TW202018052A - Composition for material of moisture-proof seal - Google Patents

Abstract

The purpose of the present invention is to provide a composition for moistureproof sealing materials which has excellent photocurability and gives cured objects excellent in terms of moistureproofness and stretachability. A composition for moistureproof sealing materials which comprises (a) at least one isocyanuric-acid-based epoxy compound selected from the group consisting of compounds represented by formula [1] and compounds represented by formula [2], (b) a polyfunctional epoxy compound having no isocyanuric acid skeleton, (c) a polyfunctional oxetane compound, and (d) a polymerization initiator which generates an acid or a base upon irradiation with actinic rays. (In formula [1], R1 represents a hydrogen atom or a methyl group and L1 represents a C2-7 alkylene group; the R1 moieties may be the same or different and the L1 moieties may be the same or different.) (In formula [2], R2 represents a hydrogen atom or a methyl group, L2 represents a C1-5 alkylene group, A represents an (n+1)-valent aliphatic hydrocarbon group optionally containing an ether bond, and n is an integer of 2-5; the R2 moieties may be the same or different, the L2 moieties may be the same or different, the A moieties may be the same or different, and the n's may be the same or different.).

Description

Composition for moisture-proof sealing material

The present invention relates to a composition for a moisture-proof sealing material, a cured product obtained therefrom, and an organic EL display obtained by mounting the cured product.

In recent years, in the electrical and electronic industries, development and manufacturing of flat panel displays (FPD) using various display elements are being carried out. Most of these displays are formed by encapsulating display elements in flat units including glass or plastic. As a representative example thereof, a liquid crystal display (LCD), an electroluminescence display (ELD), electronic paper, etc. may be mentioned.

Among these, EL displays (especially organic EL displays) are excellent in characteristics such as high brightness, high efficiency, and high-speed response in addition to the high viewing angle and high contrast unique to natural light, so It is attracting attention as a new generation of flat panel displays. In addition, since the electrodes and the light-emitting layer are very thin films, the possibility of forming them on a plastic substrate for flexible displays or large-scale planar lighting has also been studied.

The organic EL device generates light by re-bonding electrons injected into the light-emitting layer and holes injected into the light-emitting layer, and the aforementioned electrons come from the electron injection electrode and are injected directly or through the electron transport layer. For the light-emitting layer, the aforementioned holes come from the hole injection electrode and are injected into the light-emitting layer directly or through the hole transport layer. An organic EL element based on such a light-emitting mechanism uses a very active and chemically unstable alloy as the electrode system. Therefore, it is susceptible to corrosion and oxidation due to moisture or oxygen from the outside, so it was found that the formation of non-luminous parts called dark spots and their significant increase, and the decrease in brightness over time. Furthermore, since organic materials are used for the light-emitting layer or the charge transport layer of the organic EL element, they are susceptible to deterioration due to moisture or oxygen. Therefore, there is also a problem that the formation of dark spots or the reduction of brightness is caused.

Therefore, when manufacturing a practical organic EL element, in order to prevent moisture or oxygen from entering the organic material or the electrode material, the element needs to be effectively encapsulated (sealed). As a packaging method of FPD, a method of using a thermosetting epoxy resin has been used in the packaging of LCDs in the past, but such a thermosetting epoxy resin needs to be heated at a so-called high temperature of 150 to 180°C In about 2 hours, there is a problem that the productivity cannot be improved. Furthermore, organic EL elements are excellent in characteristics such as high brightness, high efficiency, and high-speed responsiveness. On the other hand, the heat resistance is low, and the heat resistance temperature is generally about 80 to 100°C. Therefore, in the sealing of an organic EL display, even if a thermosetting epoxy resin is used, there is a problem that it cannot be sufficiently cured by heating.

In order to solve these problems, the development of light-curing sealing materials capable of rapid hardening at low temperature is being attempted. As the light-curing sealing material, there are generally a light radical-curing sealing material and a photo-cation-curing sealing material. As the light radical hardening type sealing material, acrylic resin can be mainly used. On the other hand, as the photo-cation-curable sealing material, epoxy resins (for example, Patent Documents 1 and 2) can be mainly used. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 11-224771 [Patent Document 2] Japanese Patent Laid-Open No. 2014-105286

[Problems to be solved by the invention]

The above-mentioned acrylic resin has the advantage that various acrylate monomers and oligomers can be used, but in general, moisture resistance is insufficient, and it also has the problems of so-called large curing shrinkage and insufficient adhesion. So far there is no material that can meet the performance. In addition, the above-mentioned epoxy resin generally has relatively good adhesiveness, but lacks photocurability such as photosensitivity and rapid curing, and usually has a problem in terms of so-called hardness and brittleness. Furthermore, in recent years, the development of flexible displays such as rollable or foldable has also prevailed, so not only photocurability but also sealing materials with high mechanical properties (especially extensibility) after curing are required. . However, in the technique described in the above-mentioned Patent Document 1, a compound having a hydroxyl group is blended in order to improve the photocationic curability, and a high molecular weight polymer cannot be obtained due to chain transfer due to the hydroxyl group, so it cannot be expected to improve mechanical properties.

Therefore, an object of the present invention is to provide a composition for a moisture-proof sealing material, which can obtain a cured product having excellent photocurability, and further having excellent moisture resistance and extensibility. [Means to solve the problem]

(式中，R¹ 表示氫原子或甲基，L¹ 表示碳原子數2~7的伸烷基，於此，各別的R¹ 可互為相同或相異，各別的L¹ 可互為相同或相異)

(式中，R² 表示氫原子或甲基，L² 表示碳原子數1~5的伸烷基，A表示可包含(n+1)價的醚鍵的脂肪族烴基，n表示2~5的整數，於此，各別的R² 可互為相同或相異，各別的L² 可互為相同或相異，各別的A可互為相同或相異，各別的n可互為相同或相異)。 作為第2觀點係關於如第1觀點之防濕密封材用組成物，其中，前述(b)不具有異三聚氰酸骨架的多官能環氧化合物係選自由雙酚A型環氧樹脂、雙酚F型環氧樹脂、氫化雙酚A型環氧樹脂、氫化雙酚F型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、雙酚F酚醛清漆型環氧樹脂及脂環式聚縮水甘油醚型環氧樹脂所成之群組之至少1種。 作為第3觀點係關於如第2觀點之防濕密封材用組成物，其中，前述(b)不具有異三聚氰酸骨架的多官能環氧化合物係選自由雙酚A二縮水甘油醚、雙酚F二縮水甘油醚、氫化雙酚A二縮水甘油醚、氫化雙酚F二縮水甘油醚、雙酚A酚醛清漆聚縮水甘油醚及二環戊二烯二甲醇二縮水甘油醚所成之群組之至少1種。 作為第4觀點係關於如第3觀點之防濕密封材用組成物，其中，前述(b)不具有異三聚氰酸骨架的多官能環氧化合物為雙酚F二縮水甘油醚。 作為第5觀點係關於如第1觀點至第4觀點中任一項之防濕密封材用組成物，其中，前述(d)藉由活性能量線來產生酸或鹼的聚合起始劑為光酸產生劑。 作為第6觀點係關於如第1觀點至第5觀點中任一項之防濕密封材用組成物，其中，前述(a)異三聚氰酸系環氧化合物為前述式[1]所表示之化合物。 作為第7觀點係關於如第1觀點至第6觀點中任一項之防濕密封材用組成物，其中，將該硬化物依據JIS Z 0208 (1976)的防濕包裝材的透濕度試驗方法的杯模法(cup method)中的條件B(溫度40℃、相對濕度90%)所測定的透濕度，以厚度100μm換算時為20g/m² ·24h以下。 作為第8觀點係關於如第1觀點至第7觀點中任一項之防濕密封材用組成物，其係有機EL顯示器防濕密封材用組成物。 作為第9觀點係關於一種硬化物，其係將第1觀點至第8觀點中任一項之防濕密封材用組成物硬化而成。 作為第10觀點係關於一種有機EL顯示器，其係搭載第9觀點之硬化物。 [發明的效果]In order to solve the above-mentioned problems, the present inventors have conducted intensive studies and found that they contain an isocyanurate-based epoxy compound and a specific polyfunctional epoxy compound and a polyfunctional compound, which are contained in various epoxy resins and have a specific structure. The cured product of the composition of the oxetane compound has moisture resistance, extensibility, and high adhesion to substrates, electrodes, etc., so it is excellent as a moisture-proof sealing material for organic EL elements, for example, and is completed this invention. That is, the first aspect in the present invention relates to a composition for a moisture-proof sealing material, comprising (a) at least one selected from the group consisting of a compound represented by formula [1] and a compound represented by formula [2] 1 type of isocyanuric epoxy compound, (b) polyfunctional epoxy compound without isocyanuric acid skeleton, (c) polyfunctional oxetane compound and (d) by active energy Line to produce acid or alkali polymerization initiators,

(In the formula, R ¹ represents a hydrogen atom or a methyl group, L ¹ represents an alkylene group having 2 to 7 carbon atoms, where each R ¹ may be the same or different from each other, and each L ¹ may be mutually Are the same or different)

(In the formula, R ² represents a hydrogen atom or a methyl group, L ² represents an alkylene group having 1 to 5 carbon atoms, A represents an aliphatic hydrocarbon group which may include a (n+1)-valent ether bond, and n represents 2 to 5 Integer of, here, each R ² may be the same or different from each other, each L ² may be the same or different from each other, each A may be the same or different from each other, each n may be mutually Are the same or different). As a second aspect, the composition for a moisture-proof sealing material according to the first aspect, wherein the (b) polyfunctional epoxy compound having no isocyanuric acid skeleton is selected from bisphenol A type epoxy resin, Bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin and alicyclic poly At least one type of glycidyl ether type epoxy resin. As a third aspect, the composition for a moisture-proof sealing material according to the second aspect, wherein the (b) polyfunctional epoxy compound having no isocyanuric acid skeleton is selected from the group consisting of bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, bisphenol A novolac polyglycidyl ether and dicyclopentadiene dimethanol diglycidyl ether At least one group. The fourth aspect relates to the composition for a moisture-proof sealing material according to the third aspect, wherein the (b) polyfunctional epoxy compound having no isocyanuric acid skeleton is bisphenol F diglycidyl ether. The fifth aspect relates to the composition for a moisture-proof sealing material according to any one of the first aspect to the fourth aspect, wherein the polymerization initiator that generates acid or alkali by active energy ray (d) is light Acid generator. As a sixth aspect, the composition for a moisture-proof sealing material according to any one of the first aspect to the fifth aspect, wherein the (a) isocyanurate-based epoxy compound is represented by the above formula [1] Of compounds. As the seventh viewpoint, it is about the composition for moisture-proof sealing materials as described in any one of the first viewpoint to the sixth viewpoint, in which the moisture permeability test method of the moisture-proof packaging material according to JIS Z 0208 (1976) is applied to the cured product The moisture permeability measured under condition B (temperature 40°C, relative humidity 90%) in the cup method of the present invention is 20 g/m ² ·24h or less when converted to a thickness of 100 μm. As the eighth point, the composition for a moisture-proof sealing material according to any one of the first point to the seventh point is a composition for a moisture-proof sealing material for an organic EL display. The ninth aspect relates to a cured product obtained by curing the composition for moisture-proof sealing material according to any one of the first to eighth aspects. As the tenth aspect, it relates to an organic EL display, which is equipped with the cured product of the ninth aspect. [Effect of invention]

Epoxy resins are excellent in heat resistance, insulation resistance and adhesion. Among them, the isocyanurate-based epoxy compound, which is a feature of the present invention, contains many polar elements, so it has excellent adhesion to various substrates and the like. The alkylene or alkylene and ester linkages between the polycyanic acid skeleton and the epoxy ring are excellent in elongation. By combining with the polyfunctional epoxy compound and polyfunctional oxetane that do not contain the cyanuric acid skeleton The alkane compound hardens and can be a sealing material excellent in adhesion, moisture resistance, and extensibility. In addition, since the epoxy ring and the oxetane ring are highly reactive in the presence of an acid or a base, the use of a polymerization initiator that generates an acid or a base by an active energy ray does not require heating. The reaction can be carried out by irradiation of active energy rays such as light. Therefore, according to the present invention, it is possible to provide a composition for a moisture-proof sealing material, which can obtain a cured product having excellent photocurability, and further having excellent moisture resistance and extensibility. In addition, according to the present invention, curing can be performed by active energy rays, and a cured product having excellent moisture resistance and extensibility can be obtained. Therefore, it can be provided as an organic EL display having low heat resistance and being easily exposed to moisture or moisture. The moisture-proof sealing material of a device deteriorated by oxygen is a useful hardened material (moisture-proof sealing material).

[Best form for carrying out the invention] <Composition for moisture-proof sealing material>

The composition for moisture-proof sealing material of the present invention is, for example, used in an organic EL display as a composition for moisture-proof sealing material for forming a moisture-proof sealing material for effectively encapsulating an organic EL element, which contains the above (a) An isocyanurate-based epoxy compound selected from the compound represented by the formula [1] and the compound represented by the formula [2], (b) a polyfunctional epoxy compound that does not have an isocyanuric skeleton, (c ) A polyfunctional oxetane compound and (d) a polymerization initiator that generates an acid or a base by active energy rays.

[(a) component] <Epoxy compound represented by formula [1]> In the above formula [1], R ¹ represents a hydrogen atom or a methyl group, and L ¹ represents an alkylene group having 2 to 7 carbon atoms, here , Each R ¹ may be the same or different from each other, and each L ¹ may be the same or different from each other. Examples of the alkylene group having 2 to 7 carbon atoms represented by L ¹ include ethylidene group, trimethylene group (trimethylene group), 1-methylidene group, tetramethylene group (tetramethylene group), 1 -Methyltrimethylene, 1,1-dimethylethylene, pentamethylene (pentamethylene group), 1-methyltetramethylene, 2-methyltetramethylene, 1,1-bis Methyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-ethyltrimethylene, hexamethylene group, 1-methylpenta Methylene, 2-methylpentamethylene, 3-methylpentamethylene, 1,1-dimethyltetramethylene, 1,2-dimethyltetramethylene, 2,2- Dimethyltetramethylene, 1-ethyltetramethylene, 1,1,2-trimethyltrimethylene, 1,2,2-trimethyltrimethylene, 1-ethyl-1- Methyltrimethylene, 1-ethyl-2-methyltrimethylene, cyclohexane-1,4-diyl, heptamethylene (heptamethylene group), etc. Among them, trimethylene and hexamethylene are preferred.

上述式中，R¹ 及L¹ 係表示與前述為相同之意思。The compound represented by the above formula [1] can be produced by, for example, the following synthesis method: using isocyanuric acid and an olefin compound having a cleavage group X as starting materials, and known from the past (such as international It is manufactured by the synthesis method of the epoxide disclosed in the specification No. 2010/092947, Japanese Unexamined Patent Publication No. 2012-25688, etc.). Specifically, after isocyanuric acid is reacted with an olefin compound represented by CH ₂ =CR ₁ -L ₁ -X to produce an olefin-substituted isocyanurate (intermediate) having an unsaturated bond, By reacting this compound (intermediate) with peroxide, the epoxy compound represented by the above formula [1] can be produced. As an example, the synthesis flowchart is shown below. In addition, the leaving group X is not particularly limited as long as it can react with the NH group of isocyanuric acid, and examples thereof include a hydroxyl group, mesylate, trifluoromethanesulfonyloxy, and tosylate. Oxygen, nifedisulfonyloxy, ethoxy, trifluoroethoxy, halogen atoms, etc.

In the above formula, R ¹ and L ¹ represent the same meaning as described above.

Examples of the epoxy compound include ginseng (3,4-epoxybutyl) isocyanurate, ginseng (4,5-epoxypentyl) isocyanurate, ginseng (5 , 6-epoxyhexyl) isocyanurate, ginseng (6,7-epoxyheptyl) isocyanurate, ginseng (7,8-epoxyoctyl) isocyanurate Ester, ginseng (8,9-epoxynonyl) isocyanurate, etc. Moreover, the said epoxy compound system can use a commercial item suitably, for example, TEPIC (registered trademark)-VL, the same FL [all are Nissan Chemical Co., Ltd.], etc. are mentioned. These epoxy compounds may be used alone or in a mixture of two or more.

<Compound represented by formula [2]> In the above formula [2], R ² represents a hydrogen atom or a methyl group, L ² represents an alkylene group having 1 to 5 carbon atoms, and A represents that (n+1) valence may be included Aliphatic hydrocarbon group of ether bond of n, n represents an integer of 2~5, here, each R ² may be the same or different from each other, each L ² may be the same or different from each other, each A may They are the same or different from each other, and each n can be the same or different from each other. Examples of the alkylene group having 1 to 5 carbon atoms represented by L ² include methylene group, ethylidene group, trimethylene group, methylethylidene group, tetramethylene group, and 1-methyl group. Trimethylene, 2-methyltrimethylene, 1,1-dimethylethylene, pentamethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1 -Dimethyltrimethylene, 1,2-dimethyltrimethylene, 2,2-dimethyltrimethylene, 1-ethyltrimethylene, etc. Among them, ethylidene is preferred.

Examples of the aliphatic hydrocarbon group represented by A which may include a (n+1)-valent ether bond include, for example, those derived by removing (n+1) hydrogen atoms from an aliphatic hydrocarbon having 1 to 10 carbon atoms (n+1) valence base. In addition, these groups may include an ether bond (-O-) between any carbon-carbon bonds. Examples of the aliphatic hydrocarbons having 1 to 10 carbon atoms include methane, ethane, propane, cyclopropane, butane, isobutane, cyclobutane, pentane, isopentane, neopentane, and cyclopentane. Alkane, hexane, isohexane, neohexane, diisopropyl, cyclohexane, heptane, octane, 2-ethylhexane, nonane, decane, adamantane, etc. Specifically, it can be selected from, for example, glycerin, diglycerin, triglycerin, 2-hydroxy-1,4-butanediol, trimethylolmethane, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, bis (trimethylolpropane), pentaerythritol and dipentaerythritol in the group of polyols to remove the hydroxyl group derived (n+1) valent groups. Among them, a trivalent group derived from 1,1,1-trimethylolpropane by removing a hydroxyl group is preferred.

The compound represented by the above formula [2] can be produced by, for example, the following synthesis method: an olefin compound having ginseng (carboxyalkyl) ester of isocyanurate and a group Y and an ether bond that reacts with a carboxyl group As a starting material, it is manufactured by a conventionally well-known (for example, described in International Publication No. 2012/128325 specification, etc.) epoxide synthesis method.

上述式中，R² 、L² 及A係表示與前述為相同之意思。Specifically, ginseng (carboxyalkyl) isocyanurate is reacted with an olefin compound represented by (CH ₂ =CR ² -CH ₂ -O) _n -AY to produce an olefin having an unsaturated bond After substituting the isocyanurate (intermediate), the compound (intermediate) is reacted with peroxide to produce the epoxy compound represented by the above formula [2]. As an example, the synthesis flow chart is shown below. In addition, the group Y is not particularly limited as long as it can react with the carboxyl group of isocyanuric acid, and examples thereof include a hydroxyl group and a halogen atom.

In the above formula, R ² , L ² and A represent the same meaning as described above.

Examples of the epoxy compound include 1,3,5-ginseng (2-(2,2-bis(glycidoxymethyl)butoxycarbonyl)ethyl)isocyanurate, 1, 3,5-ginseng (2-(2,2-bis(glycidoxymethyl)-3-(glycidyloxy)propoxycarbonyl)ethyl) isocyanurate, 1,3, 5-ginseng (2-(1-(glycidoxymethyl)-2-(glycidyloxy)ethoxycarbonyl)ethyl)isocyanurate, etc. Among them, 1,3,5-ginseng (2-(2,2-bis(glycidoxymethyl)butoxycarbonyl)ethyl)isocyanurate is preferred. In addition, as the epoxy compound system, commercially available products can be suitably used, and examples thereof include TEPIC (registered trademark)-UC [manufactured by Nissan Chemical Co., Ltd.] and the like. These epoxy compounds may be used alone or in a mixture of two or more.

The composition for the moisture-proof sealing material of the present invention can form a semiconductor substrate, a semiconductor element, a lead electrode bonded to the semiconductor element, etc., particularly with a metal or ceramic by using an isocyanuric epoxy compound, And the cured semiconductor encapsulating resin is a moisture-proof sealing material having excellent adhesion. In addition, in the isocyanuric epoxy compound of the present invention, L ¹ in formula [1] represents an alkylene group having 2 to 7 carbon atoms, and L ² in formula [2] represents a carbon number 1 ~5 alkylene group, and A represents an aliphatic hydrocarbon group which may include a (n+1)-valent ether bond, therefore, compared to when, for example, L ¹ in formula [1] is a composition representing methylene, The composition for moisture-proof sealing material of the present invention can form a cured product having excellent extensibility.

[(b) Multifunctional epoxy compound without isocyanuric acid skeleton] The polyfunctional epoxy compound that does not have an isocyanuric acid skeleton is not particularly limited as long as it contains two or more epoxy groups in one molecule, and a commercially available product can be used. For example, 1,2,7,8-diepoxyoctane, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,6-dihydroxymethyl Perfluorohexane diglycidyl ether, (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol triglycidyl ether, diglycerol polyglycidyl ether , Trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol tetraglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether, 1, 4-cyclohexane dimethanol diglycidyl ether, dicyclopentadiene dimethanol diglycidyl ether, dibromophenyl = glycidyl = ether, 2,6-diglycidyl phenyl = glycidyl = ether, m Hydroquinone diglycidyl ether, bis(2,7-diglycidoxynaphthalene-1-yl)methane, 1,1,2,2-an (4-glycidoxyphenyl)ethane, 1 , 1,3-ginseng (4-glycidoxyphenyl) propane, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, tetrabromobisphenol A diglycidyl ether Ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, bisphenol hexafluoroacetone diglycidyl ether, bis(2,3-epoxycyclopentyl) ether, 1,2-bis (3,4-epoxycyclohexylmethoxy)ethane, ethylene glycol bis(3,4-epoxycyclohexanecarboxylate), 3,4-epoxycyclohexanecarboxylic acid ( 3,4-epoxycyclohexyl) methyl ester, 4,5-epoxy-2-methylcyclohexanecarboxylic acid 4,5-epoxy-2-methylcyclohexyl methyl ester, adipic acid Bis(3,4-epoxycyclohexylmethyl), 1,2-epoxy-4-(epoxyethyl)cyclohexane, 4-(spiro[3,4-epoxycyclohexyl Alkane-1,5'-[1,3]dioxane]-2'-yl)-1,2-epoxycyclohexane, adipic acid diglycidyl ester, phthalic acid diglycidyl ester , Diglycidyl tetrahydrophthalate, 1,2-cyclohexane dicarboxylic acid diglycidyl ester, N,N-diglycidyl-4-glycidoxyaniline, N,N,N', N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 4,4'-methylenebis(N,N- Diglycidyl aniline), 2-(4,4-dimethylpentane-2-yl)-5,7,7-trimethyloctanoic acid 2,2-bis(glycidoxymethyl)butane Base, bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, bisphenol S epoxy resin, alicyclic epoxy resin 、Phenol methane epoxy resin, tetraphenol ethane epoxy resin, alicyclic polyglycidyl ether epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, naphthol novolac epoxy resin Type epoxy resin, anthracene novolak type epoxy resin, biphenylene novolak type epoxy resin, xylol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type Lacquer type epoxy resin, triphenol methane novolak type epoxy resin, phenol novolak type epoxy resin, dicyclopentadiene novolak type epoxy resin, etc., but not limited to these.

Among them, selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol At least one polyfunctional epoxy compound of the group consisting of phenol F novolac epoxy resin and alicyclic polyglycidyl ether epoxy resin is preferred; selected from bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, bisphenol A novolac polyglycidyl ether and dicyclopentadiene dimethanol diglycidyl ether The polyfunctional epoxy compound of at least one kind of the group is further preferred; bisphenol F diglycidyl ether is particularly preferred. In addition, the above-mentioned epoxy compound system can be used in combination with commercially available products, such as jER (registered trademark) 825, the same 827, the same 828, the same 828EL, the same 828US, the same 828XA, the same 834, the same 819, the same 806, the same 806H, same 807, same 4004P, same 152, same 157S70, same 630, same 630LSD, same 871, same 1750, same YX8000, same YX8034, same YL980, same YL983U, same YX7105, same YX7110B80, same YX7400 (all are Mitsubishi Chemical (stock system)], ADEKA RESIN (registered trademark), same as EP-4100HF, same as EP-4901HF, same as EP-4000S, same as EP-4000L, same as EP-4003S, same as EP-4010S, same as EP-4010L, same EP-4088S, same as EP-4088L, same as EP-3300E, same as EP-3300S, same as EP-3950S, same as EP-3950L, same as EP-3980S, same as EPR-4030, same as EP-49-23 )Made by ADEKA], EPICLON (registered trademark) EXA-850CRP, same as EXA-830CRP, same as EXA-830LVP, same as EXA-835LV, same as HP-4032D, same as HP-7200L, same as HP-7200, same as HP-7200H, same HP-7200HH, HP-7200HHH, HP-4700, HP-4770, HP-5000, HP-6000, EXA-4850-150, EXA-4850-1000, EXA-4816 DIC (stock system)] etc. These epoxy compounds may be used alone or in a mixture of two or more. By combining these polyfunctional epoxy compounds that do not have an isocyanuric skeleton with an isocyanuric epoxy compound, a skeleton that has sufficient barrier to moisture can be obtained. Therefore, the obtained The epoxy resin composition can form a moisture-proof sealing material with high moisture permeability resistance.

In the present invention, the amount of the polyfunctional epoxy compound that does not have an isocyanuric acid skeleton is (for example) 100 to 1,000 parts by mass relative to (a) 100 parts by mass of the isocyanuric acid-based epoxy compound. It is preferably 200 to 900 parts by mass, more preferably 250 to 500 parts by mass.

[(c) Multifunctional oxetane compound] The polyfunctional oxetane compound is not particularly limited as long as it contains two or more oxetane groups in one molecule, and a commercially available product can be used. Examples of polyfunctional oxetane compounds include bis((oxetane-3-yl)methyl)ether and bis((3-methyloxetane-3-yl)methyl )Ether, bis((3-ethyloxetan-3-yl)methyl)ether (DOX), 1,2-bis((3-ethyloxetan-3-yl)methyl Oxy)ethane, 1,2-bis((3-ethyloxetane-3-yl)methoxy)propane, 1,3-bis((3-ethyloxetane- 3-yl)methoxy)propane, 1,4-bis((3-ethyloxetan-3-yl)methoxy)butane, 1,6-bis((3-ethyloxy Heterocyclobutan-3-yl)methoxy)hexane, 1,1,1-shen((3-ethyloxetan-3-yl)methoxymethyl)propane, 1,2 -Bis((3-ethyloxetan-3-yl)methoxy)benzene, 1,3-bis((3-ethyloxetan-3-yl)methoxy)benzene , 1,4-bis((3-ethyloxetan-3-yl)methoxy)benzene, 1,4-bis((3-ethyloxetan-3-yl)methyl Oxymethyl)benzene (XDO), 2,2'-bis((3-ethyloxetan-3-yl)methoxy)biphenyl, 4,4'-bis((3-ethyl Oxetan-3-yl)methoxy)biphenyl, 4,4'-bis((3-ethyloxetan-3-yl)methoxymethyl)biphenyl, bis ((3-ethyloxetan-3-yl)methyl) isophthalate, etc., especially bis((3-ethyloxetan-3-yl)methyl) Ether is preferred. In addition, the above-mentioned multifunctional oxetane compound system can be suitably used as a commercially available product, and examples thereof include ARON Oxetane (registered trademark) OXT-121, Tong 221 [both manufactured by East Asia Synthetic Co., Ltd.], and Eternacoll (registered trademark) OXBP, the same as OXIPA [both Ube Kogyo Co., Ltd.], etc. These polyfunctional oxetane compounds can be used alone or in combination of two or more. By using a polyfunctional oxetane compound, it is possible to obtain a composition for a moisture-proof sealing material having excellent curability in a short time.

In the present invention, the use amount of the (c) polyfunctional oxetane compound is, for example, 100 parts by mass of the aforementioned (a) isocyanuric epoxy compound and (b) polyfunctional epoxy compound, for example 1 to 100 parts by mass, preferably 2 to 50 parts by mass, and more preferably 5 to 25 parts by mass.

[(d) Polymerization initiator that generates acid or alkali by active energy rays] As a polymerization initiator, it generates acid or alkali by active energy rays such as light, and can start (a) isocyanuric epoxy compound, (b) polyfunctional epoxy compound, and (c) polyfunctional The polymerization of the oxetane compound may be sufficient. According to this, since the moisture-proof sealing material composition of the present invention does not immediately harden even when the components (a) to (d) are mixed, the storage stability is excellent, and sufficient working time can be obtained.

As the acid-generating polymerization initiator system, a photoacid generator can be used. The photo-acid generator is not particularly limited as long as it can directly or indirectly generate an acid (Lewis acid or Brunoester acid) by light irradiation. In addition, since the curable composition prepared with the photoacid generator is cured by light irradiation without heating, it can be suitably used as a moisture-proof sealing material for organic EL display substrates having low heat resistance.

Specific examples of the photoacid generator include onium salts such as iodonium salts, manganese salts, phosphonium salts, and selenium salts, metallocene complex compounds, iron arene complex compounds, dioxin-based compounds, and sulfonic acid derivatives Compound, triazine compound, acetophenone derivative compound, diazomethane compound, etc.

Examples of the above-mentioned tungsten salts include diphenyl tungsten, 4,4'-dichlorodiphenyl tungsten, 4,4'-dimethoxydiphenyl tungsten, 4,4'-di-tert-butyl Diphenyliodonium, 4-methylphenyl (4-(2-methylpropyl)phenyl)iodonium, 3,3'-dinitrophenylphosphonium, 4-(1-ethoxycarbonylethoxy Chloride), bromide, mesylate, tosylate, etc. of iodine) phenyl (2,4,6-trimethylphenyl) iodide, 4-methoxyphenyl (phenyl) iodide , Trifluoromethanesulfonate, tetrafluoroborate, bis(pentafluorophenyl) borate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, etc.

Examples of the above-mentioned osmium salts include triphenylammonium, diphenyl(4-tert-butylphenyl)ammonium, ginseng (4-tert-butylphenyl)ammonium, diphenyl(4-methoxy) Phenyl) agaric, ginseng (4-methylphenyl) agaric, ginseng (4-methoxyphenyl) agaric, ginseng (4-ethoxyphenyl) agaric, diphenyl (4-(phenylthio) ) Phenyl) cerium, ginseng (4- (phenylthio) phenyl) arsonium, ginseng (4- (4- acetophenylthio) phenyl) monium chloride, bromide, trifluoromethane Triaromatics such as sulfonate, tetrafluoroborate, potassium (pentafluorophenyl) borate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, ginseng (trifluoromethylsulfonyl) methanide, etc. Base salt and so on.

Examples of the phosphonium salts include tetraphenylphosphonium, ethyltriphenylphosphonium, tetrakis(p-methoxyphenyl)phosphonium, ethyltris(p-methoxyphenyl)phosphonium, and benzyltriphenylbenzene. Aryl phosphonium salts such as chloride, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, etc.

Examples of the selenium salt include triaryl selenium salt such as triphenyl selenium hexafluorophosphate.

Examples of the iron aromatic hydrocarbon complex compound include bis(η5-cyclopentadiene)(η6-cumene) iron(II) hexafluorophosphate and the like.

In addition, the photoacid generator system can be obtained from commercially available products, such as CPI (registered trademark)-100P, the same 101A, the same 200K, the same 210S, the same 310B, the same 310FG, the same 410S, IK-1 [all are San-apro (share)], IRGACURE (registered trademark) 250, same 270, same 290, GSID26-1 [all BASF JAPAN (share)], WPAG-145, same 149, same 170, same 199, same 336, Tong 367, Tong 370, Tong 469, Tong 638, Tong 699, WPI-113, Tong 116, Tong 169, Tong 170, Tong 124 [all made by FUJIFILM Wako Pure Chemical Co., Ltd.], etc. These photoacid generators may be used alone or in combination of two or more. Among these, as the polymerization initiator, a samium salt compound or a gallium salt compound is preferred, for example, a (pentafluorophenyl) borate, hexafluorophosphate, hexafluoroantimonate exhibiting strong acidity For compounds having anionic species, etc., in particular, from the viewpoint of not generating hydrogen fluoride by-product during the reaction, a salt compound of (pentafluorophenyl) borate is preferred.

In the moisture-proof sealing material composition of the present invention, with respect to the total of 100 masses of (a) isocyanuric epoxy compound, (b) polyfunctional epoxy compound, and (c) polyfunctional oxetane compound Parts, the content of the photoacid generator can be, for example, 0.1 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 10 parts by mass.

Moreover, a photobase generator can be used as a polymerization initiator system for generating alkali. The photobase generator is not particularly limited as long as it can generate a base (Lewis base or Brunoester base) directly or indirectly by light irradiation. The moisture-proof sealing material composition prepared with a photobase generator is hardened by light irradiation without heating, and therefore can be suitably used as a moisture-proof sealing material for organic EL display substrates having low heat resistance.

Examples of the photobase generator include alkylamine photobase generators such as 9-anthrylmethyl=N,N-diethylcarbamate; 9-anthracene=N,N-dicyclohexyl Carbamate, 1-(9,10-anthraquinone-2-yl)ethyl=N,N-dicyclohexylcarbamate, dicyclohexylammonium=2-(3-benzophenone) Group) propionate, 9-anthracenyl=N-cyclohexylcarbamate, 1-(9,10-anthraquinone-2-yl)ethyl=N-cyclohexylcarbamate, cyclohexyl Ammonium = 2-(3-benzoylphenyl) propionate, (E)-N-cyclohexyl-3-(2-hydroxyphenyl) acrylamide and other cycloalkylamine photobase generators; 9 -Anthracenylmethyl=pyridin-1-carboxylate, (E)-1-piperidin-3-(2-hydroxyphenyl)-2-propen-1-one, (2-nitrophenyl) Methyl = 4-hydroxypyridin-1-carboxylate, (2-nitrophenyl) methyl = 4-(methacryloxy) pyridine-1-carboxylate, etc. Photobase generator; guanidinium=2-(3-benzoylphenyl) propionate, 1,2-diisopropyl-3-(bis(dimethylamino)methylene)guanidinium= 2-(3-Benzoylphenyl) propionate, 1,2-dicyclohexyl-4,4,5,5-tetramethyl biguanide=n-butyltriphenylborate, 1,5 ,7-triazabicyclo[4.4.0]dec-5-enium=2-(9-oxobenzofluoren-2-yl)propionate and other guanidine photobase generators; 1-(9 , 10-anthraquinone-2-yl)ethyl=imidazole-1-carboxylate and other imidazole-based photobase generators. In addition, the photobase generator system can be obtained from commercially available products, such as WPBG-174, the same 018, the same 041, the same 015, the same 172, the same 166, the same 140, the same 168, the same 025, the same 167, the same 300, Tong 266, Tong 158, Tong 165, Tong 082, Tong 027 [all made by FUJIFILM Wako Pure Chemical Co., Ltd.], etc. These photobase generators may be used alone or in combination of two or more.

In the moisture-proof sealing material composition of the present invention, relative to 100 masses of (a) isocyanuric epoxy compound, (b) polyfunctional epoxy compound, and (c) polyfunctional oxetane compound The content of the photobase generator can be, for example, 0.1 to 30 parts by mass, preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass.

[Other ingredients] In addition, the moisture-proof sealing material composition of the present invention may contain conventional additives within a range that does not impair the effects of the present invention. Examples of such additives include solvents, surfactants, adhesion promoters, thickeners, sensitizers, defoamers, leveling agents, coating improvers, lubricants, and stabilizers (antioxidants , Heat stabilizers, light stabilizers, etc.), plasticizers, dissolution accelerators, fillers (silica, etc.), antistatic agents, silane coupling agents, etc. These additives may be used alone or in combination of two or more.

[Silane coupling agent] The silane coupling agent is not particularly limited as long as it contains an alkoxysilane group and other reactive functional groups in the molecule, and a commercially available product can be used.

Examples of the silane coupling agent include vinyl-containing silane coupling agents such as trimethoxy (vinyl) silane, triethoxy (vinyl) silane, trimethoxy (7-octenyl) silane; 2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyldimethoxy(methyl)silane, 3-glycidoxypropyltrimethoxysilane, di Ethoxy (3-glycidoxypropyl) (methyl) silane, triethoxy (3-glycidoxypropyl) silane, 8-glycidoxy octyl trimethoxy silane, triethyl Oxygen (8-glycidoxyoctyl) silane and other epoxy group-containing silane coupling agents; trimethoxy (4-vinylphenyl) silane and other vinyl group-containing silane coupling agents; 3- Methacryloyloxypropyldimethoxy(meth)silane, 3-methacryloyloxypropyltrimethoxysilane, diethoxy(3-methacryloyloxypropyl) Contains methacryloyl groups such as methyl) silane, triethoxy (3-methacryloyloxypropyl) silane, trimethoxy (8-methacryloyloxyoctyl) silane, etc. Silane coupling agent; 3-propene acetyl propyl trimethoxy silane and other silane coupling agent containing acryl group; 3- ((2-aminoethyl) amino) propyl dimethoxy (methyl Group) silane, 3-((2-aminoethyl)amino)propyltrimethoxysilane, 8-((2-aminoethyl)amino)octyltrimethoxysilane, 3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(1,3-dimethylbutylene)-3-triethoxysilylpropylamine, trimethoxy(3-benzene Amino group-containing silane coupling agents such as aminoaminopropyl) silane, trimethoxy (3-((2-((vinylbenzyl)amino)ethyl)amino)propyl) silane acid acid, etc.; Trimethoxy (3-ureapropyl) silane, triethoxy (3-ureapropyl) silane and other urea group-containing silane coupling agent; triethoxy (3-isocyanate propyl) silane, etc. Silane coupling agent containing isocyanate groups; ginseng (3-trimethoxysilylpropyl) isocyanurate, ginseng (3-triethoxysilylpropyl) isocyanurate, etc. Polycyanate type silane coupling agent; 3-mercaptopropyl dimethoxy (methyl) silane, 3-mercaptopropyl trimethoxy silane and other thiol group-containing silane coupling agent; (3-trimethoxy silane group Anhydride type silane coupling agent such as propyl) succinic anhydride. Among them, silane coupling agents containing epoxy groups are preferred, silane coupling agents containing glycidyl groups are more preferred, and 3-glycidoxypropyltrimethoxysilane and triethoxy (3 -Glycidoxypropyl) silane is particularly preferred.

In addition, the aforementioned silane coupling agent system can be suitably used as a commercially available product, and examples thereof include Shin-Etsu Silicone (registered trademark) KBM-1003, the same KBE-1003, the same KBM-1083, the same KBM-303, the same KBM-402, the same KBM-403, same as KBE-402, same as KBE-403, same as KBM-4803, same as KBM-1403, same as KBM-502, same as KBM-503, same as KBE-502, same as KBE-503, same as KBM-5803, same KBM-5103, same as KBM-602, same as KBM-603, same as KBM-6803, same as KBM-903, same as KBE-903, same as KBE-9103P, same as KBM-573, same as KBM-575, same as KBE-585, same KBE-9007, same as KBM-9659, same as KBE-9659, same as KBM-802, same as KBM-803, same as X-12-967C [all are made by Shin-Etsu Chemical Industry Co., Ltd.], etc.

These silane coupling agents can be used alone or in a mixture of two or more. By adding these silane coupling agents, a composition for a moisture-proof sealing material excellent in ionic migration resistance can be obtained.

In the present invention, when a silane coupling agent is added, the total of (a) the isocyanuric epoxy compound, (b) polyfunctional epoxy compound, and (c) polyfunctional oxetane compound is 100 The mass parts are, for example, 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 2 parts by mass.

[Method for preparing composition for moisture-proof sealing material] The composition for moisture-proof sealing material of the present invention can be prepared by mixing the components according to a well-known method. The mixing is not particularly limited as long as it can be uniformly mixed. For example, when considering the viscosity, it is carried out under heating according to need, and the temperature is 10 to 100° C. for 0.5 to 1 hour. If necessary, degassing and stirring are performed to remove bubbles in the composition.

[Organic EL display] The composition for moisture-proof sealing material of the present invention can be used as an encapsulation (sealing) material or a shielding material in an electrical device such as an organic EL display (especially an organic EL element of an organic EL display), and a bonding material to a substrate or an electrode To use. According to this, the organic EL element can prevent corrosion and oxidation caused by moisture or oxygen from the outside, and thus can prevent the formation of dark spots or the reduction of brightness. In addition, the method for curing the composition for moisture-proof sealing material of the present invention is not particularly limited, and a well-known method such as irradiation with active energy rays such as light can be used. Examples of the active energy rays include ultraviolet rays, electron rays, X rays, and the like, and ultraviolet rays are particularly preferred. As a light source used for ultraviolet irradiation, solar rays, chemical lamps, low-pressure mercury lamps, high-pressure mercury lamps, metal halogen lamps, xenon lamps, UV-LEDs, etc. can be used. The composition for moisture-proof sealing material of the present invention is hardened by coating and irradiating with active energy rays, so it does not require a high-temperature heating (baking) step to harden it. Therefore, it can be suitably used for the production of organic EL elements with low heat resistance. [Industry availability]

The moisture-proof sealing material composition of the present invention is excellent in photocurability and can form a cured product excellent in moisture-proofness, and therefore can be suitably used for sealing various elements. Furthermore, the moisture-proof sealing material composition of the present invention can form a hardened product having excellent extensibility, and is therefore very suitable as a sealing material for sealing display elements such as organic EL elements used in flexible displays. [Example]

The following examples and comparative examples are used to explain the present invention more specifically, but the present invention is not limited to the following examples. In addition, the apparatus and conditions used for sample preparation and physical property analysis in the examples are as follows.

(1) Stirring and deaeration Device: Thinky (shares) made 　rotation and revolution mixer 　 defoaming mixer (except foaming training Taro) (registered trademark) ARE-310 (2) Rod coating Device: SMT (stock) system 　PM-9050MC Bar coating machine: SA-203 No. 65 manufactured by TESTER Industries Co., Ltd., wet film thickness 148.6 μm Coating speed: 4m/min (3) Moisture permeability Constant-temperature and constant-humidity device: ESPEC (stock) made "small environmental tester" SH-262 Moisture-permeable cup mold: 　moisture-permeable cup mold (screw fixing method) manufactured by Jingyuan Manufacturing Co., Ltd. (4) Tensile test Device: Shimadzu Corporation's 　 desktop precision universal testing machine (Autograph) AGS-5kNX Clamp: Air type flat clamp Jaws: rubber coated jaws Stretching speed: 5mm/min Measuring temperature: room temperature (about 23℃) (5) Ion migration assessment Evaluation device: ESPEC (share) system 　 electrochemical migration evaluation system AMI-025-U-5 Constant temperature and humidity device: small environmental tester made by ESPEC (share) SH-222

In addition, the meaning of the code used is as follows. ADGIC: Monoallyl diglycidyl isocyanurate [MA-DGIC manufactured by Shikoku Chemical Industry Co., Ltd.] TEOIC: Participate in (7,8-epoxyoctyl) isocyanurate [Nissan Chemical Co., Ltd. TEPIC (registered trademark)-FL] TEPeIC: Ginseng (4,5-epoxypentyl) isocyanurate [TEPIC (registered trademark)-VL manufactured by Nissan Chemical Co., Ltd.] TGIC: Triglycidyl isocyanurate [TEPIC (registered trademark)-L manufactured by Nissan Chemical Co., Ltd.] BPAN: Bisphenol A novolac epoxy resin [jER (registered trademark) 157S70 made by Mitsubishi Chemical Corporation] BPF: Bisphenol F type epoxy resin [jER (registered trademark) 807 by Mitsubishi Chemical Corporation] DCP: Dicyclopentadiene dimethanol diglycidyl ether [ADEKA RESIN (registered trademark) EP-4088L made by (ADEKA) ADEKA] DOX: 3,3’-(oxybis(methylene))bis(3-ethyloxetane) [ARON Oxetane (registered trademark) OXT-221 manufactured by East Asia Synthetic Co., Ltd.] C100P: Diphenyl (4-(phenylthio)phenyl) alkane hexafluorophosphate [San-apro (shared) CPI (registered trademark)-100P, 50% propyl carbonate solution] C101A: Diphenyl (4- (phenylthio) phenyl) alkane hexafluoroantimonate (V) [San-apro (share) CPI (registered trademark) -101A, 50% propyl carbonate solution] C310B: Triaryl carbamide (pentafluorophenyl) borate [San-apro (shared) CPI (registered trademark) -310B] GTMS: 3-glycidoxypropyltrimethoxysilane [Shin-Etsu Chemical Industry Co., Ltd. Shin-Etsu Silicone (registered trademark) KBM-403]

[Example 1] 20 parts by mass of TEPeIC as an isocyanurate-based epoxy compound, 70 parts by mass of BPF as a multifunctional epoxy compound having no isocyanurate skeleton, and a polyfunctional oxetane compound 10 parts by mass of DOX and 3 parts by mass of C101A as a polymerization initiator (effective component conversion). The mixture was stirred and defoamed (at 2,000 rpm for 4 minutes, then at 1,000 rpm for 4 minutes) to prepare Composition 1. This composition was bar-coated on a PET film [Lumirror (registered trademark) S10 made by Toray Co., Ltd.]. By applying this coating film, a high-pressure mercury lamp was used in an air environment, and UV light was irradiated at 20 mW/cm ^{2 for} 50 seconds to harden it. The cured product was peeled from the PET film to obtain a cured film having a film thickness of approximately 100 μm.

The moisture permeability and elongation at break of the obtained cured film were evaluated. The evaluation procedures are shown below. The results are shown in Table 1.

[Moisture permeability] According to JIS Z 0208:1976 moisture permeability test method (cup mold method) of moisture-proof packaging materials, put the calcium chloride into the moisture-permeable cup mold, and cut out from the hardened film The test piece is mounted on the opening of the moisture-permeable cup mold to make a test body (the transmission area is 28.3 cm ² ). The test body was placed in a constant temperature and humidity device set at a temperature of 40°C and a relative humidity of 90% (Condition B). After 24 hours, the test body was taken out and the quality of the test body was measured. Repeat the operation of putting the test body in the constant temperature and humidity device again, taking out the test body at 24 hour intervals and weighing it until the mass increase becomes constant, and calculate the moisture permeability of the film (actual measurement). Still, in this test, considering the influence caused by the difference in the film thickness of the test piece, a cured film was made in such a way that the film thickness became in the range of 80 to 500 μm, and the moisture permeability was measured, and the value converted to 100 μm thickness was taken as the following formula The assessed value. Moisture permeability [g/m ² · 24h] = Moisture permeability (measured) × Test piece film thickness [μm] ÷ 100 [μm]

[Elongation at break] The cured film was cut into a rectangle with a length of 60 mm and a width of 15 mm to prepare a test piece. From both ends of the test piece in the longitudinal axis direction, each 20 mm was mounted by a gripper of a universal testing machine to mount and perform a tensile test. The length I [mm] between the punctuation points (between the grippers) at the time of making the fracture face-to-face measurement was measured so that the center line of the two fractured pieces of the test piece became a straight line, and the fracture elongation was calculated according to the following formula. Elongation at break δ[%]=(II ₀ )÷I ₀ ×100 (I ₀ : distance between original points=20[mm])

[Examples 2 to 4, Comparative Examples 1, 2] Each cured film was obtained in the same manner as in Example 1 except that each composition was changed to the description in Table 1. In addition, the compositions 5 and 6 are underhardened under the same curing conditions (exposure conditions). Since the surface of the cured product still sticks, it is further heated for 30 minutes on a 100°C hot plate (post-curing). Table 1 shows the moisture permeability and elongation at break of each cured film.

As shown in Table 1, it can be confirmed that the moisture permeability of the cured products obtained from the compositions of Examples 1 to 4 is lower than that of the cured products obtained from the compositions of Comparative Examples 1 and 2. , Elongation at break is also high. That is to say, the composition of the present invention can obtain a cured product excellent in moisture resistance and extensibility. In addition, the composition of Examples 1 to 4 is a cured product excellent in moisture resistance and extensibility only by UV exposure, so it can be confirmed that the photocurability is excellent.

[Examples 5 to 10] Except changing each composition to the description of Table 2, it carried out similarly to Example 1, and prepared the composition 7-10.

Except for using the obtained composition, the same procedure as in Example 1 was carried out to produce cured films having a film thickness of approximately 100 μm. The moisture permeability of each cured film was evaluated in the same manner as in Example 1. The results are shown in Table 3.

In addition, on a glass substrate with two silver electrodes formed as shown in FIG. 1, as shown in FIG. 2, a spacer made of polysilicone rubber with a thickness of 500 μm was placed and coated so as to cover both electrodes Each composition. The coated substrate covers a quartz glass substrate, and the quartz glass substrate is the same size as the coated substrate, and the mold release treatment is performed in advance using Optool (registered trademark) DSX [manufactured by Daikin Industries Co., Ltd.]. By using a UV-LED (wavelength: 365 nm), UV light was irradiated from the quartz glass substrate side at 100 mW/cm ² for 10 seconds to harden the applied composition. After that, the quartz glass substrate and the spacer were removed to obtain a test piece in which both electrodes were encapsulated by a hardened material with a thickness of 500 μm.

In a constant temperature and humidity device set to the temperature and humidity described in Table 3, apply DC voltages described in Table 3 to both electrodes of the obtained test piece, and measure until ion migration occurs (the resistance value between the two electrodes becomes 10 ⁵ Ω or less) and evaluate the time. Table 3 summarizes the results.

As shown in Table 3, it can be confirmed that as the polymerization initiator, a hardened product obtained from the composition using a cerium salt compound having (pentafluorophenyl) borate ion (Example 6) ~10) The system maintains a low moisture permeability state and is excellent in ion migration resistance. In addition, it can be confirmed that by adding a silane coupling agent, the ion migration resistance is further excellent (Example 10).

1: silver electrode 2: composition 3: spacer

[FIG. 1] FIG. 1 is a schematic diagram of a glass substrate formed with silver electrodes for ion migration evaluation. [FIG. 2] FIG. 2 is a schematic diagram showing the production process of a test piece for ion migration evaluation.

Claims (10)

A composition for moisture-proof sealing material, comprising (a) at least one kind of isocyanuric epoxy selected from the group consisting of a compound represented by formula [1] and a compound represented by formula [2] Compound, (b) polyfunctional epoxy compound without isocyanuric acid skeleton, (c) polyfunctional oxetane compound, and (d) polymerization initiator that generates acid or base by active energy ray ,

(In the formula, R ¹ represents a hydrogen atom or a methyl group, L ¹ represents an alkylene group having 2 to 7 carbon atoms, where each R ¹ may be the same or different from each other, and each L ¹ may be mutually Are the same or different)

(In the formula, R ² represents a hydrogen atom or a methyl group, L ² represents an alkylene group having 1 to 5 carbon atoms, A represents an aliphatic hydrocarbon group which may include a (n+1)-valent ether bond, and n represents 2 to 5 Integer of, here, each R ² may be the same or different from each other, each L ² may be the same or different from each other, each A may be the same or different from each other, each n may be mutually Are the same or different). The composition for moisture-proof sealing material according to claim 1, wherein the aforementioned (b) polyfunctional epoxy compound having no isocyanuric acid skeleton is selected from the group consisting of bisphenol A type epoxy resin and bisphenol F type epoxy resin Resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, bisphenol A novolac epoxy resin, bisphenol F novolac epoxy resin and alicyclic polyglycidyl ether epoxy resin At least one type of resin. The composition for moisture-proof sealing material according to claim 2, wherein the aforementioned (b) polyfunctional epoxy compound having no isocyanuric acid skeleton is selected from the group consisting of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether At least one of the group consisting of ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, bisphenol A novolac polyglycidyl ether, and dicyclopentadiene dimethanol diglycidyl ether . The composition for a moisture-proof sealing material according to claim 3, wherein the aforementioned (b) polyfunctional epoxy compound having no isocyanuric acid skeleton is bisphenol F diglycidyl ether. The composition for a moisture-proof sealing material according to any one of claim 1 to claim 4, wherein the polymerization initiator in which (d) the acid or alkali is generated by active energy rays is a photoacid generator. The composition for moisture-proof sealing materials according to any one of claim 1 to claim 5, wherein the (a) isocyanurate-based epoxy compound is a compound represented by the above formula [1]. The composition for a moisture-proof sealing material according to any one of claim 1 to claim 6, wherein the hardened material in the cup mold method according to the moisture permeability test method of the moisture-proof packaging material according to JIS Z 0208 (1976) The moisture permeability measured under Condition B (temperature 40°C, relative humidity 90%), when converted to a thickness of 100 μm, is 20 g/m ² ·24h or less. The composition for a moisture-proof sealing material according to any one of claim 1 to claim 7, which is a composition for a moisture-proof sealing material for an organic EL display. A hardened product obtained by hardening the composition for moisture-proof sealing material of any one of claim 1 to claim 8. An organic EL display equipped with the hardened product of claim 9.

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