylate; dimethylaminoethyl (meth) acrylate, butoxyethyl (meth) acrylate, caprolactone (meth) acrylate Ester, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, octafluoropentyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, (methyl) Isodecyl acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, (methyl) (meth) acrylate having alkyl group such as isomyristyl acrylate and lauryl (meth) acrylate; ethoxy diethylene glycol (meth) acrylate, 2-ethylhexyl carbitol (methyl) (meth)acrylates of polyvalent alcohols such as acrylate, polyethylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate.

The (meth) acrylate monomer having two functional groups may, for example, be a heterocyclic (meth) acrylate such as hydrogen penovanon-modified trimethylolpropane di(meth)acrylate. (poly)ethoxy modified bisphenol A di(meth)acrylate, (poly)propoxy modified bisphenol A di(meth)acrylate, (poly)ethoxy modified bisphenol F Di(meth)acrylate, (poly)propoxy modified bisphenol F di(meth)acrylate, (poly)ethoxy modified bisphenol S di(meth)acrylate, (poly)propene Oxygen-modified bisphenol S di(meth) acrylate, hexahydrophthalic acid di(meth) acrylate, and bis(oxy) ethoxy fluorene (meth) acrylate having an aromatic ring (meth) acrylate having a heteroaromatic ring such as biphenyl dimethanol di(meth) acrylate; binaphthol di(meth) acrylate, binaphthol (poly) ethoxy di (a) a (meth)acrylic acid having a condensed ring such as acrylate, binaphthol (poly)propoxy di(meth)acrylate, and (poly)caprolactone modified binaphthol di(meth)acrylate Ester; bisphenol quinone di(meth) acrylate, bisphenoxymethanol bis(methyl) propyl Polycyclic aromatic (meth)acrylic acid, such as enoate, bisphenoxyethanol hydrazine di(meth) acrylate, and bisphenoxycaprolactone bis(meth) acrylate Acrylate; acrylate of isocyanate such as diacrylated isocyanurate; 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9 - (meth) acrylate having a linear methylene structure such as decanediol di(meth) acrylate and polybutylene glycol di(meth) acrylate; tricyclodecane dimethanol (meth) acrylate Alicyclic (meth) acrylates such as esters; ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and polypropylene glycol di(methyl) a di(meth)acrylate of a polyhydric alcohol such as an acrylate.

The above polyfunctional (meth) acrylate monomer is exemplified by ginseng (propylene oxyethyl) isomeric cyanurate and (poly) caprolactone modified ginseng (propylene oxyethyl) Polyfunctional (meth) acrylate having an isomeric cyanurate ring such as cyanuric acid; neopentyl alcohol tri(meth) acrylate, neopentyl alcohol tetra (meth) acrylate, (poly) Ethoxylated modified pentaerythritol tetra(meth)acrylate, (poly)propoxy modified neopentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate (poly)caprolactone modified dipentaerythritol penta (meth) acrylate, (poly) ethoxylated dipentaerythritol penta (meth) acrylate, (poly) propoxy Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (poly) caprolactone modified dipentaerythritol hexa (meth) acrylate, (poly Ethoxylated modified dipentaerythritol hexa(meth) acrylate, (poly) propoxy modified dipentaerythritol hexa(meth) acrylate, polypentaerythritol poly(methyl) Acrylate, trimethylolpropane tri(meth)acrylate, (poly)ethoxy modified trimethylolpropane (Meth)acrylate, (poly)propoxy modified trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate and glycerol tri(meth)acrylate Polyfunctional (meth) acrylate such as polyhydric alcohol; phosphorus-containing polyfunctional (meth) acrylate such as tris(meth) acrylate; trimethylolpropane benzoate (meth) acrylate Aromatic polyfunctional (meth) acrylate; 2, 2, 2 gin An acid-modified polyfunctional (meth) acrylate such as ethenyloxymethyl succinic acid; a polyfunctional (meth) acrylate having a polyfluorene skeleton such as polyoxyhexa(hexa) acrylate or the like .

The urethane (meth) acrylate may, for example, be a diol compound or a polyester diol of a reaction product of the diol compound with a dibasic acid or an anhydride thereof, and an organic polymer. The isocyanate is reacted, and then a reaction product of a hydroxyl group-containing (meth) acrylate is added.

The diol compound may, for example, be 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 glycol, polypropylene glycol, bisphenol A Polyethoxy diol, bisphenol A polypropoxy diol, and the like.

The dibasic acid or an acid anhydride thereof may, for example, be a dibasic acid such as succinic acid, adipic acid, sebacic acid, dimer acid, isophthalic acid, terephthalic acid or phthalic acid; or These acid anhydrides and the like.

In the case of the above organic polyisocyanate, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexa Chain-like saturated hydrocarbon isocyanate such as methyl diisocyanate; isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, methylene bis(4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, a cyclic saturated hydrocarbon isocyanate such as hydrogenated xylene diisocyanate or hydrogenated toluene diisocyanate; 2,4-tolyl diisocyanate, 1,3-xylylene diisocyanate, p-phenylene diisocyanate, 3,3'- Dimethyl-4,4'-diisocyanate, 6-isopropyl-1,3-phenyldiisocyanate An aromatic polyisocyanate such as an acid ester or a 1,5-naphthalene diisocyanate.

The polyester (meth) acrylate may, for example, be a polyester diol of a reaction product of a diol compound with a dibasic acid or an acid anhydride thereof, or a reaction product of (meth)acrylic acid.

Among them, a (meth) acrylate which is used in the resin composition of the present invention can be suitably used as a material having a low curing shrinkage ratio. Specifically, a (meth) acrylate having a ring structure is preferred, isodecyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, (methyl) Dicyclopentenyloxyethyl acrylate, cyclohexyl (meth)acrylate, p-cumylphenol (poly)ethoxy (meth) acrylate, naphthol (poly) ethoxy (A) Acrylate, naphthol (poly)propoxy (meth) acrylate, phenylphenol (poly) ethoxy (meth) acrylate, phenyl phenol (poly) propoxy (meth) acrylate Ester, benzyl (meth)acrylate, tricyclodecane dimethanol (meth) acrylate, hydrogen pentanal modified trimethylolpropane di(meth) acrylate and biphenyl dimethanol di(a) Base) acrylate and the like. Particularly preferred is a phenylphenol (poly)ethoxy (meth) acrylate, a tricyclodecane dimethanol (meth) acrylate, and a hydropivalaldehyde modified three having a high Tg and a low hardening shrinkage of the cured product. Hydroxymethylpropane di(meth)acrylate and biphenyldimethanol di(meth)acrylate.

Further, when the above-mentioned (meth) acrylate of the other component is used in the resin composition of the present invention, it may be used singly or in combination of plural kinds. When the (meth) acrylate is used in the resin composition of the present invention, the amount of the compound is preferably 10 to 200 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B). It is preferably 50 to 150 parts by mass.

Further, in the resin composition of the present invention, when the above (meth) acrylate is used, photopolymerization initiation other than the above photocationic polymerization initiator is used. The agent is preferred.

The photopolymerization initiator other than the photocationic polymerization initiator may, for example, be a benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether or benzoin isobutyl ether; acetophenone, 2, 2-Diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl -Phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl Propane-1-one and acetophenone such as oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone]; 2-ethyl hydrazine, 2 - anthracene such as tert-butyl hydrazine, 2-chloroindole and 2-pentyl hydrazine; 2,4-diethyl thianonanone, 2-isopropyl thioxanthone and 2-chloro Thiol ketones such as thioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; diphenyl ketone, 4-benzylidene-4'-methyl Diphenyl ketones and diphenyl ketones such as 4,4'-bismethylaminodiphenyl ketone; 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis (2, 4,6-trimethylbenzimidyl)-phenylphosphine oxide and diphenyl-(2,4 , 6-trimethyl benzhydryl) phosphine oxides such as phosphine oxides, and the like. The photopolymerization initiator other than the photocationic polymerization initiator is preferably an acetophenone, more preferably, for example, 2-hydroxy-2-methyl-phenylpropan-1-one and a 1-hydroxyl ring. Hexyl-phenyl ketone. When a photopolymerization initiator is used in the resin composition of the present invention, it is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the (meth) acrylate component. More preferably, it is 1 to 5 parts by mass. Further, in the resin composition of the present invention, the photopolymerization initiator may be used singly or in combination of plural kinds.

The ratio of use of each component of the resin composition of the present invention is determined in consideration of a desired refractive index, durability, viscosity, or adhesion. When the total amount of the component (A) and the component (B) is 100 parts by mass, the content of the component (A) is 20 to 80 parts by mass, preferably 30 to 70 parts by mass, and the content of the component (B) is 20 Up to 80 quality It is preferably 30 to 70 parts by mass. The content of the component (C) at this time is usually from 0.05 to 5 parts by mass, preferably from 0.1 to 3 parts by mass, based on the photocationic polymerization initiator or the thermal cationic polymerization initiator.

With respect to the total amount of the resin composition of the present invention, generally, the total amount of the component (A) and the component (B) is preferably from 50 to 99% by mass, more preferably from 70 to 99% by mass, most preferably from 80 to 8%. 99% by mass, as the case may be, may be 90 to 99% by mass, and more preferably 95 to 99% by mass. The remainder is the above component (C) and any optional components.

In the resin composition of the present invention, in addition to the above-mentioned components, in order to improve the convenience during handling, etc., a release agent, an antifoaming agent, a leveling agent, a light stabilizer, an antioxidant, and a polymerization inhibitor may be combined depending on the situation. Other additives such as plasticizers and antistatic agents.

In the resin composition of the present invention, a plasticizer may be used in order to obtain durability or flexibility. The material of the plasticizer to be used can be selected depending on 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 ethylphthalylethyl glycolate and butylphthalylbutyl glycolate; and trimellitic acid ginseng (2-ethylhexyl) ester Triphenyl ester; dibutyl adipate, diisobutyl adipate, bis(2-ethylhexyl) adipate, diisononyl adipate, diisononyl adipate, Bis(2-(2-butoxyethoxy)ethyl) dicarboxylate, bis(2-ethylhexyl) sebacate, dibutyl sebacate, di(2-ethyl) sebacate Aliphatic dibasic acid such as hexyl ester and diethyl succinate Ester; trimethyl phosphate, triethyl phosphate, tributyl phosphate, gin (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, tris(dimethylphenyl) phosphate Ethyl phosphate such as ester, cresyl diphenyl phosphate and 2-ethylhexyl diphenyl phosphate; ricinoleate such as methyl ethyl ricinoleate; poly(1,3 butanediol) Polyester such as hexanoate); acetate such as glyceryl triacetate; sulfonamide such as N-butylbenzenesulfonamide; polyethylene glycol benzoate, polyethylene glycol dibenzoate Polypropylene oxide (di)benzoate such as polypropylene glycol benzoate, polypropylene glycol dibenzoate, polybutylene glycol benzoate and polybutylene glycol benzoate; polypropylene glycol, polyethylene Polyether such as diol and polybutylene glycol; polyalkoxy modified bisphenol A and polypropoxy modified bisphenol A and other polyalkoxy modified bisphenol A; polyethoxy modified bisphenol F and Polypropoxy modified bisphenol F such as polypropoxy modified bisphenol F; polycyclic aromatic hydrocarbons such as naphthalene, phenanthrene and anthracene; (bin) naphthol, (poly)ethoxy modified (bi) naphthol , (poly) propoxy modified (linked) naphthol, (poly) butanediol modified (linked) naphthol and (poly) Lactone modified naphthol derivatives such as naphthol; diphenyl sulfide, diphenyl polysulfide, benzothiazolyl disulfide, diphenylthiourea, morpholinyl dithiobenzothiazole , cyclohexylbenzothiazole-2-sulfenylamine, tetramethylthiuram disulfide disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, hydrazine A sulfur-containing compound such as (2-ethylhexyl)thiuram disulfide, tetramethylthiuram monosulfide, and dipentamethylene thiuram tetrasulfide. Preferred plasticizers are, for example, (poly)ethylene glycol dibenzoate, (poly)propylene glycol dibenzoate, binaphthol, (poly)ethoxy modified (bi)naphthol, (Poly)propoxy modified (linked) naphthol and diphenyl sulfide.

In the resin composition of the present invention, a coupling agent may be added for the purpose of improving the adhesion. The coupling agent to be used is not particularly limited, but is preferably a decane coupling agent.

The decane coupling agent may, for example, be 3-glycidoxypropyltrimethoxydecane, 3- Glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy矽, N-phenyl-γ-aminopropyltrimethoxydecane, N-(2-aminoethyl) 3-aminopropylmethyldimethoxydecane, N-(2-Amino B 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-thiolpropyltrimethoxydecane, vinyltrimethoxydecane, N-(2-( Vinylbenzylamino)ethyl)3-aminopropyltrimethoxydecane hydrochloride, 3-methylpropenyloxypropyltrimethoxydecane, 3-chloropropylmethyldimethoxy Alkane, 3-chloropropyltrimethoxydecane, and the like.

Examples of the coupling agent other than the decane coupling agent include isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearate titanate, and titanium bis(dioctyl). Pyrophosphate) oxyacetate, tetraisopropylbis(dioctylphosphite) titanate, neoalkoxytris(p-N-(β-aminoethyl)aminophenyl) Titanium coupling agent such as titanate; Zr-acetamidineacetone, Zr-methacrylate, Zr-propionate, neoalkoxy zirconate, neoalkoxytrisinyl zirconate, new Alkoxy stilbene (dodecyl decyl) benzene sulfonyl zirconate, neoalkoxy (ethylidene diamine ethyl) zirconate, neoalkoxy (m-aminophenyl) Zirconium or aluminum coupling agents such as zirconate, ammonium zirconium carbonate, Al-acetonitrile, Al-methacrylate, and Al-propionate.

These coupling agents may be used singly or in combination of two or more. Among these coupling agents, a decane coupling agent is preferred, and an amine decane coupling agent or an epoxy decane coupling agent is more preferred. By using a coupling agent, it is possible to obtain a sealing material which is excellent in moisture resistance reliability and which has little reduction in adhesion strength after moisture absorption. The content of the resin composition of the present invention when the coupling agent is used is about 0.05 to 3 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, it may be further added as needed A polymer such as an acrylic polymer, a polyester elastomer, an amine ester polymer or a nitrile rubber is added. For the component having no reactive group, the weight average molecular weight is preferably 10,000 g/mol from the point of compatibility. Further, in order to reduce the water vapor permeability, an organometallic compound such as an aluminum alkyl may be added. A solvent may also be added, but it is preferred to add no solvent.

The resin composition of the present invention is preferably a resin composition containing a weight average molecular weight of each component of 10,000 g/mol or less, more preferably 5,000 g/mol or less. Since the component having a large weight average molecular weight is not dissolved with other components, the prepared resin composition becomes a turbid liquid. This is not suitable because the uniformity of the resin composition used in the display is indispensable.

Further, the resin composition of the present invention is intended to have properties excellent in transmittance. Specifically, when the resin composition of the present invention is cured to form a cured product having a thickness of 100 μm , the light transmittance of each of the wavelengths of the cured product having a 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-Tech Co., Ltd.

The resin composition of the present invention can be prepared by mixing and dissolving each component according to a general method. For example, each component can be placed in a round bottom flask equipped with a stirring device and a thermometer, and stirred at 40 to 80 ° C for 0.5 to 6 hours.

The viscosity of the resin composition of the present invention is preferably a workability which is suitable for workability at the time of production of a display or the like, and is particularly suitable for a surface mount of an organic EL element. The organic EL element is generally surrounded by a barrier material, and a metal electrode (lower electrode), an organic EL layer containing at least an organic light-emitting layer, and an ITO electrode (upper electrode) are sequentially laminated on the substrate such as glass. And a protective film, which is filled with a film (resin composition for surface encapsulation) on the protective film, on which The structure of a package substrate package such as glass. This film is embedded in the space between the substrate on the metal electrode side and the package substrate on the opposite side, and the organic light-emitting layer is protected from external moisture or the like, and a general curable resin composition can be used. After filling the film material of the curable resin composition, a package substrate such as glass is placed thereon, and the resin composition is cured to encapsulate the organic light-emitting layer. The resin composition used as the film material is a resin composition for surface encapsulation. Therefore, the resin composition for the surface encapsulation is preferably low in viscosity in order to completely enclose the space between the substrates.

The viscosity of the resin composition for surface encapsulation of the organic EL device of the present invention is preferably 15 Pa using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. Below s, more preferably 3500mPa. Below s, the best is 1000mPa. Below s, especially good for 500mPa. Below s, the most excellent is 300mPa. s below. The lower limit of the viscosity is not particularly limited, but is 50 mPa. s or so.

In the present invention, a resin composition containing a hardener which initiates a hardening reaction by an energy ray as a curing agent (C) can be easily hardened by an energy ray. Here, specific examples of the energy ray include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays (γ-rays), and laser rays; α-rays, β-rays, and electron beams; Particle lines and so on. In the present invention, among these, ultraviolet rays, laser rays, visible rays or electron rays are preferable.

According to a general method, the cured product of the present invention can be obtained by irradiating the resin composition of the present invention with the aforementioned energy ray. The resin composition of the present invention has a liquid refractive index of usually from 1.45 to 1.70, preferably from 1.50 to 1.65. The refractive index can be measured by an Abbe refractometer (model: DR-M2, manufactured by ATAGO Co., Ltd.).

Further, the resin composition of the present invention is preferably a small shrinkage ratio (hardening shrinkage ratio) at the time of curing, more preferably 5% or less, most preferably 4% or less, and particularly preferably 3.5% or less.

Further, in the cured product of the resin composition of the present invention, in order to protect the organic light-emitting layer from external moisture or the like, the water vapor permeability is preferably 45 g/m ² . It is 24 hours (measured at 60 ° C, humidity 90%, the same below), and more preferably 35 g/m ² . Below 24h.

Further, the glass transition temperature (Tg) of the cured product is preferably a certain degree. In the resin composition of the present invention, the Tg is preferably 80 ° C or higher, more preferably 90 ° C or higher, and most preferably 100. Above °C.

Preferred embodiments of the resin composition of the present invention are exemplified below.

(I) A resin composition comprising a resin composition for surface encapsulation of an organic EL device comprising an alicyclic compound (A), a cyclic compound (B) and a curing agent (C); and the component (A) is selected a skeleton of the group of the above (A-1), and a compound of an epoxy group or an oxetanyl group; the component (B) is an aliphatic ring skeleton having a group selected from the above (B-1) or the foregoing ( The heterocyclic skeleton of the group described in B-3) and the compound of an epoxy group or an oxetanyl group have a structure different from the compound used as the component (A).

(II) The resin composition of the above (I), wherein the component (A) is a compound having a skeleton selected from the group (A-2) and an epoxy group or an oxetane group.

(III) The resin composition of the above (I) or (II), wherein the component (A) is an alicyclic epoxy compound or an oxetane compound or ring having a hydrogenated bisphenol A skeleton or a tricyclodecane skeleton An oxygen compound or an alicyclic epoxy compound having a cyclohexane skeleton in which an epoxy group is formed.

(IV) The resin composition according to any one of the above (I) to (III), wherein the component (A) contains an epoxy compound having a tricyclodecane skeleton or an alicyclic epoxy compound having a cyclohexane skeleton. .

(V) The resin composition according to any one of the above (I) to (IV) wherein the component (A) contains a bicyclic ring Pentadiene dimethanol diglycidyl ether or 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate.

(VI) The resin composition according to any one of the above (1) to (V), wherein the component (B) is an aliphatic ring skeleton having a group selected from the above (B-2) or the aforementioned (B-4) a compound of a heterocyclic skeleton of a group.

(VII) The resin composition according to any one of the above (1) to (VI), wherein the component (B) contains an alicyclic epoxy compound, or has a tricyclodecane skeleton, an adamantane skeleton or isomeric cyanide An epoxy compound of an acid ester backbone.

(B) The resin composition according to any one of the above (1) to (VII), wherein the component (B) contains a component selected from the group consisting of (b-1a), (b-1b) and (b-1c) above. Group of alicyclic epoxy compounds.

(IX) The resin composition according to any one of the above (I) to (VIII), wherein the component (B) contains an alicyclic epoxy compound having a cyclohexane skeleton.

(X) The resin composition according to any one of the above (I) to (IX), wherein the compound contained as the component (A) or the component (B) is a bifunctional oxetane compound or a 2-functional compound Epoxy compound.

(XI) The resin composition according to any one of the above (1) to (X) wherein the component (A) contains dicyclopentadiene dimethanol diepoxypropyl ether, and the component (B) contains 3, 4 - Epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate.

(XII) The resin composition according to any one of the above (I) to (XI), wherein the hardener (C) is a photocationic polymerization initiator or a thermal cationic polymerization initiator.

(XIII) The resin composition according to any one of the above (I) to (XII), wherein the curing agent (C) is a photocationic polymerization initiator selected from the group of the above (C-1).

(XIV) The resin composition according to any one of the above (I) to (XIII), wherein the hardener (C) is ruthenium salt.

(XV) The resin composition of any one of the above (I) to (XIV), wherein the resin composition has a viscosity of 1000 mPa. Below s, preferably 500 mPa. Below s, more preferably 300mPa. s below.

(XVI) The resin composition according to any one of the above (1) to (XV), wherein the resin composition is cured to form a cured product having a thickness of 100 μm , and the hardening is measured at 60 ° C and a relative humidity of 90%. The moisture permeability (water vapor permeability) of the material was 45 g/m ² . Below 24hr.

(XVII) The resin composition according to any one of the above (I) to (XVI), wherein the cured product of the resin composition has a glass transition temperature (Tg) of 80 ° C or more, more preferably 100 ° C or more.

(XVIII) The resin composition according to any one of the above (I) to (XVII), wherein the curing shrinkage ratio is 4% or less.

(XIX) The resin composition according to any one of the above (I) to (XVIII), wherein the resin composition has a liquid refractive index of from 1.54 to 1.7.

(XX) The resin composition according to any one of the above (I) to (XIX), wherein the content of the component (A) is 20 to 80 by mass based on 100 parts by mass of the total of the component (A) and the component (B) The content of the component (B) is 20 to 80 parts by mass, and the content of the curing agent (C) is 0.05 to 5 parts by mass.

According to the solid-state sealing method of the organic EL device of the present invention, the method further comprises the steps of: forming a protective film on the organic EL element formed on the substrate; applying a resin composition for surface encapsulation on the protective film, and providing a transparent package And a step of curing the resin composition for surface encapsulation; and using the curable resin composition according to the present invention as the resin composition for the surface encapsulation.

The organic EL device to be surface-sealed includes a substrate, an organic EL layer including a lower electrode, at least a light-emitting layer, and an element portion of the upper electrode. Body composition. In the substrate, a glass substrate, a transparent organic material made of a cycloolefin, a polycarbonate, or a polymethyl methacrylate, or an electrically insulating substance such as an organic/inorganic hybrid transparent substrate having a high hardness such as glass fiber is used. A flat substrate is constructed. Further, the representative configuration of the element body is, for example, the following.

(1) Lower electrode / luminescent layer / upper electrode

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

(3) Lower electrode / luminescent layer / hole 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 form a lower electrode (cathode) composed of an Al-Li alloy or the like by a resistance heating vapor deposition method or a sputtering method on one surface of the substrate. And then sequentially laminating by thin film formation methods such as resistance heating evaporation or ion beam sputtering Electron transport layer composed of oxadiazole derivative, triazole derivative, etc., luminescent layer, TPD (N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1- It is produced by a hole transport layer composed of a biphenyl-4,4'-diamine or the like and an upper electrode (anode) organic EL layer. In addition, the layer structure or material of the organic EL element is not particularly limited as long as it can function as a display element. Further, the solid packaging method of the present invention can be applied even to any organic EL device having a structure.

The protective film is formed to cover the organic EL element. The protective film can be formed by forming an inorganic material such as tantalum nitride or hafnium oxide by a method such as vapor deposition or sputtering. The protective film is provided to prevent penetration of moisture, impurities, or the like into the organic EL element. The thickness of the protective film is preferably in the range of 10 nm to 100 μm , and more preferably in the range of 100 nm to 10 μm . The protective film system can also be laminated for the purpose of improving reliability.

The protective film system is also determined by the film forming method, and is generally an incomplete film in which pinholes are present, and is often a film having weak mechanical strength. Therefore, the solid packaging method is based on a protective film. The adhesive is applied to the upper surface, and the transparent substrate for encapsulation is used to pressurize the adhesive to harden the adhesive, thereby improving the reliability of the package.

[Examples]

Then, the present invention will be described in more detail by way of examples. The present invention is not limited by the following examples. Furthermore, the unit "part" of the numerical value means a part by mass.

The resin composition of the present invention having the composition shown in the following Table 1, the resin composition of Comparative Example 1, and the resin composition of Reference Example 1 were produced, and a cured product of each resin composition was obtained by the following method. The obtained resin composition and cured product (cured film) were evaluated by the following evaluation methods and evaluation criteria.

(1) Viscosity: The viscosity (unit: mPa.s) of each resin composition shown in the following Table 1 at 25 ° C was measured using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.).

(2) Liquid Refractive Index: The refractive index (25 ° C) of each of the resin compositions described in Table 1 below was measured by an Abbe refractometer (DR-M2; manufactured by ATAGO Co., Ltd.).

(3) Water vapor permeability: Each resin composition described in the following Table 1 was sandwiched between glass substrates, and a film thickness was adjusted using a spacer of 100 μm . Then, the resin compositions of Example 1, Example 2, Comparative Example 1, and Reference Example 1 were irradiated with ultraviolet rays having an integrated irradiation amount of 3000 mJ/cm ² in a high pressure mercury lamp (80 W/cm, no ozone). The resin composition of Example 3 was cured by heating at 100 ° C for 1 hour to prepare a test piece. For the obtained test piece, a Lyssy water vapor permeability meter L80-5000 (manufactured by Systech Illinois Co., Ltd.) was used to measure the moisture permeability in an environment of 60 ° C and 90% RH (unit: g/m ^{2 )} .24hr).

(4) Tg (glass transition temperature): hardening in the same manner as in the above (3) The Tg point of the obtained cured product was measured by a viscoelasticity measuring system EXSTAR DMS-6000 (manufactured by SII Nanotechnology Co., Ltd.), a tensile mode, and a frequency of 1 Hz.

(5) Curing shrinkage ratio: A resin layer composed of each of the resin compositions described in Table 1 below was applied to a substrate. Then, the resin compositions of Example 1, Example 2, Comparative Example 1, and Reference Example 1 were irradiated with ultraviolet rays having an integrated irradiation amount of 3000 mJ/cm ² by a high pressure mercury lamp (80 W/cm, no ozone). The resin composition of Example 3 was cured by heating in a drier at 100 ° C for 1 hour to cure the resin composition, thereby producing a cured product for measuring the specific gravity of the film. Further, the specific gravity (DS) of the cured product was measured in accordance with JIS K7112 B. Further, the specific gravity (DL) of the resin composition was measured at 23 ± 2 ° C, and the curing shrinkage ratio was calculated from the following formula. The measurement results are expressed as the average of the results of the four measurements.

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

(6) Light penetration rate

In the same manner as in the above (3), the resin compositions of Examples 1 to 3 were cured to prepare a test piece having a film thickness of 100 μm . For each of the obtained test pieces, a light transmittance (%) of each wavelength of a wavelength of 380 to 780 nm was measured using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, product name: U-3900H). The light transmittance of the cured film (film thickness: 100 μm) of the resin compositions of Examples 1 to 3 was 90% or more in any of the above wavelengths.

EP-4088S: ADEKA AG, dicyclopentadiene dimethanol diepoxypropyl ether

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

OXT-121: Dimethylphenyl dioxetane manufactured by East Asia Synthetic Co., Ltd.

MA-DGIC: monoallyl digoxypropyl isomeric cyanurate manufactured by Shikoku Chemical Industry Co., Ltd.

GSID 26-1: [4-(4-Ethylphenylsulfonyl)phenyl]indole [(trifluoromethyl)sulfonyl] methanide, manufactured by BASF.

SUNAID SI-100 main agent: benzylmethyl-p-hydroxyphenyl hexafluoroantimonate manufactured by Sanshin Chemical Industry Co., Ltd.

EPOLIGHT 80MF: glycerol diepoxypropyl ether produced by Kyoeisha Chemical Co., Ltd.

EPOLIGHT 100MF: Trimethylolpropane triepoxypropyl ether, manufactured by Kyoeisha Chemical Co., Ltd.

From the evaluation results of Examples 1 to 3, Reference Example 1, and Comparative Example 1, it was found that the cured product obtained from the resin composition of the present invention having a specific composition had high Tg, low hardening shrinkage, and low water vapor permeability. . Therefore, the cured product obtained from the resin composition of the present invention is suitable for, for example, a coating agent for a barrier film, or a surface encapsulating material of various encapsulating materials, particularly an organic EL element.

[Industry use possibility]

The resin composition and the cured product of the present invention are excellent in visible light transmittance and light resistance, have high Tg, low curing shrinkage ratio, and low water vapor transmission rate, and are therefore suitable for various packaging materials, and are particularly suitable for the surface of organic EL elements. Packaging material.

Claims (19)

A resin composition for surface encapsulation of an organic EL device, which comprises an alicyclic compound (A) having an oxetanyl group or an epoxy group, and an oxetane group or an epoxy group a cyclic compound (B) which satisfies the following conditions; the condition of the cyclic compound (B): the ring of the cyclic compound (B) is an aliphatic ring or a heterocyclic ring, and when the ring is an aliphatic ring, The cyclic compound is a compound having a structure different from that of the compound used as the alicyclic compound (A). The resin composition according to claim 1, wherein the alicyclic compound (A) is a skeleton having a group selected from the group consisting of the following (A-1); A-1: tricyclodecane, isoindole Base, adamantane, cyclopentane, cyclohexane, hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S. The resin composition according to claim 1 or 2, wherein the alicyclic compound (A) has a group selected from the group consisting of tricyclodecane, adamantane, cyclohexane and hydrogenated bisphenol A. The skeleton serves as an oxetane compound or an epoxy compound of an aliphatic ring. The resin composition according to any one of claims 1 to 3, wherein the cyclic compound (B) has a skeleton selected from the group (B-1) below; B-1: three Cyclodecane, isodecyl, adamantane, cyclopentane, cyclohexane, hydrogenated bisphenol A, hydrogenated bisphenol F, and hydrogenated bisphenol S. The resin composition according to claim 4, wherein the cyclic compound (B) is a skeleton having a group selected from the group consisting of tricyclodecane, adamantane, cyclohexane, and hydrogenated bisphenol A as a fat. a cyclized oxetane compound or an epoxy compound. The resin composition according to any one of claims 1 to 3, wherein the cyclic compound (B) has a skeleton selected from the group (B-3) below; B-3: Porphyrin, tetrahydrofuran, Alkane, two Alkane, three (triazine), carbazole, pyrrolidine, and piperididine. The resin composition according to claim 6, wherein the cyclic compound (B) is selected from the group consisting of Alkane, two Alkane and three The skeleton of the resulting group serves as a heterocyclic epoxy compound. The resin composition according to any one of claims 1 to 7, which further contains a hardener (C). The resin composition according to claim 8, wherein the hardener (C) is a photocationic polymerization initiator. The resin composition according to claim 9, wherein the photocationic polymerization initiator is a compound selected from the group consisting of the following (C-1); C-1: a phosphonium salt, a phosphonium salt, a phosphonium salt, Ammonium salts and citrates. The resin composition according to claim 8, wherein the curing agent (C) is a thermal curing agent, and the resin composition is a thermosetting resin composition. The resin composition according to claim 11, wherein the thermosetting agent is a compound selected from the group consisting of the following (C-2); and C-2: an amine compound, an acid anhydride compound, and a guanamine compound. A phenolic compound, a carboxylic acid compound, an imidazole compound, an isomeric cyanuric acid addition product, a metal compound, a phosphonium salt, an ammonium salt, a cerium salt, a phosphonium salt, and a microcapsule-type curing agent. The resin composition according to any one of claims 1 to 12, wherein the resin composition contains 20 parts by mass based on 100 parts by mass of the total of the alicyclic compound (A) and the cyclic compound (B). Up to 80 parts by mass of the aforementioned alicyclic compound (A). The resin composition according to any one of claims 1 to 13, wherein the resin composition contains 20 parts by mass based on 100 parts by mass of the total of the alicyclic compound (A) and the cyclic compound (B). Up to 80 parts by mass of the aforementioned cyclic compound (B). The resin composition according to any one of claims 1 to 14, wherein the resin composition contains 0.1 part by mass based on 100 parts by mass of the total of the alicyclic compound (A) and the cyclic compound (B). Up to 5 parts by mass of the aforementioned hardener (C). The resin composition according to any one of claims 1 to 15, wherein the viscosity measured at 25 ° C is 15 Pa. s below. An organic electroluminescence (EL) display obtained by surface-sealing a cured product obtained by curing the resin composition according to any one of claims 1 to 16. A film for surface encapsulation of an organic EL display, which has a barrier property by applying a resin composition according to any one of claims 1 to 16 to a substrate and hardening it. A surface-encapsulation of an organic EL display, which uses the resin composition according to any one of claims 1 to 16.