JP7368348B2 - Resin composition, sealing sheet and sealing body - Google Patents

Description

The present invention provides a resin composition with excellent sheet processability (film-forming properties), a sealing sheet formed using this resin composition and having an adhesive layer with excellent adhesive strength, colorless transparency, and water vapor barrier properties; The present invention also relates to a sealed body in which an object to be sealed is sealed using the sealing sheet.

In recent years, organic EL elements have attracted attention as light-emitting elements that can emit high-intensity light by low-voltage DC drive.
However, organic EL devices have a problem in that their light-emitting properties such as luminance, luminous efficiency, and uniformity of luminescence tend to deteriorate over time.
The cause of this problem of deterioration in luminescent properties is thought to be that oxygen, moisture, etc. enter the inside of the organic EL element and deteriorate the electrodes and organic layers, so the organic EL element is sealed using a sealing material. However, efforts have been made to prevent the infiltration of oxygen and moisture.
In addition, when sealing an object to be sealed such as an organic EL element using a sealing material, if outgas is generated from the sealing material, the organic EL element etc. will deteriorate, so we are developing a sealing material with low outgassing properties. has also been carried out.

For example, Patent Document 1 describes a composition for sealing an organic EL device containing a specific cationic curable compound, a photocationic polymerization initiator, and a specific glycoluril compound.
Further, Patent Document 1 also describes that the cured product of the sealing composition has moisture-proofing properties and low outgas properties, and thus can prevent deterioration of organic EL elements due to moisture and outgas.

International Publication 2017/094809

By the way, objects to be sealed such as organic EL elements are often used under harsh conditions such as outdoors or inside a car. Therefore, there is a demand for a sealing sheet that has excellent adhesive strength as well as excellent moisture resistance and low outgassing properties, and a resin composition that can be suitably used as a raw material for such a sealing sheet. Furthermore, the cured product of the composition for encapsulating an organic EL element as described in Patent Document 1 is also required to have excellent colorless transparency due to its specific optical use.
However, Patent Document 1 does not describe physical property evaluation results of adhesive strength and colorless transparency of a cured product of an organic EL element sealing composition.

The present invention provides a resin composition with excellent sheet processability (film-forming properties), a sealing sheet formed using this resin composition and having an adhesive layer with excellent adhesive strength, colorless transparency, and water vapor barrier properties; Another object of the present invention is to provide a sealed body in which an object to be sealed is sealed using the sealing sheet.

As a result of intensive study by the present inventors to solve the above problems,
(i) The resin composition containing a modified polyolefin resin, a compound having a cyclic ether group, and a photocationic polymerization initiator has excellent sheet processability (film forming property), and (ii) this resin composition The sealing sheet having an adhesive layer formed using the above method has excellent adhesive strength, colorless transparency, and water vapor barrier properties;
They discovered this and completed the present invention.

Thus, according to the present invention, the following resin compositions [1] to [10], sealing sheets [11] to [14], and sealed bodies [15] and [16] are provided.

[1] A resin composition containing the following components (A), (B), and (C).
(A) Component: Modified polyolefin resin (B) Component: Compound having a cyclic ether group (C) Component: Photocationic polymerization initiator

[2] The resin composition according to [1], wherein the component (A) is an acid-modified polyolefin resin.
[3] The resin composition according to [1] or [2], wherein the cyclic ether group of the component (B) is an oxirane group or an oxetane group.
[4] The resin composition according to any one of [1] to [3], wherein the content of the component (B) is 5 to 50 parts by mass based on 100 parts by mass of the component (A).

[5] The resin composition according to any one of [1] to [4], wherein the component (C) is an aromatic sulfonium salt compound.
[6] The resin composition according to any one of [1] to [5], wherein the content of the component (C) is 0.04 to 2 parts by mass based on 100 parts by mass of the component (B). thing.

[7] The resin composition according to any one of [1] to [6], further containing a tackifier.
[8] The resin composition according to [7], wherein the content of the tackifier is 1 to 200 parts by mass based on 100 parts by mass of component (A).
[9] The resin composition according to any one of [1] to [8], further containing a silane coupling agent.
[10] The resin composition according to [9], wherein the content of the silane coupling agent is 0.01 to 10 parts by mass based on 100 parts by mass of component (A).

[11] A sealing sheet consisting of a base material or a release film, and an adhesive layer formed on the base material or release film,
A sealing sheet, wherein the adhesive layer is formed using the resin composition according to any one of [1] to [10].
[12] A sealing sheet consisting of two release films and an adhesive layer sandwiched between the two release films,
A sealing sheet, wherein the adhesive layer is formed using the resin composition according to any one of [1] to [10].
[13] A sealing sheet comprising a release film, a gas barrier film, and an adhesive layer sandwiched between the release film and the gas barrier film,
A sealing sheet, wherein the adhesive layer is formed using the resin composition according to any one of [1] to [10].
[14] The sealing sheet according to [13], wherein the gas barrier film is a metal foil, a resin film, or a thin glass.

[15] A sealed body in which an object to be sealed is sealed using the sealing sheet according to any one of [11] to [14].
[16] The sealed body according to [15], wherein the object to be sealed is an electronic device.

According to the present invention, a resin composition with excellent sheet processability (meaning that it can be easily molded into a sheet-like object; also referred to as "film-forming property"), adhesive strength, A sealing sheet having an adhesive layer with excellent colorless transparency (high total light transmittance and very little coloring) and excellent water vapor barrier properties, and an object to be sealed that can be sealed using the sealing sheet. A sealed body is provided.

Hereinafter, the present invention will be explained in detail by dividing into 1) resin composition, 2) sealing sheet, and 3) sealing body.

1) Resin composition The resin composition of the present invention contains the following components (A), (B), and (C).
(A) Component: Modified polyolefin resin (B) Component: Compound having a cyclic ether group (C) Component: Photocationic polymerization initiator

[Component (A): modified polyolefin resin]
The resin composition of the present invention contains a modified polyolefin resin as component (A).
By containing the modified polyolefin resin, it is possible to obtain a resin composition with excellent sheet processability (film forming property) and a cured product of the resin composition with excellent adhesive strength. Further, by using a resin composition containing a modified polyolefin resin, an adhesive layer having the thickness described below can be efficiently formed.

A modified polyolefin resin is a polyolefin resin into which a functional group has been introduced, which is obtained by subjecting a polyolefin resin as a precursor to a modification treatment using a modifier.

Polyolefin resin refers to a polymer containing repeating units derived from olefin monomers. The polyolefin resin may be a polymer consisting of only one type or two or more types of repeating units derived from olefinic monomers, or a polymer consisting of repeating units derived from olefinic monomers and olefinic monomers. It may also be a polymer consisting of repeating units derived from other polymerizable monomers.

The olefinic monomer is preferably an α-olefin having 2 to 8 carbon atoms, more preferably ethylene, propylene, 1-butene, isobutylene, or 1-hexene, and even more preferably ethylene or propylene.
Other monomers copolymerizable with the olefinic monomer include vinyl acetate, (meth)acrylic acid ester, styrene, and the like. Here, "(meth)acrylic acid" represents acrylic acid or methacrylic acid (the same applies below).

Polyolefin resins include very low density polyethylene (VLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), polypropylene (PP), and ethylene. -Propylene copolymers, olefin elastomers (TPO), ethylene-vinyl acetate copolymers (EVA), ethylene-(meth)acrylic acid copolymers, ethylene-(meth)acrylic acid ester copolymers, etc. .

A modifier used for modifying a polyolefin resin is a compound having a functional group in its molecule.
Functional groups include carboxyl group, carboxylic anhydride group, carboxylic ester group, hydroxyl group, epoxy group, amide group, ammonium group, nitrile group, amino group, imide group, isocyanate group, acetyl group, thiol group, and ether group. , thioether group, sulfone group, phosphone group, nitro group, urethane group, alkoxysilyl group, silanol group, halogen atom, and the like. Among these, carboxyl groups, carboxylic anhydride groups, carboxylic ester groups, hydroxyl groups, ammonium groups, amino groups, imide groups, isocyanate groups, and alkoxysilyl groups are preferred, and carboxylic anhydride groups and alkoxysilyl groups are more preferred. , carboxylic acid anhydride groups are particularly preferred.
A compound having a functional group may have two or more kinds of functional groups in the molecule.

Examples of the modified polyolefin resin include acid-modified polyolefin resins and silane-modified polyolefin resins, and acid-modified polyolefin resins are preferred from the viewpoint of obtaining better effects of the present invention.

Acid-modified polyolefin resin refers to a polyolefin resin graft-modified with an acid. For example, polyolefin resins may be reacted with unsaturated carboxylic acids to introduce carboxyl groups (graft modification). In addition, in this specification, acid includes the concept of acid anhydride, unsaturated carboxylic acid includes the concept of unsaturated carboxylic acid anhydride, and carboxyl group includes the concept of carboxylic acid anhydride group. It includes.

Examples of unsaturated carboxylic acids to be reacted with the polyolefin resin include maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, aconitic acid, maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, Examples include aconitic anhydride, norbornene dicarboxylic anhydride, and tetrahydrophthalic anhydride.
These can be used alone or in combination of two or more. Among these, maleic anhydride is preferred since it is easy to obtain a resin composition with excellent sheet processability (film-forming properties) and a cured product of the resin composition with excellent adhesive strength.

The amount of unsaturated carboxylic acid to be reacted with the polyolefin resin is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight, even more preferably 0.2 to 3 parts by weight, per 100 parts by weight of the polyolefin resin. It is 1 part by mass. The resin composition containing the acid-modified polyolefin resin obtained in this way can easily yield a cured product with excellent adhesive strength.

Commercially available products can also be used as the acid-modified polyolefin resin. Commercially available products include, for example, Admer (registered trademark) (manufactured by Mitsui Chemicals), Unistol (registered trademark) (manufactured by Mitsui Chemicals), BondyRam (manufactured by Polyram), orevac (registered trademark) (manufactured by ARKEMA), Examples include Modic (registered trademark) (manufactured by Mitsubishi Chemical Corporation).

The silane-modified polyolefin resin refers to a polyolefin resin graft-modified with an unsaturated silane compound. The silane-modified polyolefin resin has a structure in which an unsaturated silane compound as a side chain is graft-copolymerized to a polyolefin resin as a main chain. Examples include silane-modified polyethylene resins and silane-modified ethylene-vinyl acetate copolymers, and silane-modified polyethylene resins such as silane-modified low-density polyethylene, silane-modified ultra-low-density polyethylene, and silane-modified linear low-density polyethylene are preferred.

The unsaturated silane compound reacted with the polyolefin resin is preferably a vinyl silane compound. Vinyl silane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltripentyloxysilane, vinyltriphenoxysilane, vinyltribenzyloxysilane, and vinyltribenzyloxysilane. Examples include methylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, and vinyltricarboxysilane.
These can be used alone or in combination of two or more.
Note that the conditions for graft polymerizing the unsaturated silane compound to the main chain polyolefin resin may be any conventional graft polymerization method known in the art.

The amount of the unsaturated silane compound to be reacted with the polyolefin resin is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 7 parts by weight, even more preferably 0.5 to 7 parts by weight, based on 100 parts by weight of the polyolefin resin. 5 parts by mass. The resin composition containing the silane-modified polyolefin resin obtained in this way can easily yield a cured product with excellent adhesive strength.

Commercially available products can also be used as the silane-modified polyolefin resin. Examples of commercially available products include Linkron (registered trademark) (manufactured by Mitsubishi Chemical Corporation). Among these, low-density polyethylene-based Linkron, linear low-density polyethylene-based Linkron, ultra-low-density polyethylene-based Linkron, and ethylene-vinyl acetate copolymer-based Linkron can be preferably used. .

The modified polyolefin resins can be used alone or in combination of two or more.

The number average molecular weight (Mn) of the modified polyolefin resin is preferably 10,000 to 2,000,000, more preferably 20,000 to 1,500,000.
The number average molecular weight (Mn) of the modified polyolefin resin can be determined as a standard polystyrene equivalent value by performing gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[Component (B): compound having a cyclic ether group]
The resin composition of the present invention contains a compound having a cyclic ether group as the component (B).
A compound having a cyclic ether group has excellent compatibility with component (A), so by using this compound, a resin composition with excellent sheet processability (film forming property), colorless transparency, and water vapor barrier can be obtained. A cured product of the resin composition with excellent properties can be obtained.

Examples of the cyclic ether group include oxirane group (epoxy group), oxetane group (oxetanyl group), tetrahydrofuryl group, and tetrahydropyranyl group.
A compound having a cyclic ether group refers to a compound having at least one cyclic ether group in the molecule. Among these, from the viewpoint of being able to obtain a resin composition with excellent sheet processability (film-forming property) and a cured product of a resin composition with excellent adhesive strength, compounds having an oxirane group or an oxetane group are preferred. are preferred, and compounds having two or more oxirane groups or oxetane groups in the molecule are particularly preferred.

Examples of the compound having an oxirane group in the molecule include aliphatic epoxy compounds (excluding alicyclic epoxy compounds), aromatic epoxy compounds, alicyclic epoxy compounds, and the like.
Examples of aliphatic epoxy compounds include monofunctional epoxy compounds such as glycidyl etherified aliphatic alcohols and glycidyl esters of alkyl carboxylic acids;
Examples include polyglycidyl etherified products of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, and polyfunctional epoxy compounds such as poxy compounds having a triazine skeleton.

Typical examples of these aliphatic epoxy compounds include allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C12-13 mixed alkyl glycidyl ether, 1,4-butanediol diglycidyl ether, and neopentyl glycidyl ether. Glycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, dicyclopentadiene dimethanol Polyether polyols obtained by adding one or more alkylene oxides to glycidyl ethers of polyhydric alcohols such as diglycidyl ether, or aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, and glycerin. Polyglycidyl etherified product, diglycidyl ester of aliphatic long chain dibasic acid;
Monoglycidyl ethers of aliphatic higher alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized polybutadiene;
Examples include 2,4,6-tri(glycidyloxy)-1,3,5-triazine.

Moreover, a commercially available product can also be used as the aliphatic epoxy compound. Commercially available products include Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931 ( Manufactured by Nagase ChemteX);
Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.);
ADEKA GLYCILLOL ED-503, ADEKA GLYCILLOL ED-503G, ADEKA GLYCILLOL ED-506, ADEKA GLYCILLOL ED-523T, ADEKA GLYCILLOL EP-4088S, ADEKA GLYCILLOL EP-4088L, ADEKA GLYCILLOL EP-4080E (manufactured by ADEKA);
Examples include TEPIC-FL, TEPIC-PAS, and TEPIC-UC (all manufactured by Nissan Chemical Co., Ltd.).

Examples of the aromatic epoxy compound include polyhydric phenols having at least one aromatic ring, such as phenol, cresol, and butylphenol, or mono/polyglycidyl etherified products of alkylene oxide adducts thereof.
Typical examples of these aromatic epoxy compounds include bisphenol A, bisphenol F, or glycidyl etherified compounds obtained by adding alkylene oxide to these, and epoxy novolac resins;
Mono/polyglycidyl etherified aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, and catechol;
Glycidyl etherified aromatic compounds having two or more alcoholic hydroxyl groups such as phenyldimethanol, phenyldiethanol, phenyldibutanol;
Examples thereof include glycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid, and trimellitic acid, glycidyl esters of benzoic acid, and epoxidized products of styrene oxide or divinylbenzene.

Moreover, a commercially available product can also be used as the aromatic epoxy compound. Commercially available products include Denacol EX-146, Denacol EX-147, Denacol EX-201, Denacol EX-203, Denacol EX-711, Denacol EX-721, Oncoat EX-1020, Oncoat EX-1030, and Oncoat EX. -1040, Oncoat EX-1050, Oncoat EX-1051, Oncoat EX-1010, Oncoat EX-1011, Oncoat 1012 (all manufactured by Nagase ChemteX);
Ogusol PG-100, Ogusol EG-200, Ogusol EG-210, Ogusol EG-250 (manufactured by Osaka Gas Chemical Co., Ltd.);
HP4032, HP4032D, HP4700 (manufactured by DIC);
ESN-475V (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.);
JER (formerly Epicote) YX8800 (manufactured by Mitsubishi Chemical Corporation);
Marproof G-0105SA, Marproof G-0130SP (manufactured by NOF Corporation);
Epicron N-665, Epicron HP-7200 (manufactured by DIC);
EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (all manufactured by Nippon Kayaku Co., Ltd.);
Adeka Resin EP-4000, Adeka Resin EP-4005, Adeka Resin EP-4100, Adeka Resin EP-4901 (manufactured by ADEKA);
Examples include TECHMORE VG-3101L (manufactured by Printech Co., Ltd.).

Examples of the alicyclic epoxy compound include polyglycidyl etherified polyhydric alcohols having at least one alicyclic structure, or cyclohexene oxide and cyclopentene obtained by epoxidizing a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. Examples include oxide-containing compounds.
Representative compounds of these alicyclic epoxy compounds include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 3,4-epoxy-1-methylcyclohexyl. -3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl -3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate , 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), propane-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3, 4-epoxycyclohexyl) propane, dicyclopentadiene diepoxide, ethylene bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3 , 4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, α-pinene oxide, limonene dioxide and the like.

Moreover, a commercially available product can also be used as the alicyclic epoxy compound. Commercially available products include Celloxide 2021P, Celloxide 2081, Celloxide 2000, Celloxide 3000 (manufactured by Daicel), and the like.

Examples of compounds having an oxetane group in the molecule include 3,7-bis(3-oxetanyl)-5-oxanonane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1, 2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy) butane, difunctional aliphatic oxetane compounds such as 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, 3-ethyl-3-[(phenoxy)methyl]oxetane, 3-ethyl-3-(hexyloxy) Monofunctional oxetane compounds such as methyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(hydroxymethyl)oxetane, 3-ethyl-3-(chloromethyl)oxetane, etc. can be mentioned.

As the compound having an oxetane group in the molecule, commercially available products can also be used. Commercially available products include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, and 4-hydroxybutyl vinyl ether (manufactured by Maruzen Petrochemical Co., Ltd.);
Aronoxetane OXT-121, OXT-221, EXOH, POX, OXA, OXT-101, OXT-211, OXT-212 (manufactured by Toagosei Co., Ltd.);
Examples include etanacol OXBP and OXTP (all manufactured by Ube Industries, Ltd.).

Among these compounds having a cyclic ether group, it is possible to obtain a resin composition with excellent sheet processability (film forming property) and a cured product of a resin composition with excellent adhesive strength. Those in liquid form are preferred. Further, it is preferable that the cyclic ether group is an oxirane group.

The molecular weight of the compound having a cyclic ether group is usually 700 to 5,000, preferably 1,200 to 4,000.
The cyclic ether equivalent of the compound having a cyclic ether group is preferably 100 g/eq or more and 500 g/eq or less, more preferably 150 g/eq or more and 300 g/eq or less.
By using a resin composition in which the cyclic ether equivalent of the compound having a cyclic ether group is within the above range, a sealing material with strong adhesive strength and excellent curability can be efficiently produced.
These compounds having a cyclic ether group can be used alone or in combination of two or more.
The cyclic ether equivalent in the present invention means the value obtained by dividing the molecular weight by the number of cyclic ether groups.

The content of the compound having a cyclic ether group is preferably 5 to 50 parts by weight, more preferably 5 to 40 parts by weight, and even more preferably 5 to 25 parts by weight, based on 100 parts by weight of component (A). It is.
By setting the content of the compound having a cyclic ether group within the above range, a cured product of the resin composition with better adhesive strength can be easily obtained.

[Component (C): Photocationic polymerization initiator]
The resin composition of the present invention contains a photocationic polymerization initiator as component (C).
A photocationic polymerization initiator is a compound that generates cationic species upon irradiation with light to initiate a curing reaction of a cationically curable compound, and consists of a cationic part that absorbs light and an anionic part that becomes a source of acid.

Examples of photocationic polymerization initiators include sulfonium salt compounds, iodonium salt compounds, phosphonium salt compounds, ammonium salt compounds, antimonate compounds, diazonium salt compounds, selenium salt compounds, and oxonium salt compounds. , bromine salt compounds, and the like. Among these, sulfonium salt compounds are preferred, and aromatic sulfonium salt compounds having an aromatic group are more preferred, from the viewpoint of excellent compatibility with component (B) and excellent storage stability of the resulting resin composition. preferable.

Examples of sulfonium salt compounds include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, and 4,4'-bis[diphenylsulfonio]diphenylsulfide-bishexafluoro. Phosphate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfide-bishexafluoroantimonate, 7-[di(p-tolyl)sulfonio]-2-isopropylthioxanthone hexafluorophosphate, 7 -[di(p-tolyl)sulfonio]-2-isopropylthioxanthone hexafluoroantimonate, 7-[di(p-tolyl)sulfonio]-2-isopropyltetrakis(pentafluorophenyl)borate, phenylcarbonyl-4'-diphenyl Sulfonio-diphenylsulfide-hexafluorophosphate, phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-hexafluoroantimonate, 4-tert-butylphenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-hexafluorophosphate, 4-tert-butylphenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-hexafluoroantimonate, 4-tert-butylphenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide-tetrakis(pentafluorophenyl)borate, thio Phenyldiphenylsulfonium hexafluoroantimonate, thiophenyldiphenylsulfonium hexafluoroantimonate, 4-{4-(2-chlorobenzoyl)phenylthio}phenylbis(4-fluorophenyl)sulfonium hexafluorantimonate, thiophenyldiphenylsulfonium hexafluoroantimonate 4,4',4''-tri(β-hydroxyethoxyphenyl)sulfonium hexafluoroantimonate, 4,4'-bis[diphenylsulfonio]diphenylsulfide-bishexafluoroantimonate, diphenyl[ Examples include 4-(phenylthio)phenyl]sulfonium trifluorotrispentafluoroethyl phosphate, tris[4-(4-acetylphenylsulfanyl)phenyl]sulfonium tris[(trifluoromethyl)sulfonyl]methanide, and the like.

Examples of iodonium salt compounds include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di(4-nonylphenyl)iodonium hexafluorophosphate, and (tricumyl)iodonium tetrakis(pentafluorophosphate). Examples include phenyl)borate and the like.

Examples of the phosphonium salt compounds include tri-n-butyl(2,5-dihydroxyphenyl)phosphonium bromide, hexadecyltributylphosphonium chloride, and the like.

Examples of ammonium salt compounds include benzyltrimethylammonium chloride, phenyltributylammonium chloride, benzyltrimethylammonium bromide, and the like.

Antimonate compounds include triphenylsulfonium hexafluoroantimonate, p-(phenylthio)phenyldiphenylsulfonium hexafluoroantimonate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis[4-(diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate and diallyliodonium hexafluoroantimonate.

These photocationic polymerization initiators can be used alone or in combination of two or more.

Moreover, a commercially available product can also be used as a photocationic polymerization initiator. Commercially available products include Cylacure UVI-6970, Cylacure UVI-6974, Cylacure UVI-6990, Cylacure UVI-950 (all manufactured by Union Carbide), Irgacure 250, Irgacure 261, and Irgacure 264 (all manufactured by Ciba Specialty Chemicals). SP-150, SP-151, SP-170, Optomer SP-171 (manufactured by ADEKA), CG-24-61 (manufactured by Ciba Specialty Chemicals), DAICAT II (manufactured by Daicel), UVAC1590, UVAC1591 (manufactured by Daicel Cytec), CI-2064, CI-2639, CI-2624, CI-2481, CI-2734, CI-2855, CI-2823, CI-2758, CIT-1682 (and above) , manufactured by Nippon Soda), PI-2074 (manufactured by Rhodia), FFC509 (manufactured by 3M), BBI-102, BBI-101, BBI-103, MPI-103, TPS-103, MDS-103, DTS-103 , NAT-103, NDS-103 (manufactured by Midori Kagaku Co., Ltd.), CD-1010, CD-1011, CD-1012 (manufactured by Sartomer), CPI-100P, CPI-101A, CPI-200K, CPI-310B ( (manufactured by Sun-Apro), etc.

The content of the photocationic polymerization initiator is usually 0.02 to 2 parts by mass, preferably 0.03 to 1 part by mass, and more preferably 0.04 to 0 parts by mass, per 100 parts by mass of component (B). .5 parts by mass.
By setting the content of the photocationic polymerization initiator within the above range, a cured product of the resin composition with better adhesive strength can be easily obtained.
If the content of the photocationic polymerization initiator is too large, the elastic modulus after curing will become too high, and there is a risk that the adhesive strength of the cured product of the resin composition will decrease.

The resin composition of the present invention may contain components other than the component (A), component (B), and component (C).
Components other than the component (A), component (B), and component (C) include a tackifier, a silane coupling agent, a solvent, and the like.

Examples of tackifiers include rosin resins such as rosin resins, rosin ester resins, and rosin-modified phenol resins; hydrogenated rosin resins obtained by hydrogenating these rosin resins;
Terpene resins such as terpene resins, aromatic modified terpene resins, and terpene phenol resins; hydrogenated terpene resins obtained by hydrogenating these terpene resins;
α-methylstyrene homopolymer resin, α-methylstyrene/styrene copolymer resin, styrene monomer/aliphatic monomer copolymer resin, styrenic monomer/α-methylstyrene/aliphatic monomer copolymer resin Styrenic resins such as resins, styrenic monomer homopolymer resins, styrenic monomer/aromatic monomer copolymer resins; Hydrogenated styrenic resins obtained by hydrogenating these styrenic resins;
C5 petroleum resin obtained by copolymerizing C5 fractions such as pentene, isoprene, piperine, 1,3-pentadiene, etc. produced by thermal decomposition of petroleum naphtha, and hydrogenated petroleum resin of this C5 petroleum resin;
Examples include C9 petroleum resins obtained by copolymerizing C9 fractions such as indene and vinyltoluene produced by thermal decomposition of petroleum naphtha, and hydrogenated petroleum resins using this C9 petroleum resin. Among these, styrene resins are preferred, and styrene monomer/aliphatic monomer copolymer resins are more preferred.
These tackifiers can be used alone or in combination of two or more.

Commercially available products can also be used as the tackifier. Commercially available products include terpene resins such as YS Resin P and A series, Clearon (registered trademark) P series (manufactured by Yasuhara Chemical), Picolite A and C series (manufactured by PINOVA);
Aliphatic petroleum resins such as Quinton (registered trademark) A, B, R, CX series (manufactured by Nippon Zeon Co., Ltd.);
Styrenic resins such as FTR (registered trademark) series (manufactured by Mitsui Chemicals);
Alcon P, M series (manufactured by Arakawa Chemical Co., Ltd.), ESCOREZ (registered trademark) series (manufactured by ExxonMobil Chemical Company), EASTOTAC (registered trademark) series (manufactured by Eastman Chemical Company), IMARV (registered trademark) series (manufactured by Idemitsu Alicyclic petroleum resins such as those manufactured by Kosansha;
Examples include ester-based resins such as Foral series (manufactured by PINOVA), Pencel (registered trademark) A series, Ester gum, Super Ester, and Pine Crystal (registered trademark) (manufactured by Arakawa Chemical Industries, Ltd.).

The weight average molecular weight of the tackifier is preferably 100 to 10,000, more preferably 500 to 5,000 from the viewpoint of imparting excellent tackiness.
The softening point of the tackifier is preferably 50 to 160°C, more preferably 60 to 140°C, and even more preferably 70 to 130°C, from the viewpoint of imparting excellent tackiness.

When the resin composition of the present invention contains a tackifier, its content is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass, based on 100 parts by mass of component (A). .
By setting the content of the tackifier within the above range, a cured product of the resin composition with better adhesive strength can be easily obtained.

Examples of the silane coupling agent include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane. A silane coupling agent having a (meth)acryloyl group such as methoxysilane;
A silane coupling agent having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltris(2-methoxyethoxy)silane;
Epoxy groups such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. A silane coupling agent having;
A silane coupling agent having a styryl group such as p-styryltrimethoxysilane and p-styryltriethoxysilane;
N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane , 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N -(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride and other silane coupling agents having an amino group;
A silane coupling agent having a ureido group such as 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane;
A silane coupling agent having a halogen atom such as 3-chloropropyltrimethoxysilane and 3-chloropropyltriethoxysilane;
A silane coupling agent having a mercapto group such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane;
A silane coupling agent having a sulfide group such as bis(trimethoxysilylpropyl)tetrasulfide and bis(triethoxysilylpropyl)tetrasulfide;
A silane coupling agent having an isocyanate group such as 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane;
A silane coupling agent having an allyl group such as allyltrichlorosilane, allyltriethoxysilane, allyltrimethoxysilane;
Examples include silane coupling agents having a hydroxyl group such as 3-hydroxypropyltrimethoxysilane and 3-hydroxypropyltriethoxysilane.
These silane coupling agents can be used alone or in combination of two or more.

When the resin composition of the present invention contains a silane coupling agent, the content thereof is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 10 parts by mass, based on 100 parts by mass of component (A). 5 parts by mass.
By setting the content of the silane coupling agent within the above range, a cured product of the resin composition with better adhesive strength can be easily obtained.

As a solvent, an aliphatic hydrocarbon solvent such as n-hexane or n-heptane;
Aromatic hydrocarbon solvents such as toluene and xylene;
Halogenated hydrocarbon solvents such as dichloromethane, ethylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, and monochlorobenzene;
Alcohol solvents such as methanol, ethanol, propanol, butanol, propylene glycol monomethyl ether;
Ketone solvents such as acetone, methyl ethyl ketone, 2-pentanone, isophorone, cyclohexanone;
Ester solvents such as ethyl acetate and butyl acetate;
Cellosolve solvents such as ethyl cellosolve;
Examples include ether solvents such as 1,3-dioxolane; and the like.
These solvents can be used alone or in combination of two or more. The content of the solvent can be appropriately determined in consideration of coatability, film thickness, etc.

Furthermore, the resin composition of the present invention may contain components other than the tackifier, silane coupling agent, and solvent within a range that does not impede the effects of the present invention.
Components other than the tackifier, silane coupling agent, and solvent include antistatic agents, stabilizers, antioxidants, plasticizers, lubricants, color pigments, and the like. These contents may be determined as appropriate depending on the purpose.

The resin composition of the present invention can be prepared by appropriately mixing and stirring predetermined components according to a conventional method.

2) Sealing sheet The sealing sheet of the present invention is the following sealing sheet (α), sealing sheet (β), or sealing sheet (γ).
Sealing sheet (α): A sealing sheet consisting of a base material or release film and an adhesive layer formed on the base material or release film, the adhesive layer being made of the resin composition of the present invention. A sealing sheet that is formed using
Sealing sheet (β): A sealing sheet consisting of two release films and an adhesive layer sandwiched between the two release films, wherein the adhesive layer contains the resin composition of the present invention. A sealing sheet that is formed using
Sealing sheet (γ): A sealing sheet consisting of a release film, a gas barrier film, and an adhesive layer sandwiched between the release film and the gas barrier film, wherein the adhesive layer is made of the resin composition of the present invention. A sealing sheet that is formed using a material.
Note that these sealing sheets represent the state before use, and when using the sealing sheet of the present invention, the release film is usually peeled off and removed.

As a base material constituting the sealing sheet (α), a resin film can usually be used.
The resin components of the resin film include polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, acrylic resin, cyclo Examples include olefin polymers, aromatic polymers, polyurethane polymers, and the like.
The thickness of the base material is not particularly limited, but from the viewpoint of heat shrinkage in the drying process of the adhesive layer and versatility, it is preferably 10 to 500 μm, more preferably 10 to 300 μm, and even more preferably 15 to 200 μm. be.

The release film that constitutes the sealing sheet (α) functions as a support during the manufacturing process of the sealing sheet (α), and also protects the adhesive layer until the sealing sheet (α) is used. Functions as a sheet.

As the release film, conventionally known release films can be used. For example, a release film having a release layer treated with a release agent on a base material for release film may be mentioned.
Examples of base materials for release films include paper bases such as glassine paper, coated paper, and high-quality paper; laminated paper in which thermoplastic resin such as polyethylene is laminated to these paper bases; polyethylene terephthalate resin, polybutylene terephthalate resin, Examples include plastic films such as polyethylene naphthalate resin, polypropylene resin, and polyethylene resin.
Examples of the release agent include rubber elastomers such as silicone resins, olefin resins, isoprene resins, and butadiene resins, long-chain alkyl resins, alkyd resins, and fluorine resins.
The thickness of the release film is not particularly limited, but is usually about 20 to 250 μm.

The method for manufacturing the sealing sheet (α) is not particularly limited. For example, the sealing sheet (α) can be manufactured using a casting method.
When producing the sealing sheet (α) by a casting method, the resin composition of the present invention is applied to the release layer surface of the base material or release film that has been subjected to release treatment using a known method. A sealing sheet (α) can be obtained by drying the film.

Examples of methods for applying the resin composition include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.

Methods for drying the coating film include conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation.
The conditions for drying the coating film are, for example, 80 to 150° C. for 30 seconds to 5 minutes.

The adhesive layer of the sealing sheet (α) can be formed by photocuring a coating film formed using the resin composition of the present invention.

Conditions for photocuring are not particularly limited. The adhesive layer can be photocured by irradiation with active energy rays such as ultraviolet rays, visible rays, X-rays, and electron beams.
In the present invention, photocuring by ultraviolet irradiation is preferred from the viewpoint of being able to obtain a sealing sheet with excellent transparency.

Specific examples of ultraviolet sources that irradiate ultraviolet rays include light sources such as ultra-high-pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, black light fluorescent lamps, and metal halide lamps. Further, as the wavelength of the ultraviolet rays to be irradiated, a wavelength range of 190 to 380 nm can be used.
The amount of ultraviolet rays to be irradiated is preferably about 50 to 1000 mW/cm ² in illuminance and 50 to 1000 mJ/cm ² in light intensity.
The irradiation time of ultraviolet rays is usually about 0.1 to 1000 seconds, preferably about 1 to 500 seconds.

The thickness of the adhesive layer of the sealing sheet (α) is usually 1 to 50 μm, preferably 5 to 30 μm. An adhesive layer having a thickness within the above range is suitably used as a sealing material.
The thickness of the adhesive layer can be measured according to JIS K 7130 (1999) using a known thickness meter.

The adhesive layer of the sealing sheet of the present invention has excellent adhesive strength.
The adhesive strength of the adhesive layer is usually 1 to 20 N/25 mm, preferably 2.5 to 15 N/25 mm, when a 180° peel test is performed at a temperature of 23° C. and a relative humidity of 50%. This 180° peel test can be measured by the method described in Examples.

The adhesive layer of the sealing sheet of the present invention has excellent colorless transparency.
The total light transmittance of the adhesive layer having a thickness of 20 μm after the photocuring treatment is preferably 85% or more, more preferably 90% or more. There is no particular upper limit to the total light transmittance, but it is usually 95% or less.
As mentioned above, in the resin composition of the present invention, a modified polyolefin resin is used as the component (A), and a compound having a cyclic ether group that is highly compatible with the component (A) is used as the component (B). Use as. As a result, the adhesive layer of the sealing sheet of the present invention has a high total light transmittance. This total light transmittance can be measured by the method described in Examples.

In addition, the adhesive layer with a thickness of 20 μm obtained by the photocuring treatment has L* in the CIE1976L*a*b* color system defined in JIS Z 8781-4 (2013) when measured. The value is between 90 and 98. Further, the a* value is between -2 and 2. Further, the b* value is between -2 and 2.

In the L*a*b* color system, L* indicates lightness, and a* and b* indicate hue and saturation, respectively. If a* is a positive value, the color will be red, if a* is a negative value, the color will be green, if b* is a positive value, the color will be yellow, and if b* is a negative value, the color will be blue. Indicates saturation. As the absolute values of a* and b* become smaller, the color becomes colorless.

The L* value of the adhesive layer obtained by the photocuring treatment is preferably 92 to 98, more preferably 94 to 98.
Further, the a* value is usually -2 to 2, preferably -1 to 1, more preferably -0.5 to 0.5.
Further, the b* value is usually -2 to 2, preferably -1 to 1, and more preferably -0.5 to 0.5.
The adhesive layer obtained by the photocuring treatment has little bias in the red direction (+a*), green direction (-a*), yellow direction (+b*), and blue direction (-b*).
A resin composition that can form an adhesive layer in which L* is in the above range and the color gamut of a* and b* is in the above range has a high total light transmittance and has very little coloring. Therefore, it is suitably used as a sealing material for light emitting devices such as organic EL elements.
Therefore, the sealing sheet of the present invention is suitably used in optical applications such as sealing materials for light emitting devices such as organic EL elements.
The L*a*b* value in the CIE1976L*a*b* color system can be measured by the method described in Examples.

The yellowness (YI value) of the sealing sheet is usually 0.01 to 2, preferably 0.01 to 1. This yellowness can be measured by the method described in Examples.

Furthermore, the adhesive layer of the sealing sheet of the present invention has excellent water vapor barrier properties.
The water vapor permeability of the adhesive layer having a thickness of 20 μm obtained by the photocuring treatment is usually 0.1 to 200 g/m ² /day, preferably 0.1 to 150 g/m ² /day. This water vapor transmission rate can be measured by the method described in Examples.

The release film and adhesive layer constituting the sealing sheet (β) may be the same as those shown as the release film and adhesive layer constituting the sealing sheet (α), respectively.

The two release films in the sealing sheet (β) may be the same or different, but preferably the two release films have different release forces. Since the peeling forces of the two release films are different, problems are less likely to occur when using the sealing sheet. That is, by making the peeling forces of the two release films different, the step of first peeling off the release film can be performed more efficiently.

The method for manufacturing the sealing sheet (β) is not particularly limited.
For example, when manufacturing the sealing sheet (β) by a casting method, the resin composition of the present invention is applied to a release film after being peeled off using a method similar to the method for manufacturing the sealing sheet (α). An adhesive layer with a release film is produced by coating the surface of the release layer, drying the resulting coating film, and photo-curing the coating film, and then applying another release film on the adhesive layer. A sealing sheet (β) can be obtained by stacking the sheets on top of each other.

The release film and adhesive layer constituting the sealing sheet (γ) are the same as those shown as the release film and adhesive layer constituting the sealing sheet (α) or the sealing sheet (β), respectively. Can be mentioned.
The gas barrier film constituting the sealing sheet (γ) is not particularly limited as long as it has water vapor barrier properties.

The gas barrier film preferably has a water vapor permeability of 0.1 g/m ² /day or less under an environment of a temperature of 40° C. and a relative humidity of 90% (hereinafter abbreviated as “90% RH”). It is more preferably .05 g/m ² /day or less, and even more preferably 0.005 g/m ² /day or less.
If the water vapor permeability of the gas barrier film is 0.1 g/m ² /day or less in an environment with a temperature of 40°C and 90% RH, oxygen and moisture will not be present inside the device, such as an organic EL device formed on the substrate. It is possible to effectively suppress the deterioration of the electrodes and organic layer due to the infiltration of substances such as the like.
The permeability of water vapor and the like of the gas barrier film can be measured using a known gas permeability measuring device.

Examples of the gas barrier film include metal foil, thin glass, and resin films. Among these, resin films are preferred, and gas barrier films having a base material and a gas barrier layer are more preferred.

Examples of the resin component constituting the base material include those similar to those of the resin film that can be used as the base material constituting the sealing sheet (α).
The thickness of the base material is not particularly limited, but from the viewpoint of ease of handling, it is preferably 0.5 to 500 μm, more preferably 1 to 200 μm, and still more preferably 5 to 100 μm.

The material of the gas barrier layer is not particularly limited as long as it can provide desired gas barrier properties. The gas barrier layer is obtained by performing a modification treatment on a gas barrier layer made of an inorganic vapor-deposited film, a gas barrier layer containing a gas barrier resin, or a layer containing a polymer compound (hereinafter sometimes referred to as a "polymer layer"). Gas Barrier Layer [In this case, the gas barrier layer does not mean only a region modified by ion implantation treatment, etc., but also means a "polymer layer including a modified region." ], etc.
Among these, a gas barrier layer made of an inorganic vapor-deposited film or a gas barrier layer obtained by subjecting a polymer layer to a modification treatment is preferred because a thin layer with excellent gas barrier properties can be efficiently formed. The gas barrier film may have two or more of these gas barrier layers.

Examples of the inorganic vapor deposited film include vapor deposited films of inorganic compounds and metals.
Inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, zinc oxide, indium oxide, tin oxide, zinc tin oxide, etc. are used as raw materials for the deposited film of inorganic compounds;
Inorganic nitrides such as silicon nitride, aluminum nitride, titanium nitride;
Inorganic carbides; Inorganic sulfides; Inorganic oxynitrides such as silicon oxynitride;
Examples include inorganic oxycarbide; inorganic nitride carbide; inorganic oxynitride carbide.
Examples of raw materials for the metal vapor deposition film include aluminum, magnesium, zinc, and tin.
These can be used alone or in combination of two or more.

Among these, inorganic vapor-deposited films made from inorganic oxides, inorganic nitrides, or metals are preferred from the viewpoint of gas barrier properties, and from the viewpoint of colorless transparency, films made from inorganic oxides or inorganic nitrides are preferred. Inorganic vapor deposited films are preferred. Further, the inorganic vapor deposited film may be a single layer or a multilayer.

The thickness of the inorganic vapor-deposited film is usually 1 nm or more and 2000 nm or less, preferably 3 nm or more and 1000 nm or less, more preferably 5 nm or more and 500 nm or less, and even more preferably 40 nm or more and 200 nm or less, from the viewpoint of gas barrier properties and handleability.

The method of forming the inorganic vapor deposited film is not particularly limited, and any known method can be used. Examples of methods for forming the inorganic vapor deposition film include PVD (physical vapor deposition) methods such as vacuum evaporation method, sputtering method, and ion plating method, thermal CVD (chemical vapor deposition) method, plasma CVD method, and photoCVD method. Examples include CVD methods such as, and atomic layer deposition methods (ALD methods).

In the gas barrier layer containing a gas barrier resin, examples of the gas barrier resin used include polyvinyl alcohol or a partially saponified product thereof, ethylene-vinyl alcohol copolymer, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, and polychlorotrifluoro. Examples include resins such as ethylene that are difficult for oxygen, water vapor, etc. to permeate.

From the viewpoint of gas barrier properties, the thickness of the gas barrier layer containing the gas barrier resin is usually 1 nm or more and 2000 nm or less, preferably 3 nm or more and 1000 nm or less, more preferably 5 nm or more and 500 nm or less, and even more preferably 40 nm or more and 200 nm or less.

Examples of a method for forming a gas barrier layer containing a gas barrier resin include a method of applying a gas barrier layer forming solution containing a gas barrier resin onto a base material or other layer, and drying the resulting coating film as appropriate. .

The method for applying the solution for forming a gas barrier layer is not particularly limited, and the methods mentioned above as the method for applying the resin composition can be used.
The method for drying the coating film is not particularly limited either, and the methods listed above as methods for drying the coating film of the resin composition can be used.

In the gas barrier layer formed by modifying the surface of the polymer layer, examples of the polymer compound used include silicon-containing polymer compounds, polyimide, polyamide, polyamideimide, polyphenylene ether, polyether ketone, polyether ether ketone, polyolefin, and polyester. , polycarbonate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, acrylic resin, alicyclic hydrocarbon resin, aromatic polymer, and the like.
These polymer compounds can be used alone or in combination of two or more.

Among these polymer compounds, silicon-containing polymer compounds are preferred from the viewpoint of being able to form a gas barrier layer with better gas barrier properties. Examples of silicon-containing polymer compounds include polysilazane compounds, polycarbosilane compounds, polysilane compounds, polyorganosiloxane compounds, poly(disilanylenephenylene) compounds, and poly(disilanylene ethynylene) compounds. can be mentioned. Among these, polysilazane compounds are preferred from the viewpoint of being able to form a gas barrier layer having excellent gas barrier properties even if it is thin. By subjecting a layer containing a polysilazane compound to a modification treatment, a layer (silicon oxynitride layer) containing oxygen, nitrogen, and silicon as main constituent atoms can be formed.

A polysilazane compound is a polymer compound having a repeating unit containing a -Si-N- bond (silazane bond) in the molecule. Specifically, formula (1)

A compound having a repeating unit represented by is preferred. Further, the number average molecular weight of the polysilazane compound used is not particularly limited, but is preferably 100 to 50,000.

In the formula (1), n represents any natural number.
Rx, Ry, and Rz each independently represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted cycloalkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted alkenyl group It represents a non-hydrolyzable group such as an aryl group or an alkylsilyl group having a group.

Among these, Rx, Ry, and Rz are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and a hydrogen atom is particularly preferred.

Examples of the polysilazane compound having a repeating unit represented by the formula (1) include inorganic polysilazane in which Rx, Ry, and Rz are all hydrogen atoms, and organic polysilazane in which at least one of Rx, Ry, and Rz is not a hydrogen atom. It may be.

Furthermore, in the present invention, a polysilazane modified product can also be used as the polysilazane compound. Examples of polysilazane modified products include JP-A-62-195024, JP-A-2-84437, JP-A-63-81122, JP-A-1-138108, JP-A-2-175726, JP-A-5-238827, JP-A-6-122852, JP-A-6-306329, JP-A-6-299118, JP-A-9-31333, JP-A-5-345826, JP-A-Heisei Examples include those described in Publication No. 4-63833.
Among these, perhydropolysilazane in which Rx, Ry, and Rz are all hydrogen atoms is preferred as the polysilazane compound from the viewpoint of easy availability and ability to form an ion-implanted layer having excellent gas barrier properties.
Furthermore, as the polysilazane compound, commercially available products such as glass coating materials can be used as they are.
The polysilazane compounds can be used alone or in combination of two or more.

In addition to the above-mentioned polymer compound, the polymer layer may contain other components as long as they do not impede the object of the present invention. Other components may include the additives listed above as components other than component (A), component (B), and component (C).
The content of the polymer compound in the polymer layer is preferably 50% by mass or more, more preferably 70% by mass or more, since a gas barrier layer with better gas barrier properties can be formed.

The thickness of the polymer layer is not particularly limited, but is usually 20 nm or more and 50 μm or less, preferably 30 nm or more and 1 μm or less, and more preferably 40 nm or more and 500 nm or less.

The polymer layer is formed, for example, by applying a liquid obtained by dissolving or dispersing a polymer compound in an organic solvent onto a base material or other layer using a known coating method, and drying the resulting coating film. be able to.

As the organic solvent, those listed as components other than the component (A), component (B), and component (C) can be used.
These organic solvents can be used alone or in combination of two or more.

The coating method is not particularly limited, and the methods mentioned above as the method for coating the resin composition can be used.
The method for drying the coating film is not particularly limited either, and the methods listed above as methods for drying the coating film of the resin composition can be used.
The heating temperature is usually 80 to 150°C, and the heating time is usually several tens of seconds to several tens of minutes.

Examples of methods for modifying the surface of the polymer layer include ion implantation treatment, plasma treatment, ultraviolet irradiation treatment, heat treatment, and the like.
The ion implantation process is a method of modifying the polymer layer by injecting accelerated ions into the polymer layer, as will be described later.
Plasma treatment is a method of exposing a polymer layer to plasma to modify the polymer layer. For example, plasma treatment can be performed according to the method described in JP-A-2012-106421.
The ultraviolet irradiation treatment is a method of modifying the polymer layer by irradiating the polymer layer with ultraviolet rays. For example, ultraviolet modification treatment can be performed according to the method described in JP-A-2013-226757.

Among these gas barrier layers, ion implantation is used in layers containing silicon-containing polymer compounds from the viewpoint of efficiently modifying the inside of the polymer layer without roughening the surface and forming a gas barrier layer with better gas barrier properties. Those obtained by processing are preferred.

The ions to be implanted into the polymer layer include ions of rare gases such as argon, helium, neon, krypton, and xenon;
Ions such as fluorocarbons, hydrogen, nitrogen, oxygen, carbon dioxide, chlorine, fluorine, and sulfur;
Ions of alkane gases such as methane and ethane;
Ions of alkene gases such as ethylene and propylene;
Ions of alkadiene gases such as pentadiene and butadiene;
Ions of alkyne gases such as acetylene;
Ions of aromatic hydrocarbon gases such as benzene and toluene;
Ions of cycloalkane gases such as cyclopropane;
Ions of cycloalkene gases such as cyclopentene;
Examples include metal ions; organosilicon compound ions; and the like.
These ions can be used alone or in combination of two or more.
Among these, ions of rare gases such as argon, helium, neon, krypton, and xenon are preferred because ions can be more easily implanted and a gas barrier layer having better gas barrier properties can be formed.

The amount of ions to be implanted can be determined as appropriate depending on the intended use of the gas barrier film (required gas barrier properties, colorless transparency, etc.).

Examples of methods for implanting ions include a method of irradiating ions accelerated by an electric field (ion beam), a method of implanting ions in plasma (plasma ions), and the like. Among these, the latter method of implanting plasma ions (plasma ion implantation method) is preferred from the viewpoint of easily forming the desired gas barrier layer.

In the plasma ion implantation method, for example, plasma is generated in an atmosphere containing a plasma-generating gas such as a rare gas, and ions (positive ions) in the plasma are generated by applying a negative high voltage pulse to a polymer layer. This can be done by injecting it into the surface of the polymer layer. More specifically, the plasma ion implantation method can be carried out by the method described in WO2010/107018 pamphlet and the like.

The thickness of the region into which ions are implanted can be controlled by the type of ions, applied voltage, processing time, and other implantation conditions, and can be controlled depending on the thickness of the polymer layer and the purpose of use of the gas barrier film. Although it may be determined, it is usually 10 nm or more and 400 nm or less.

The implantation of ions can be confirmed by elemental analysis measurement at a depth of about 10 nm from the surface of the polymer layer using X-ray photoelectron spectroscopy (XPS).

The method for manufacturing the sealing sheet (γ) is not particularly limited. For example, in the method for manufacturing the sealing sheet (β) described above, the sealing sheet (γ) can be manufactured by replacing one of the release films with a gas barrier film.
Alternatively, after manufacturing the sealing sheet (β), peeling off one release film and pasting the exposed adhesive layer with a gas barrier film, the sealing sheet (γ) can be manufactured. You can also do it. In this case, when the sealing sheet (β) has two release films having different peeling forces, from the viewpoint of ease of handling, it is preferable to peel the release film with the smaller peeling force.

As described above, the adhesive layer of the sealing sheet of the present invention has excellent adhesive strength, colorless transparency, and water vapor barrier properties. Therefore, the sealing sheet of the present invention is suitably used in optical applications such as sealing materials for light emitting devices such as organic EL elements.

3) Sealed body The sealed body of the present invention is obtained by sealing an object to be sealed using the sealing sheet of the present invention.
"Sealed using the sealing sheet of the present invention" means that the release film constituting the sealing sheet of the present invention is removed to expose the adhesive layer, and the adhesive layer is applied to the object to be sealed. This refers to covering the object by bringing it into close contact with the object.
The sealed body of the present invention includes, for example, a substrate, an element (sealed object) formed on the substrate, and a sealing material for sealing the element, Examples include those in which the sealing material is an adhesive layer of the sealing sheet of the present invention.

The substrate is not particularly limited, and various substrate materials can be used. In particular, it is preferable to use a substrate material with high visible light transmittance. Further, it is preferable to use a material that has high blocking performance for blocking moisture and gas from entering from the outside of the element, and has excellent solvent resistance and weather resistance. Specifically, transparent inorganic materials such as quartz and glass; polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, polyvinylidene fluoride, acetyl cellulose, brominated phenoxy, aramids, polyimides, Examples include transparent plastics such as polystyrenes, polyarylates, polysulfones, and polyolefins, and the above-mentioned gas barrier films.
The thickness of the substrate is not particularly limited, and can be appropriately selected in consideration of light transmittance and ability to block the inside and outside of the element.

Examples of the object to be sealed include organic EL elements, organic EL display elements, liquid crystal display elements, solar cell elements, and the like.

The method for manufacturing the sealed body of the present invention is not particularly limited.
For example, in the case of the structure of the sealing sheet (α) of the present invention, the object to be sealed is sealed by the adhesive layer of the sealing sheet by pasting the adhesive layer onto the object to be sealed. If a release film is used for the sealing sheet (α), the release film is removed after sealing.
In the case of the structure of the sealing sheet (β) of the present invention, one release film of the sealing sheet (β) is removed, a gas barrier film is laminated to the exposed adhesive layer, and then the other release film is attached. By removing the adhesive layer and pasting the adhesive layer onto the object to be sealed, the object to be sealed is sealed with the adhesive layer of the sealing sheet.
In the case of the structure of the sealing sheet (γ) of the present invention, the release film is removed and the adhesive layer is pasted onto the object to be sealed, so that the object is sealed with the adhesive layer of the sealing sheet. make it stop

Adhesion conditions for bonding the adhesive layer of the sealing sheet and the object to be sealed are not particularly limited. The bonding temperature is, for example, 23 to 100°C, preferably 23 to 80°C, more preferably 23 to 40°C. This adhesion treatment may be performed while applying pressure.
In addition, in the present invention, a sealing sheet having an uncured adhesive layer (a dry coating film of the resin composition of the present invention) is used, and the uncured adhesive layer of the sealing sheet and the to-be-sealed After the objects are bonded, the uncured adhesive layer may be photocured.
As the curing conditions at this time, the conditions described above can be used.

The sealed body of the present invention is obtained by sealing an object with the sealing sheet of the present invention.
Therefore, in the sealed body of the present invention, the performance of the sealed object is maintained over a long period of time.

Hereinafter, the present invention will be explained in more detail with reference to Examples. However, the present invention is not limited to the following examples.
Parts and percentages in each example are by weight unless otherwise specified.

In the following examples and comparative examples, the modified polyolefin resin [component (A)], the compound having a cyclic ether group [component (B)], and the photocationic polymerization initiator [component (C)] are as follows: I used the one from
Modified polyolefin resin [(A) component]
Acid-modified α-olefin polymer [manufactured by Mitsui Chemicals, trade name: UNISTOL H-200, number average molecular weight: 47,000]

Compound having a cyclic ether group [component (B)]
(1) Compound having a cyclic ether group (B-1)
Dicyclopentadiene dimethanol diglycidyl ether [manufactured by ADEKA, trade name: ADEKA RIN EP-4088L, cyclic ether equivalent: 165 g/eq, liquid at 25°C]
(2) Compound having a cyclic ether group (B-2)
2-Ethylhexyloxetane [manufactured by Toagosei Co., Ltd., product name: OXT-212, cyclic ether equivalent: 226 g/eq, liquid at 25°C]
(3) Compound having a cyclic ether group (B-3)
Triglycidyl isocyanurate [manufactured by Nissan Chemical Industries, Ltd., trade name: TEPIC-FL, cyclic ether equivalent: 165-185 g/eq, liquid at 25°C]
(4) Compound having a cyclic ether group (B-4)
Hydrogenated bisphenol A epoxy resin [manufactured by Mitsubishi Chemical Corporation, product name: YX8034, cyclic ether equivalent: 270 g/eq, liquid at 25°C]

Photocationic polymerization initiator [component (C)]
(1) Photocationic polymerization initiator (C-1)
Triarylsulfonium salt [manufactured by San-Apro Co., Ltd., product name: CPI-200K, anion: anion having a hexafluorophosphate skeleton]
(2) Photocationic polymerization initiator (C-2)
Triarylsulfonium salt [manufactured by San-Apro, trade name: CPI-310B, anion: tetrakis(pentafluorophenyl)borate]

[Example 1]
100 parts of acid-modified α-olefin polymer (A), 25 parts of compound having a cyclic ether group (B-1), 0.1 part of photocationic polymerization initiator (C-1), tackifier [styrenic monomer/ 50 parts of aliphatic monomer copolymer resin (manufactured by Mitsui Chemicals, trade name: FTR6100, softening point 95°C), and silane coupling agent [8-glycidoxyoctyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., (Product name: KBM4803)] was dissolved in toluene to prepare a resin composition (1) having a solid content concentration of 27%.
This resin composition (1) was applied onto the release-treated surface of a release film (manufactured by Lintec Corporation, product name: SP-PET382150), and the resulting coating film was dried at 100°C for 2 minutes to give a thickness of 20 μm. An adhesive layer was formed, and the release-treated surface of another release film (manufactured by Lintec, trade name: SP-PET381031) was laminated thereon. After that, using an ultraviolet irradiation device (manufactured by Eye Graphics, product name: US2-0801 <2>), the coating film is cured by irradiating ultraviolet rays at an illuminance of 200 mW/cm ² and a light amount of 200 mJ/cm ² and sealing. A sheet (1) was obtained.

[Examples 2 to 4]
Resin compositions (2) to (4) were prepared in the same manner as in Example 1, except that the compound (B-1) having a cyclic ether group was used in the amount shown in Table 1. Sealing sheets (2) to (4) were obtained using the following methods.

[Example 5]
A resin composition was prepared in the same manner as in Example 1, except that the compound (B-2) having a cyclic ether group was used instead of the compound (B-1) having a cyclic ether group. (5) was prepared, and a sealing sheet (5) was obtained using this resin composition.

[Example 6]
A resin composition was prepared in the same manner as in Example 1, except that the compound (B-3) having a cyclic ether group was used instead of the compound (B-1) having a cyclic ether group. (6) was prepared, and a sealing sheet (6) was obtained using this resin composition.

[Example 7 and 8]
Resin compositions (7) and (8) were prepared in the same manner as in Example 1, except that the photocationic polymerization initiator (C-1) was used in the amount shown in Table 1. Using this method, sealing sheets (7) and (8) were obtained.

[Example 9]
In Example 1, the resin composition (9 ) was prepared, and a sealing sheet (9) was obtained using this resin composition.

[Example 10]
A resin composition (10) was prepared in the same manner as in Example 1, except that the content of the tackifier was changed to 25 parts, and a sealing sheet (10) was obtained using this resin composition.

[Comparative example 1]
A resin composition (11) was prepared in the same manner as in Example 1, except that the acid-modified α-olefin polymer (A) was not used.
Although an attempt was made to produce a sealing sheet using this resin composition in the same manner as in Example 1, the sheet processability (film-forming property) was low and it was not possible to obtain a sealing sheet.

[Comparative example 2]
In Example 1, a resin composition (12) was prepared in the same manner as in Example 1 except that the compound having a cyclic ether group (B-1) was not used, and this resin composition was used to form a sealing sheet. (12) was obtained.

[Comparative example 3]
In Example 1, instead of using the compound (B-1) having a cyclic ether group, the compound (B-4) having a cyclic ether group was used, and the photocationic polymerization initiator (C-1) was used. A resin composition (13) was prepared in the same manner as in Example 1 except that it was not used, and a sealing sheet (13) was obtained using this resin composition.

The following measurements and evaluations were performed on the sealing sheets (1) to (10), (12) and (13) obtained in Examples 1 to 10 and Comparative Examples 2 and 3. The results are shown in Table 1.
[Adhesive force measurement]
One release film of the sealing sheet having a width of 25 mm was peeled off to expose the adhesive layer. The exposed adhesive layer was bonded to a polyethylene terephthalate film (manufactured by Lintec, thickness 50 μm, single layer product). Next, the other release film of the sealing sheet was peeled off, and the exposed adhesive layer was pressed onto alkali-free glass (manufactured by Corning, trade name: Eagle XG) using a pressure roll to prepare a test piece.
The produced test piece was subjected to a 180° peel test under conditions of a temperature of 23° C. and a relative humidity of 50%.
In this peel test, the test conditions other than those described above were performed in accordance with the method for measuring adhesive force described in JIS Z0237:2009.

[Total light transmittance measurement]
One release film of the sealing sheet was peeled off to expose the adhesive layer. This sealing sheet was placed on soda lime glass (thickness 1 mm) so that the exposed adhesive layer faced the soda lime glass, and then they were laminated at 23°C using a laminator and tested. A piece was made.
The total light transmittance of the prepared test piece was measured using a total light transmittance measuring device (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name: NDH-5000).

[Color measurement]
A test piece similar to that used for total light transmittance was prepared.
The color values defined by the CIE1976L*a*b* color system for the prepared test pieces were measured using a spectrophotometer (manufactured by Shimadzu Corporation, product name: UV-3600) in accordance with JIS Z 8781-4 (2013). ).

[Yellowness evaluation]
One release film of the sealing sheet was peeled off to expose the adhesive layer. This sealing sheet was placed on soda lime glass (thickness 1 mm) so that the exposed adhesive layer faced the soda lime glass, and then they were laminated at 23°C using a laminator and tested. A piece was made.
The prepared test piece was measured in accordance with JIS K 7373:2006 using a spectrophotometer (manufactured by Shimadzu Corporation, product name: UV-3600).

[Water vapor transmission rate measurement]
Using a water vapor permeability meter (SYSTECH INSTRUMENTS Ltd., product name: LYSSY L80-5000), the water vapor permeability of the sealing sheet was measured in an environment of a temperature of 40° C. and a relative humidity of 90%.

From Table 1, the following can be seen.
Sealing sheets (1) to (10) formed using resin compositions (1) to (10) containing component (A), component (B), and component (C) were prepared at a temperature of 23°C. Excellent adhesive strength under conditions of relative humidity of 50% (Examples 1 to 10).
Furthermore, the sealing sheets (1) to (10) have high total light transmittance, small absolute values of a* value and b* value, and low yellowness YI, and are excellent in colorless transparency.
Furthermore, the sealing sheets (1) to (10) also have excellent water vapor barrier properties.
On the other hand, resin composition (11) that does not contain component (A) had low sheet processability (film-forming property) and could not obtain a sealing sheet (Comparative Example 1).
Moreover, the sealing sheets (12) and (13) formed using the resin composition (12) that does not contain the component (B) and the resin composition (13) that does not contain the component (C) have a temperature of 23 Adhesive strength is poor under conditions of ℃ and 50% relative humidity (Comparative Examples 2 and 3).

Claims (13)

A sealing sheet consisting of a base material or a release film, and an adhesive layer formed on the base material or release film,
A sealing sheet in which the adhesive layer is formed using the following resin composition 1.
(Resin composition 1)
A resin composition containing the following components (A), (B), and (C).
(A) Component: Acid-modified polyolefin resin (B) Component: Compound having an oxirane group or oxetane group (C) Component: Photocationic polymerization initiator A sealing sheet consisting of two release films and an adhesive layer sandwiched between the two release films,
A sealing sheet in which the adhesive layer is formed using the following resin composition 1.
(Resin composition 1)
A resin composition containing the following components (A), (B), and (C).
(A) Component: Acid-modified polyolefin resin (B) Component: Compound having an oxirane group or oxetane group (C) Component: Photocationic polymerization initiator A sealing sheet comprising a release film, a gas barrier film, and an adhesive layer sandwiched between the release film and the gas barrier film,
A sealing sheet in which the adhesive layer is formed using the following resin composition 1.
(Resin composition 1)
A resin composition containing the following components (A), (B), and (C).
(A) Component: Acid-modified polyolefin resin (B) Component: Compound having an oxirane group or oxetane group (C) Component: Photocationic polymerization initiator The sealing sheet according to claim 3, wherein the gas barrier film is a metal foil, a resin film, or a thin glass. The sealing sheet according to any one of claims 1 to 4, wherein the content of the component (B) is 5 to 50 parts by mass based on 100 parts by mass of the component (A). The sealing sheet according to any one of claims 1 to 5, wherein the component (C) is an aromatic sulfonium salt compound. The sealing sheet according to any one of claims 1 to 6, wherein the content of the component (C) is 0.04 to 2 parts by mass based on 100 parts by mass of the component (B). The sealing sheet according to any one of claims 1 to 7, wherein the resin composition 1 further contains a tackifier. The sealing sheet according to claim 8, wherein the content of the tackifier is 1 to 200 parts by mass based on 100 parts by mass of component (A). The sealing sheet according to any one of claims 1 to 9, wherein the resin composition 1 further contains a silane coupling agent. The sealing sheet according to claim 10, wherein the content of the silane coupling agent is 0.01 to 10 parts by mass based on 100 parts by mass of component (A). A sealed body in which an object to be sealed is sealed using the sealing sheet according to any one of claims 1 to 11,
A sealed body, wherein an adhesive layer constituting the sealing sheet or an adhesive layer derived from the sealing sheet is in close contact with the object to be sealed and covers the object. The sealed body according to claim 12, wherein the object to be sealed is an electronic device.